TW202010769A - Thermosetting compositions, cured film, and color filter - Google Patents
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- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
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Abstract
Description
本發明有關於一種可用於形成電子零件中的絕緣材料、半導體裝置中的鈍化膜、緩衝塗膜、層間絕緣膜、平坦化膜、液晶顯示元件中的層間絕緣膜、彩色濾光片(color filter)用保護膜等的熱硬化性組成物、由所述熱硬化性組成物形成的透明膜及具有所述膜的電子零件。The present invention relates to an insulating material that can be used to form an electronic component, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a liquid crystal display element, and a color filter ) A thermosetting composition such as a protective film, a transparent film formed from the thermosetting composition, and an electronic component having the film.
在液晶顯示元件等元件的製造步驟中,有時進行有機溶劑、酸、鹼溶液等的各種化學品處理,或者在通過濺鍍(sputtering)而將配線電極成膜時,將表面局部地在高溫下加熱。因此,有時出於防止各種元件的表面的劣化、損傷、變質的目的而設置表面保護膜。對這些保護膜要求可耐受如上所述的製造步驟中的各種處理的各特性。具體而言,要求耐熱性、耐溶劑性·耐酸性·耐鹼性等耐化學品性、耐水性、對玻璃等基底基板的密著性、透明性、耐劃傷性、平坦性、耐光性等。在隨著對顯示元件所要求的可靠性的要求特性提高,對顯示元件構件所要求的耐熱性提高的過程中,提倡耐熱性良好的包含聚酯醯胺酸及環氧化合物的熱硬化性組成物(專利文獻1)。進而,隨著近年來對經高精細化、薄型化的液晶顯示元件所要求的平坦性提高,提倡調整了所述發明的環氧化合物的分子量的熱硬化性組成物,除耐熱性良好以外,也改善了平坦性(專利文獻2)。In the manufacturing process of devices such as liquid crystal display devices, various chemicals such as organic solvents, acids, and alkaline solutions are sometimes treated, or when forming wiring electrodes by sputtering, the surface is partially exposed to high temperatures Under heating. Therefore, a surface protection film is sometimes provided for the purpose of preventing deterioration, damage, or deterioration of the surface of various elements. These protective films are required to withstand the characteristics of various treatments in the manufacturing steps described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to base substrates such as glass, transparency, scratch resistance, flatness, and light resistance are required Wait. With the improvement of the required characteristics of the reliability required for display elements and the improvement of the heat resistance required for display element members, a thermosetting composition containing polyester amidic acid and epoxy compounds with good heat resistance is advocated Thing (Patent Literature 1). Furthermore, in recent years, as the flatness required for high-definition and thinned liquid crystal display elements has been improved, thermosetting compositions in which the molecular weight of the epoxy compound of the invention has been adjusted are proposed, in addition to good heat resistance. The flatness is also improved (Patent Document 2).
最近對耐熱性、平坦性之外的減少基底成分的溶出的特性(以下也稱為屏障性)的要求加強。在此背景下,特別是彩色濾光片的領域中,有針對廣色域化的應對,在各彩色濾光片製造商中,可見使用色澤佳且容易溶出·分解的色素、或為了防止褪色而使光硬化的處理為最低限度等的動向。由這些動向引起的對彩色濾光片及表面保護膜的影響在形成配向膜時特別顯著。Recently, the requirements for reducing the elution of the base component (hereinafter also referred to as barrier properties) other than heat resistance and flatness have been strengthened. Against this background, especially in the field of color filters, there is a response to wide color gamut. Among the color filter manufacturers, it is obvious to use pigments with good color and easy to dissolve or decompose, or to prevent discoloration. The process of hardening the light is the minimum trend. The influence on the color filter and the surface protective film caused by these trends is particularly remarkable when forming the alignment film.
層疊於彩色濾光片側的配向膜通常塗佈於表面保護膜上,具有控制液晶分子排列的功能(以下也稱為配向性)。為了顯現配向性,使用聚醯亞胺作為主成分,但為了使所述聚醯亞胺溶解,需要使用N-甲基吡咯烷酮等樹脂溶解性高的溶媒(以下也稱為強溶媒)。迄今為止的彩色濾光片雖然對形成配向膜的步驟中所使用的所述強溶媒具有耐性,但因所述動向而彩色濾光片對強溶媒的耐性降低,容易產生溶解於強溶媒中的彩色濾光片成分溶出至配向膜層及液晶層。結果,未應對這些動向的現有的保護膜中,產生如下問題:在形成面板時,彩色濾光片成分混入至配向膜層及液晶層,使顯示器的顯示品質降低,結果使良率降低等。The alignment film laminated on the side of the color filter is usually coated on the surface protective film, and has a function of controlling the arrangement of liquid crystal molecules (hereinafter also referred to as alignment). In order to develop the alignment, polyimide is used as the main component, but in order to dissolve the polyimide, it is necessary to use a solvent having high resin solubility such as N-methylpyrrolidone (hereinafter also referred to as a strong solvent). Although the conventional color filter has resistance to the strong solvent used in the step of forming the alignment film, the resistance of the color filter to the strong solvent is reduced due to the above-mentioned trend, and it is likely to be dissolved in the strong solvent. The color filter components elute to the alignment film layer and the liquid crystal layer. As a result, in the conventional protective film that does not respond to these trends, there is a problem that when forming the panel, the color filter components are mixed into the alignment film layer and the liquid crystal layer, thereby degrading the display quality of the display, resulting in a decrease in yield, and the like.
針對所述問題,作為對保護膜所要求的具體的對策,要求有:將形成保護膜及配向膜時的熱硬化步驟中所產生的彩色濾光片的分解物等脫氣成分以不向配向膜層及液晶層飛散的方式遮蔽;在形成配向膜時抑制強溶媒浸入至彩色濾光片,從而不使彩色濾光片的色素成分或所述分解物等溶出至配向膜層及液晶層等。In response to the above-mentioned problems, as a specific countermeasure required for the protective film, it is required that the degassed components such as the decomposition products of the color filter generated during the thermosetting step when forming the protective film and the alignment film are not aligned The film layer and the liquid crystal layer are shielded by flying; when the alignment film is formed, the strong solvent is prevented from infiltrating into the color filter, so that the pigment component of the color filter or the decomposition product is not eluted to the alignment film layer and the liquid crystal layer, etc. .
為了滿足這些要求而積極地進行了各種研究,但除所述所示的熱硬化性樹脂組成物(專利文獻1及專利文獻2)以外,含有聚酯醯胺酸及N-取代馬來醯亞胺的熱硬化性聚合物組成物(專利文獻3)也為其一例。另一方面,專利文獻1及專利文獻3的組成物存在如下情況:雖然對各種處理的耐性良好,但平坦性不充分,且視情況而要求改善屏障性。另外,專利文獻2的組成物也是雖然對各種處理的耐性及平坦性良好,但對於屏障性而言有改善的餘地。 [現有技術文獻]Various studies have been actively conducted to meet these requirements, but in addition to the thermosetting resin compositions shown above (Patent Document 1 and Patent Document 2), they contain polyester amide acid and N-substituted maleimide An amine thermosetting polymer composition (Patent Document 3) is also an example. On the other hand, the compositions of Patent Literature 1 and Patent Literature 3 may have a good resistance to various treatments, but the flatness is insufficient, and the barrier properties are required to be improved depending on the situation. In addition, the composition of Patent Document 2 also has good resistance to various treatments and flatness, but there is room for improvement in barrier properties. [Prior Art Literature]
[專利文獻] [專利文獻1]日本專利特開2005-105264 [專利文獻2]日本專利特開2008-156546 [專利文獻3]日本專利特開2006-282995[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2005-105264 [Patent Document 2] Japanese Patent Laid-Open No. 2008-156546 [Patent Document 3] Japanese Patent Laid-Open No. 2006-282995
[發明所要解決的問題] 本發明的問題在於提供一種提供防止基底成分的溶出、平坦性優異且與基地基板的密著性良好的硬化膜的熱硬化性組成物及由所述熱硬化性組成物形成的硬化膜,進而提供一種具有所述硬化膜的電子零件。[Problems to be solved by the invention] The problem of the present invention is to provide a thermosetting composition that provides a cured film that prevents elution of the base component, has excellent flatness, and has good adhesion to the base substrate, and a cured film formed from the thermosetting composition, and Provided is an electronic part having the hardened film.
[解決問題的技術手段] 本發明者等人為了解決所述問題而進行了努力研究,結果發現,利用如下硬化膜而可達成所述目的,從而完成了本發明,所述硬化膜是使包含作為四羧酸二酐、二胺及多元羥基化合物的反應產物的聚酯醯胺酸、環狀醚化合物的聚合物、以及陽離子聚合起始劑的組成物硬化而獲得。 本發明包含以下的構成。[Technical means to solve the problem] The inventors of the present invention have made intensive studies in order to solve the above-mentioned problems, and as a result, have found that the above-mentioned object can be achieved by using the following cured film, which contains the tetracarboxylic dianhydride, The reaction product of the diamine and the polyhydric hydroxy compound is obtained by hardening the composition of the polyester amide acid, the polymer of the cyclic ether compound, and the cationic polymerization initiator. The present invention includes the following configurations.
[1] 一種熱硬化性組成物,其包含聚酯醯胺酸(A)、環狀醚化合物的聚合物(B)及陽離子聚合起始劑(C),且所述熱硬化性組成物中, 所述聚酯醯胺酸(A)為源自以下述式(1)及式(2)的關係成立的比率包含X莫耳的四羧酸二酐、Y莫耳的二胺及Z莫耳的多元羥基化合物的原料的反應產物, 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2) 所述環狀醚化合物的聚合物(B)為選自具有氧雜環丁基的化合物(b1)的均聚物、具有氧雜環丁基的化合物(b1)彼此的共聚物及具有氧雜環丁基的化合物(b1)與具有氧雜環丙基的化合物(b2)的共聚物中的至少一種。[1] A thermosetting composition comprising polyester amide acid (A), a polymer (B) of a cyclic ether compound, and a cationic polymerization initiator (C), and the thermosetting composition , The polyester amide acid (A) is derived from a tetracarboxylic dianhydride containing X moles, a diamine of Y moles, and a Z mole from the ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw materials of polyhydroxy compounds, 0.2≦Z/Y≦8.0······(1) 0.2≦(Y+Z)/X≦5.0··(2) The polymer (B) of the cyclic ether compound is a homopolymer selected from a compound (b1) having an oxetanyl group, a copolymer of a compound (b1) having an oxetanyl group, and having an oxa At least one of a copolymer of a cyclobutyl compound (b1) and an oxetanyl-containing compound (b2).
[2] 根據[1]項所述的熱硬化性組成物,其中所述聚酯醯胺酸(A)包含下述式(3)所表示的結構單元及下述式(4)所表示的結構單元。 式(3)及式(4)中,R1 為自四羧酸二酐除去兩個-CO-O-CO-而成的殘基,R2 為自二胺除去兩個-NH2 而成的殘基,R3 為自多元羥基化合物除去兩個-OH而成的殘基。[2] The thermosetting composition according to item [1], wherein the polyester amide acid (A) includes a structural unit represented by the following formula (3) and a formula represented by the following formula (4) Structural units. In formula (3) and formula (4), R 1 is a residue obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and R 2 is obtained by removing two -NH 2 from a diamine R 3 is a residue obtained by removing two -OH groups from a polyhydroxy compound.
[3] 根據[1]項或[2]項所述的熱硬化性組成物,其中所述具有氧雜環丁基的化合物(b1)為選自丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯及甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯中的至少一種。[3] The thermosetting composition according to item [1] or [2], wherein the compound (b1) having an oxetanyl group is selected from acrylic acid (3-ethyloxetane At least one of -3-yl) methyl ester and (3-ethyloxetan-3-yl) methyl methacrylate.
[4] 根據[1]項或[2]項所述的熱硬化性組成物,其中所述具有氧雜環丙基的化合物(b2)為選自丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸甲基縮水甘油酯及4-羥基丁基丙烯酸酯縮水甘油醚中的至少一種。[4] The thermosetting composition according to item [1] or [2], wherein the compound (b2) having an oxetanyl group is selected from glycidyl acrylate and glycidyl methacrylate At least one of methyl glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.
[5] 根據[1]至[4]中任一項所述的熱硬化性組成物,其中相對於聚酯醯胺酸(A)100重量份,所述環狀醚化合物的聚合物(B)的含量為20重量份~400重量份。[5] The thermosetting composition according to any one of [1] to [4], wherein the polymer (B) of the cyclic ether compound is relative to 100 parts by weight of the polyester amide acid (A) ) Content is 20 parts by weight to 400 parts by weight.
[6] 根據[1]至[5]中任一項所述的熱硬化性組成物,其中陽離子聚合起始劑(C)為陰離子種不含銻的陽離子聚合起始劑。[6] The thermosetting composition according to any one of [1] to [5], wherein the cationic polymerization initiator (C) is an anionic antimony-free cationic polymerization initiator.
[7] 根據[1]至[6]中任一項所述的熱硬化性組成物,其中陽離子聚合起始劑(C)為陰離子種不含銻且陽離子種為鋶鹽系的陽離子聚合起始劑。[7] The thermosetting composition according to any one of [1] to [6], wherein the cationic polymerization initiator (C) is an anionic species that does not contain antimony and the cationic species is a cationic polymer starting from the samium salt system. Initial agent.
[8] 一種硬化膜,其是使根據[1]至[7]中任一項所述的熱硬化性組成物硬化而獲得。[8] A cured film obtained by curing the thermosetting composition according to any one of [1] to [7].
[9] 一種彩色濾光片,其具有根據[8]項所述的硬化膜作為透明保護膜。[9] A color filter having the cured film according to [8] as a transparent protective film.
[發明的效果] 本發明的較佳實施方式的熱硬化性組成物為防止基底成分的溶出、且平坦性優異的材料,在用作彩色液晶顯示元件的彩色濾光片保護膜的情況下,可使顯示品質提高。特別是有效用作利用染色法、顏料分散法、電沉積法及印刷法而製造的彩色濾光片的保護膜。另外,也可用作各種光學材料的保護膜及透明絕緣膜。[Effect of invention] The thermosetting composition of the preferred embodiment of the present invention is a material that prevents elution of the base component and has excellent flatness, and when used as a color filter protective film for a color liquid crystal display element, can improve display quality . In particular, it is effectively used as a protective film for color filters manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. In addition, it can also be used as a protective film and transparent insulating film for various optical materials.
1.本發明的熱硬化性組成物 本發明的熱硬化性組成物為含有聚酯醯胺酸(A)、環狀醚化合物的聚合物(B)、以及陽離子聚合起始劑(C)的組成物,所述聚酯醯胺酸(A)為源自包含四羧酸二酐、二胺及多元羥基化合物的原料的反應產物,且環狀醚化合物的聚合物(B)為選自具有氧雜環丁基的化合物(b1)的均聚物、具有氧雜環丁基的化合物(b1)彼此的共聚物及具有氧雜環丁基的化合物(b1)與具有氧雜環丙基的化合物(b2)的共聚物中的至少一種。1. The thermosetting composition of the present invention The thermosetting composition of the present invention is a composition containing a polyester amide acid (A), a polymer (B) of a cyclic ether compound, and a cationic polymerization initiator (C), the polyester amide acid (A) is a reaction product derived from a raw material containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound, and the polymer (B) of the cyclic ether compound is selected from compounds having oxetanyl group (b1) Homopolymers, copolymers of oxetanyl compound (b1) and copolymers of oxetanyl compound (b1) and oxetanyl compound (b2) One kind.
1-1.聚酯醯胺酸(A) 聚酯醯胺酸為源自包含四羧酸二酐、二胺及多元羥基化合物的原料的反應產物。更詳細而言,所述聚酯醯胺酸為源自以下述式(1)及式(2)的關係成立的比率包含X莫耳的四羧酸二酐、Y莫耳的二胺及Z莫耳的多元羥基化合物的原料的反應產物。 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2)1-1. Polyester amide acid (A) Polyesteramide acid is a reaction product derived from raw materials containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More specifically, the polyester amide acid is derived from a tetracarboxylic dianhydride containing X moles, a diamine of Y moles, and Z from the ratio established by the relationship of the following formula (1) and formula (2) The reaction product of the raw material of polyhydric hydroxy compound of Mohr. 0.2≦Z/Y≦8.0······(1) 0.2≦(Y+Z)/X≦5.0··(2)
聚酯醯胺酸(A)較佳為具有下述式(3)所表示的結構單元及式(4)所表示的結構單元。 The polyester amide acid (A) preferably has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4).
式(3)及式(4)中,R1 為自四羧酸二酐除去兩個-CO-O-CO-而成的殘基,較佳為碳數2~30的有機基。R2 為自二胺除去兩個-NH2 而成的殘基,較佳為碳數2~30的有機基。R3 為自多元羥基化合物除去兩個-OH而成的殘基,較佳為碳數2~20的有機基。In Formula (3) and Formula (4), R 1 is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R 2 is a residue obtained by removing two —NH 2 from a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R 3 is a residue obtained by removing two -OH groups from a polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.
在聚酯醯胺酸(A)的合成中,至少需要溶劑,可使所述溶劑直接殘留而製成考慮到操作性等的液狀或凝膠狀的熱硬化性組成物,也可將所述溶劑除去而製成考慮到搬運性等的固體狀的組成物。另外,在聚酯醯胺酸(A)的合成中,視需要也可包含選自單羥基化合物及苯乙烯-馬來酸酐共聚物中的一種以上的化合物作為原料,特佳為包含單羥基化合物。另外,在聚酯醯胺酸(A)的合成中,也可在不損及本發明的目的的範圍內,視需要包含所述以外的其他化合物作為原料。In the synthesis of the polyester amide acid (A), at least a solvent is required, and the solvent can be left directly to form a liquid or gel-like thermosetting composition in consideration of operability and the like. The solvent is removed to produce a solid composition in consideration of transportability and the like. In addition, in the synthesis of polyester amide acid (A), if necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer may be included as a raw material, particularly preferably a monohydroxy compound . In addition, in the synthesis of the polyester amide acid (A), other compounds than the above may be included as a raw material as necessary within a range that does not impair the object of the present invention.
1-1-1.四羧酸二酐 在本發明中,作為用以獲得聚酯醯胺酸(A)的材料,使用四羧酸二酐。較佳的四羧酸二酐的具體例為:3,3',4,4'-二苯甲酮四羧酸二酐、2,2',3,3'-二苯甲酮四羧酸二酐、2,3,3',4'-二苯甲酮四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、2,2',3,3'-二苯基碸四羧酸二酐、2,3,3',4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2',3,3'-二苯基醚四羧酸二酐、2,3,3',4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐、乙二醇雙(脫水偏苯三酸酯)(商品名;TMEG-100,新日本理化股份有限公司)、環丁烷四羧酸二酐、甲基環丁烷四羧酸二酐、環戊烷四羧酸二酐、環己烷四羧酸二酐、乙烷四羧酸二酐及丁烷四羧酸二酐。可使用這些四羧酸二酐中的一種以上。1-1-1. Tetracarboxylic dianhydride In the present invention, as a material for obtaining polyester amide acid (A), tetracarboxylic dianhydride is used. Specific examples of preferred tetracarboxylic dianhydride are: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid Dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ash tetracarboxylic dianhydride, 2,2',3, 3'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Dianhydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis( 3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, ethylene glycol bis (dehydrated trimellitate) (trade name; TMEG- 100, New Japan Physical and Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.
這些四羧酸二酐中,更佳為賦予良好透明性的3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、2,2-[雙(3,4-二羧基苯基)]六氟丙烷二酐、1,2,3,4-丁烷四羧酸二酐及乙二醇雙(脫水偏苯三酸酯),進而較佳為3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐及1,2,3,4-丁烷四羧酸二酐。Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether which impart good transparency are more preferable. Tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and ethylene glycol bis( Dehydrated trimellitate), further preferably 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid di Anhydride and 1,2,3,4-butane tetracarboxylic dianhydride.
1-1-2.二胺 在本發明中,作為用以獲得聚酯醯胺酸(A)的材料,使用二胺。較佳的二胺的具體例為:4,4'-二胺基二苯基碸、3,3'-二胺基二苯基碸、3,4'-二胺基二苯基碸、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙[3-(4-胺基苯氧基)苯基]碸、[4-(4-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸、[4-(3-胺基苯氧基)苯基][3-(4-胺基苯氧基)苯基]碸及2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷。可使用這些二胺中的一種以上。1-1-2. Diamine In the present invention, as a material for obtaining polyester amide acid (A), diamine is used. Specific examples of preferred diamines are: 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ash, 3,4'-diaminodiphenyl ash, bis [4-(4-Aminophenoxy)phenyl] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, bis[3-(4-aminophenoxy)phenyl ] 碸, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl] 碸, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl] benzene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. One or more of these diamines can be used.
這些二胺中,更佳為賦予良好透明性的3,3'-二胺基二苯基碸及雙[4-(3-胺基苯氧基)苯基]碸,進而較佳為3,3'-二胺基二苯基碸。Among these diamines, 3,3′-diaminodiphenyl sulfone and bis[4-(3-aminophenoxy)phenyl] benzene, which impart good transparency, are more preferred, and 3, 3'-diaminodiphenyl sulfone.
1-1-3.多元羥基化合物 在本發明中,作為用以獲得聚酯醯胺酸(A)的材料,使用多元羥基化合物。1-1-3. Polyhydroxy compounds In the present invention, as a material for obtaining the polyester amide acid (A), a polyhydroxy compound is used.
較佳的多元羥基化合物的具體例可列舉:乙二醇、二乙二醇、三乙二醇、四乙二醇、重量平均分子量1,000以下的聚乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、重量平均分子量1,000以下的聚丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,2-戊二醇、1,5-戊二醇、2,4-戊二醇、1,2,5-戊三醇、1,2-己二醇、1,6-己二醇、2,5-己二醇、1,2,6-己三醇、1,2-庚二醇、1,7-庚二醇、1,2,7-庚三醇、1,2-辛二醇、1,8-辛二醇、3,6-辛二醇、1,2,8-辛三醇、1,2-壬二醇、1,9-壬二醇、1,2,9-壬三醇、1,2-癸二醇、1,10-癸二醇、1,2,10-癸三醇、1,2-十二烷二醇、1,12-十二烷二醇、甘油、三羥甲基丙烷、季戊四醇、二季戊四醇、異氰脲酸三(2-羥基乙基)酯、雙酚A(2,2-雙(4-羥基苯基)丙烷)、雙酚S(雙(4-羥基苯基)碸)、雙酚F(雙(4-羥基苯基)甲烷)、4,4'-亞異丙基雙(2-苯氧基乙醇)、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基、2-羥基苄醇、4-羥基苄醇、2-(4-羥基苯基)乙醇、二乙醇胺、三乙醇胺、Specific examples of preferred polyhydric hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, Tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol Alcohol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- Hexatriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6- Octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1, 10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, iso Tris (2-hydroxyethyl) cyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) ash), bisphenol F (Bis(4-hydroxyphenyl)methane), 4,4'-isopropylidenebis(2-phenoxyethanol), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'- Dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl) ethanol, diethanolamine, triethanolamine,
甘油單烯丙基醚、三羥甲基丙烷單烯丙基醚、季戊四醇單烯丙基醚、季戊四醇二烯丙基醚、二季戊四醇單烯丙基醚、二季戊四醇二烯丙基醚、二季戊四醇三烯丙基醚、二季戊四醇四烯丙基醚、山梨糖醇單烯丙基醚、山梨糖醇二烯丙基醚、山梨糖醇三烯丙基醚、山梨糖醇四烯丙基醚、甘油單(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、二季戊四醇單(甲基)丙烯酸酯、二季戊四醇二(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、山梨糖醇單(甲基)丙烯酸酯、山梨糖醇二(甲基)丙烯酸酯、山梨糖醇三(甲基)丙烯酸酯、山梨糖醇四(甲基)丙烯酸酯、乙二醇二縮水甘油醚的(甲基)丙烯酸改質物、丙二醇二縮水甘油醚的(甲基)丙烯酸改質物、三丙二醇二縮水甘油醚的(甲基)丙烯酸改質物、甘油二縮水甘油醚的(甲基)丙烯酸改質物、雙酚A二縮水甘油醚的(甲基)丙烯酸改質物、環氧丙烷改質雙酚A二縮水甘油醚的(甲基)丙烯酸改質物、雙酚S二縮水甘油醚的(甲基)丙烯酸改質物、環氧丙烷改質雙酚S二縮水甘油醚的(甲基)丙烯酸改質物、雙酚F二縮水甘油醚的(甲基)丙烯酸改質物、環氧丙烷改質雙酚F二縮水甘油醚的(甲基)丙烯酸改質物、聯二甲苯酚二縮水甘油醚的(甲基)丙烯酸改質物、聯苯酚二縮水甘油醚的(甲基)丙烯酸改質物、茀二酚二縮水甘油醚的(甲基)丙烯酸改質物、環己烷-1,4-二甲醇二縮水甘油醚的(甲基)丙烯酸改質物、氫化雙酚A二縮水甘油醚的(甲基)丙烯酸改質物、三環癸烷二甲醇二縮水甘油醚的(甲基)丙烯酸改質物及每一分子中包含兩個以上的環氧基的其他化合物的(甲基)丙烯酸改質物。Glycerol monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol diallyl ether, dipentaerythritol Triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, Glycerin mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol mono(meth)acrylate, Dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, sorbitol mono(meth)acrylate, sorbitol di(meth)acrylate Ester, sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (methyl) of propylene glycol diglycidyl ether Acrylic acid modified product, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, (meth)acrylic acid modified product of bisphenol A diglycidyl ether, cyclic Oxypropane modified bisphenol A diglycidyl ether (meth)acrylic modified product, bisphenol S diglycidyl ether (meth)acrylic modified product, propylene oxide modified bisphenol S diglycidyl ether ( Methacrylic acid modified product, (meth)acrylic acid modified product of bisphenol F diglycidyl ether, (meth)acrylic acid modified product of propylene oxide modified bisphenol F diglycidyl ether, bixylenol diglycidyl Modified (meth)acrylic acid of glyceryl ether, modified (meth)acrylic acid of diphenol diglycidyl ether, modified (meth)acrylic acid of stilbene diglycidyl ether, cyclohexane-1,4- Modified (meth)acrylic acid of dimethanol diglycidyl ether, modified (meth)acrylic acid of hydrogenated bisphenol A diglycidyl ether, modified (meth)acrylic acid of tricyclodecane dimethanol diglycidyl ether And (meth)acrylic acid modified products of other compounds containing more than two epoxy groups in each molecule.
這些多元羥基化合物中,較佳為對反應溶劑的溶解性良好的乙二醇、二乙二醇、三乙二醇、丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、異氰脲酸三(2-羥基乙基)酯、2,2-雙(4-羥基環己基)丙烷、4,4'-二羥基二環己基、2-羥基苄醇、4-羥基苄醇、2-(4-羥基苯基)乙醇、4,4'-亞異丙基雙(2-苯氧基乙醇)、乙二醇二縮水甘油醚的(甲基)丙烯酸改質物、丙二醇二縮水甘油醚的(甲基)丙烯酸改質物、甘油二縮水甘油醚的(甲基)丙烯酸改質物、雙酚A二縮水甘油醚的(甲基)丙烯酸改質物、環氧丙烷改質雙酚A二縮水甘油醚的(甲基)丙烯酸改質物、雙酚S二縮水甘油醚的(甲基)丙烯酸改質物、環氧丙烷改質雙酚S二縮水甘油醚的(甲基)丙烯酸改質物、雙酚F二縮水甘油醚的(甲基)丙烯酸改質物及環氧丙烷改質雙酚F二縮水甘油醚的(甲基)丙烯酸改質物。進而,特別更佳為二乙二醇、三乙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2-羥基苄醇、4-羥基苄醇、4,4'-亞異丙基雙(2-苯氧基乙醇)、2-(4-羥基苯基)乙醇、乙二醇二縮水甘油醚的(甲基)丙烯酸改質物、丙二醇二縮水甘油醚的(甲基)丙烯酸改質物、三丙二醇二縮水甘油醚的(甲基)丙烯酸改質物、甘油二縮水甘油醚的(甲基)丙烯酸改質物、雙酚A二縮水甘油醚的(甲基)丙烯酸改質物及環氧丙烷改質雙酚A二縮水甘油醚的(甲基)丙烯酸改質物。Among these polyhydric hydroxy compounds, preferred are ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1 which have good solubility in the reaction solvent. ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, tris(2-hydroxyethyl) isocyanurate, 2,2-bis(4-hydroxycyclohexyl)propane , 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-(4-hydroxyphenyl)ethanol, 4,4'-isopropylidenebis(2-phenoxy (Ethyl alcohol), (meth)acrylic acid modified product of ethylene glycol diglycidyl ether, (meth)acrylic acid modified product of propylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, bisphenol (Meth)acrylic acid modified product of A diglycidyl ether, (meth)acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth)acrylic acid modified product of bisphenol S diglycidyl ether , (Meth)acrylic acid modified product of propylene oxide modified bisphenol S diglycidyl ether, (meth)acrylic acid modified product of bisphenol F diglycidyl ether, and propylene oxide modified bisphenol F diglycidyl ether Modified (meth)acrylic acid. Furthermore, particularly preferred are diethylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol (Meth)acrylic acid modified product of alcohol, 4,4'-isopropylidenebis(2-phenoxyethanol), 2-(4-hydroxyphenyl)ethanol, ethylene glycol diglycidyl ether, propylene glycol di (Meth)acrylic acid modified product of glycidyl ether, (meth)acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth)acrylic acid modified product of glycerol diglycidyl ether, and bisphenol A diglycidyl ether ( (Meth)acrylic acid modified product and propylene oxide modified bisphenol A diglycidyl ether (meth)acrylic acid modified product.
作為乙二醇二縮水甘油醚的甲基丙烯酸改質物、丙二醇二縮水甘油醚的丙烯酸改質物、三丙二醇二縮水甘油醚的丙烯酸改質物、甘油二縮水甘油醚的丙烯酸改質物、雙酚A二縮水甘油醚的甲基丙烯酸改質物、雙酚A二縮水甘油醚的丙烯酸改質物、環氧丙烷改質雙酚A二縮水甘油醚的甲基丙烯酸改質物及環氧丙烷改質雙酚A二縮水甘油醚的丙烯酸改質物,可使用下述市售品。Modified methacrylic acid as ethylene glycol diglycidyl ether, modified acrylic acid as propylene glycol diglycidyl ether, modified acrylic acid as tripropylene glycol diglycidyl ether, modified acrylic acid as glycerol diglycidyl ether, bisphenol A Modified methacrylic acid of glycidyl ether, modified acrylic acid of bisphenol A diglycidyl ether, modified methacrylic acid of propylene oxide modified bisphenol A diglycidyl ether, and modified bisphenol A dipropylene oxide As the acrylic acid-modified product of glycidyl ether, the following commercially available products can be used.
乙二醇二縮水甘油醚的甲基丙烯酸改質物的具體例為環氧酯40EM(商品名;共榮社化學股份有限公司)。丙二醇二縮水甘油醚的丙烯酸改質物的具體例為環氧酯70PA(商品名;共榮社化學股份有限公司)。三丙二醇二縮水甘油醚的丙烯酸改質物的具體例為環氧酯200PA(商品名;共榮社化學股份有限公司)。甘油二縮水甘油醚的丙烯酸改質物的具體例為環氧酯80MFA(商品名;共榮社化學股份有限公司)。雙酚A二縮水甘油醚的甲基丙烯酸改質物的具體例為環氧酯3000MK(商品名;共榮社化學股份有限公司)。雙酚A二縮水甘油醚的丙烯酸改質物的具體例為環氧酯3000A(商品名;共榮社化學股份有限公司)。環氧丙烷改質雙酚A二縮水甘油醚的甲基丙烯酸改質物的具體例為環氧酯3002M(N)(商品名;共榮社化學股份有限公司)。環氧丙烷改質雙酚A二縮水甘油醚的丙烯酸改質物的具體例為環氧酯3002A(N)(商品名;共榮社化學股份有限公司)。A specific example of the methacrylic acid modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of glycerol diglycidyl ether is epoxy ester 80MFA (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid modified product of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of a methacrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name; Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A(N) (trade name; Kyoeisha Chemical Co., Ltd.).
1-1-4.單羥基化合物 在本發明中,作為用以獲得聚酯醯胺酸(A)的材料,可使用單羥基化合物。通過使用單羥基化合物,熱硬化性組成物的保存穩定性提高。較佳的單羥基化合物的具體例為:甲醇、乙醇、1-丙醇、異丙醇、烯丙醇、苄醇、丙二醇單***、丙二醇單甲醚、二丙二醇單***、二丙二醇單甲醚、乙二醇單***、乙二醇單甲醚、二乙二醇單***、二乙二醇單甲醚、苯酚、龍腦(borneol)、麥芽醇(maltol)、芳樟醇(linalool)、松油醇(terpineol)、二甲基苄基甲醇(dimethyl benzyl carbinol)及3-乙基-3-羥基甲基氧雜環丁烷。可使用這些單羥基化合物中的一種以上。1-1-4. Monohydroxy compound In the present invention, as a material for obtaining the polyester amide acid (A), a monohydroxy compound can be used. By using a monohydroxy compound, the storage stability of the thermosetting composition is improved. Specific examples of preferred monohydroxy compounds are: methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltol, linalool , Terpineol (terpineol), dimethyl benzyl methanol (dimethyl benzyl carbinol) and 3-ethyl-3-hydroxymethyl oxetane. One or more of these monohydroxy compounds can be used.
這些單羥基化合物中,更佳為異丙醇、烯丙醇、苄醇、丙二醇單***、或3-乙基-3-羥基甲基氧雜環丁烷。若考慮將使用這些單羥基化合物而形成的聚酯醯胺酸(A)與環狀醚化合物的聚合物(B)及陽離子聚合起始劑(C)混合的情況下的相容性,或熱硬化性組成物在彩色濾光片上的塗佈性,則單羥基化合物進而較佳為使用苄醇。Among these monohydroxy compounds, isopropyl alcohol, allyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyloxetane are more preferred. If the polyester amide acid (A) formed using these monohydroxy compounds is mixed with the polymer (B) of the cyclic ether compound and the cationic polymerization initiator (C), the compatibility, or heat For the coating property of the curable composition on the color filter, benzyl alcohol is preferably used for the monohydroxy compound.
相對於四羧酸二酐、二胺及多元羥基化合物的合計量100重量份,較佳為含有0重量份~300重量份的單羥基化合物而進行反應。更佳為5重量份~200重量份。The reaction is preferably carried out with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound, preferably containing 0 to 300 parts by weight of monohydroxy compound. More preferably, it is 5 to 200 parts by weight.
1-1-5.苯乙烯-馬來酸酐共聚物 另外,本發明中所使用的聚酯醯胺酸(A)也可在所述原料中添加具有三個以上的酸酐基的化合物而合成。添加具有三個以上的酸酐基的化合物而合成的聚酯醯胺酸(A)的透明性的提高受到期待,因此較佳。具有三個以上的酸酐基的化合物的例子為苯乙烯-馬來酸酐共聚物。關於構成苯乙烯-馬來酸酐共聚物的各成分的比率,苯乙烯/馬來酸酐的莫耳比為0.5~4,較佳為1~3。苯乙烯/馬來酸酐的莫耳比更佳為1或2,進而較佳為1。1-1-5. Styrene-maleic anhydride copolymer In addition, the polyester amide acid (A) used in the present invention can also be synthesized by adding a compound having three or more acid anhydride groups to the raw material. The transparency of the polyester amidic acid (A) synthesized by adding a compound having three or more acid anhydride groups is expected to be improved, so it is preferable. An example of a compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. Regarding the ratio of each component constituting the styrene-maleic anhydride copolymer, the mole ratio of styrene/maleic anhydride is 0.5 to 4, preferably 1 to 3. The molar ratio of styrene/maleic anhydride is more preferably 1 or 2, and further preferably 1.
苯乙烯-馬來酸酐共聚物的具體例為SMA3000P、SMA2000P及SMA1000P(均為商品名;川原油化股份有限公司)。這些苯乙烯-馬來酸酐共聚物中,特佳為耐熱性及耐鹼性良好的SMA1000P。Specific examples of styrene-maleic anhydride copolymers are SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Oil Chemical Co., Ltd.). Among these styrene-maleic anhydride copolymers, SMA1000P having excellent heat resistance and alkali resistance is particularly preferred.
相對於四羧酸二酐、二胺及多元羥基化合物的合計量100重量份,苯乙烯-馬來酸酐共聚物較佳為含有0重量份~500重量份。更佳為10重量份~300重量份。The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More preferably, it is 10 parts by weight to 300 parts by weight.
1-1-6.具有一個胺基的胺基矽烷化合物 在聚酯醯胺酸(A)的合成中,也可在不損及本發明的目的的範圍內,視需要包含所述以外的其他原料作為原料,此種其他原料的例子為具有一個胺基的胺基矽烷化合物。具有一個胺基的胺基矽烷化合物是用以與聚酯醯胺酸(A)的末端的酸酐基反應而在末端導入矽烷基。若使用含有聚酯醯胺酸(A)的本發明的熱硬化性組成物,則可改善所獲得的硬化膜的耐酸性,所述聚酯醯胺酸(A)是通過添加具有一個胺基的胺基矽烷化合物進行反應而獲得。進而,在以所述的單體的構成進行反應的情況下,也可添加單羥基化合物及具有一個胺基的胺基矽烷化合物此兩者而進行反應。1-1-6. Aminosilane compounds with one amine group In the synthesis of polyester amide acid (A), other raw materials other than those mentioned above may be included as raw materials as needed within a range that does not impair the object of the present invention. Examples of such other raw materials are having an amine group Of amino silane compounds. The aminosilane compound having one amine group is used to react with the acid anhydride group at the terminal of the polyester amide acid (A) to introduce a silane group at the terminal. If the thermosetting composition of the present invention containing polyester amide acid (A) is used, the acid resistance of the obtained cured film can be improved. The polyester amide acid (A) has one amine group by adding Obtained by reacting the aminosilane compound. Furthermore, when the reaction is carried out with the above-mentioned monomer structure, both a monohydroxy compound and an aminosilane compound having one amine group may be added and reacted.
本發明中所使用的較佳的具有一個胺基的胺基矽烷化合物的具體例為:3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、4-胺基丁基三甲氧基矽烷、4-胺基丁基三乙氧基矽烷、4-胺基丁基甲基二乙氧基矽烷、對胺基苯基三甲氧基矽烷、對胺基苯基三乙氧基矽烷、對胺基苯基甲基二甲氧基矽烷、對胺基苯基甲基二乙氧基矽烷、間胺基苯基三甲氧基矽烷及間胺基苯基甲基二乙氧基矽烷。可使用這些化合物中的一種以上。Specific examples of the preferred aminosilane compound having one amine group used in the present invention are: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-amino group Propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amine Butylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Diethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. One or more of these compounds can be used.
這些化合物中,更佳為硬化膜的耐酸性變得良好的3-胺基丙基三乙氧基矽烷及對胺基苯基三甲氧基矽烷,就耐酸性、相容性的觀點而言,進而較佳為3-胺基丙基三乙氧基矽烷。Among these compounds, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane with improved acid resistance of the cured film are more preferred. From the viewpoint of acid resistance and compatibility, Furthermore, 3-aminopropyltriethoxysilane is preferable.
相對於四羧酸二酐、二胺及多元羥基化合物的合計量100重量份,具有一個胺基的胺基矽烷化合物較佳為含有0重量份~300重量份。更佳為5重量份~200重量份。The aminosilane compound having one amine group preferably contains 0 to 300 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine and polyhydroxy compound. More preferably, it is 5 to 200 parts by weight.
1-1-7.聚酯醯胺酸(A)的合成反應中所使用的溶劑 用以獲得聚酯醯胺酸(A)的合成反應中所使用的溶劑(以下有時稱為“反應溶劑”)的具體例為:二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二***、二乙二醇單***乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、乳酸乙酯、環己酮、N-甲基-2-吡咯烷酮及N,N-二甲基乙醯胺。這些溶劑中,較佳為丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯及二乙二醇甲基乙基醚。1-1-7. Solvent used in the synthesis reaction of polyester amide acid (A) Specific examples of the solvent used in the synthesis reaction to obtain polyester amide acid (A) (hereinafter sometimes referred to as "reaction solvent") are: diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, 3-ethyl Ethyloxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone and N,N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and diethylene glycol methyl ethyl ether are preferred.
1-1-8.聚酯醯胺酸(A)的合成方法 本發明中所使用的聚酯醯胺酸(A)較佳為通過在所述溶劑中使四羧酸二酐X莫耳、二胺Y莫耳及多元羥基化合物Z莫耳反應而合成,此時將X、Y及Z確定為在這些間下述式(1)及式(2)的關係成立的比例。若為所述範圍,則聚酯醯胺酸(A)在溶劑中的溶解性高,因此組成物的塗佈性得到提高,結果可獲得平坦性優異的硬化膜。 0.2≦Z/Y≦8.0·······(1) 0.2≦(Y+Z)/X≦5.0···(2) 式(1)中,較佳為0.7≦Z/Y≦7.0,更佳為1.0≦Z/Y≦5.0。另外,式(2)中,較佳為0.5≦(Y+Z)/X≦4.0,更佳為0.6≦(Y+Z)/X≦2.0。1-1-8. Synthesis method of polyester amide acid (A) The polyester amide acid (A) used in the present invention is preferably synthesized by reacting tetracarboxylic dianhydride X mole, diamine Y mole and polyhydroxy compound Z mole in the solvent. At the time, X, Y, and Z are determined as the ratios in which the relationship of the following formula (1) and formula (2) is established. Within the above range, the solubility of the polyester amidic acid (A) in the solvent is high, so the coating property of the composition is improved, and as a result, a cured film excellent in flatness can be obtained. 0.2≦Z/Y≦8.0······(1) 0.2≦(Y+Z)/X≦5.0··(2) In formula (1), preferably 0.7≦Z/Y≦7.0, more preferably 1.0≦Z/Y≦5.0. In addition, in formula (2), 0.5≦(Y+Z)/X≦4.0 is preferable, and 0.6≦(Y+Z)/X≦2.0 is more preferable.
可認為本發明中所使用的聚酯醯胺酸(A)是在所述反應條件下,相對於(Y+Z)而過剩使用X的條件下,比在末端具有胺基或羥基的分子更過剩地生成在末端具有酸酐基(-CO-O-CO-)的分子。在以此種單體的構成進行反應的情況下,為了與分子末端的酸酐基反應而對末端進行酯化,視需要可添加所述的單羥基化合物。通過添加單羥基化合物進行反應而獲得的聚酯醯胺酸(A)可改善與環狀醚化合物的聚合物(B)及陽離子聚合起始劑(C)的相容性,且可改善包含這些化合物的本發明的熱硬化性組成物的塗佈性。It can be considered that the polyester amide acid (A) used in the present invention is more than the molecule having an amine group or a hydroxyl group at the terminal under the reaction conditions under the excessive use of X relative to (Y+Z) A molecule having an acid anhydride group (-CO-O-CO-) at the end is excessively generated. When reacting with such a monomer structure, in order to react with an acid anhydride group at the molecular terminal to esterify the terminal, the above-mentioned monohydroxy compound may be added as necessary. The polyester amide acid (A) obtained by adding a monohydroxy compound to the reaction can improve the compatibility with the polymer (B) of the cyclic ether compound and the cationic polymerization initiator (C), and can improve the inclusion of these The coatability of the thermosetting composition of the present invention of the compound.
若相對於四羧酸二酐、二胺及多元羥基化合物的合計100重量份而使用100重量份以上的反應溶劑,則反應順利地進行,因此較佳。反應以在40℃~200℃下反應0.2小時~20小時為宜。If 100 parts by weight or more of a reaction solvent is used with respect to a total of 100 parts by weight of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at 40°C to 200°C for 0.2 hours to 20 hours.
反應原料在反應系統中的添加順序並無特別限定。即,也可使用以下的任意方法:將四羧酸二酐、二胺及多元羥基化合物同時加入至反應溶劑中的方法;使二胺及多元羥基化合物溶解於反應溶劑中後,添加四羧酸二酐的方法;使四羧酸二酐與多元羥基化合物預先反應後,在其反應產物中添加二胺的方法;或者使四羧酸二酐及二胺預先反應後,在其反應產物中添加多元羥基化合物的方法等。The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, any of the following methods may also be used: a method of adding tetracarboxylic dianhydride, diamine, and polyhydroxy compound to the reaction solvent at the same time; after dissolving the diamine and polyhydroxy compound in the reaction solvent, adding tetracarboxylic acid The method of dianhydride; the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride with the polyhydroxy compound in advance; or the method of adding the diamine to the reaction product after reacting the tetracarboxylic dianhydride and the diamine in advance Methods of polyhydric hydroxy compounds, etc.
在使所述具有一個胺基的胺基矽烷化合物反應的情況下,在四羧酸二酐、以及二胺及多元羥基化合物的反應結束後,將反應後的溶液冷卻至40℃以下後,添加具有一個胺基的胺基矽烷化合物,在10℃~40℃下反應0.1小時~6小時為宜。另外,可在反應的任意階段添加單羥基化合物。In the case of reacting the amine silane compound having one amine group, after the reaction of the tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound is completed, the solution after the reaction is cooled to 40°C or less, and then added The aminosilane compound having one amine group is preferably reacted at 10°C to 40°C for 0.1 to 6 hours. In addition, the monohydroxy compound may be added at any stage of the reaction.
以所述方式合成的聚酯醯胺酸(A)包含式(3)所表示的結構單元及式(4)所表示的結構單元,且其末端為源自作為原料的四羧酸二酐、二胺或多元羥基化合物的酸酐基、胺基或羥基,或者這些化合物以外的添加物構成其末端。通過包含此種構成,硬化性變得良好。The polyester amide acid (A) synthesized in the above manner includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from the tetracarboxylic dianhydride as a raw material, The anhydride group, amine group or hydroxyl group of the diamine or polyhydroxy compound, or additives other than these compounds constitute the terminal. By including such a structure, curability becomes good.
所獲得的聚酯醯胺酸(A)的重量平均分子量較佳為1,000~200,000,更佳為2,000~50,000。若處於這些範圍,則平坦性及耐熱性變得良好。The weight average molecular weight of the obtained polyester amide acid (A) is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. Within these ranges, flatness and heat resistance become good.
本說明書中的重量平均分子量為利用凝膠滲透層析(Gel Permeation Chromatography,GPC)法(管柱溫度:35℃、流速:1 ml/min)而求出的聚苯乙烯換算的值。標準的聚苯乙烯使用分子量為645~132900的聚苯乙烯(例如,安捷倫科技(Agilent Technologies)股份有限公司的聚苯乙烯校準套組(calibration kit)PL2010-0102),管柱使用PL凝膠混合(PLgel MIXED)-D(安捷倫科技(Agilent Technologies)股份有限公司),可使用四氫呋喃(Tetrahydrofuran,THF)作為流動相而進行測定。再者,本說明書中的市售品的重量平均分子量為目錄(catalogue)記載值。The weight-average molecular weight in this specification is a polystyrene conversion value obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) method (column temperature: 35°C, flow rate: 1 ml/min). For standard polystyrene, use polystyrene with a molecular weight of 645 to 132900 (for example, Agilent Technologies Co., Ltd. polystyrene calibration kit (PL2010-0102), and use PL gel for column mixing (PLgel MIXED)-D (Agilent Technologies Co., Ltd.) can be measured using tetrahydrofuran (Tetrahydrofuran, THF) as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is the value described in a catalog.
1-2.環狀醚化合物的聚合物(B) 本發明中所使用的環狀醚化合物的聚合物(B)為選自具有氧雜環丁基的化合物(b1)的均聚物、具有氧雜環丁基的化合物(b1)彼此的共聚物及具有氧雜環丁基的化合物(b1)與具有氧雜環丙基的化合物(b2)的共聚物中的至少一種。環狀醚化合物的聚合物(B)可為一種,也可使用兩種以上。1-2. Polymer of cyclic ether compound (B) The polymer (B) of the cyclic ether compound used in the present invention is a copolymer selected from a homopolymer of a compound (b1) having an oxetanyl group and a compound (b1) having an oxetanyl group. And at least one copolymer of an oxetanyl group-containing compound (b1) and an oxetanyl group-containing compound (b2). The polymer (B) of the cyclic ether compound may be one kind, or two or more kinds may be used.
在使具有氧雜環丁基的化合物(b1)與具有氧雜環丙基的化合物(b2)共聚的情況下,若具有氧雜環丁基的化合物(b1)的比例在環狀醚化合物的聚合物(B)中為50重量%~90重量%,則就屏障性的觀點而言較佳。若具有氧雜環丁基的化合物(b1)的比例為70重量%~90重量%,則屏障性進一步提高。In the case where the compound (b1) having an oxetanyl group is copolymerized with the compound (b2) having an oxetanyl group, if the ratio of the compound (b1) having an oxetanyl group is From 50% by weight to 90% by weight in the polymer (B), it is preferable from the viewpoint of barrier properties. If the ratio of the compound (b1) having an oxetanyl group is 70% by weight to 90% by weight, the barrier property is further improved.
作為具有氧雜環丁基的化合物(b1)的具體例,可列舉:丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(例如,商品名;OXE-10、大阪有機化學工業股份有限公司)、甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯(例如,商品名;OXE-30、大阪有機化學工業股份有限公司)。Specific examples of the compound (b1) having an oxetanyl group include: (3-ethyloxetan-3-yl)methyl acrylate (for example, trade name; OXE-10, Osaka Organic Chemistry Industrial Co., Ltd.), (3-ethyloxetan-3-yl) methyl methacrylate (for example, trade name; OXE-30, Osaka Organic Chemical Industry Co., Ltd.).
作為具有氧雜環丙基的化合物(b2)的具體例,可列舉:丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸甲基縮水甘油酯、4-羥基丁基丙烯酸酯縮水甘油醚。Specific examples of the compound (b2) having an oxetanyl group include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate, and 4-hydroxybutyl acrylate glycidyl ether. .
1-3.環狀醚化合物的聚合物(B)相對於聚酯醯胺酸(A)的比例 相對於本發明的熱硬化性組成物中的聚酯醯胺酸(A)100重量份,環狀醚化合物的聚合物(B)的總量的比例為20重量份~400重量份。若環狀醚化合物的聚合物(B)的總量的比例為所述範圍,則屏障性、平坦性、耐熱性的平衡良好。1-3. Ratio of polymer (B) of cyclic ether compound to polyester amide (A) The ratio of the total amount of the polymer (B) of the cyclic ether compound relative to 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention is 20 parts by weight to 400 parts by weight. When the ratio of the total amount of polymers (B) of the cyclic ether compound is within the above range, the balance of barrier properties, flatness, and heat resistance is good.
1-4.陽離子聚合起始劑(C) 在本發明的熱硬化性組成物中使用陽離子聚合起始劑(C)。本發明中所使用的陽離子聚合起始劑(C)為鎓鹽,作為陽離子種,使用銨鹽、鋶鹽、碘鎓鹽、鏻鹽,作為陰離子種,使用六氟化銻或六氟化磷等。這些陽離子聚合起始劑中,就安全方面的觀點而言,理想的是使用陰離子種為六氟化磷的陽離子聚合起始劑。1-4. Cationic polymerization initiator (C) In the thermosetting composition of the present invention, a cationic polymerization initiator (C) is used. The cationic polymerization initiator (C) used in the present invention is an onium salt, and as a cationic species, an ammonium salt, a monium salt, an iodonium salt, and a phosphonium salt are used, and as an anionic species, antimony hexafluoride or phosphorus hexafluoride is used Wait. Among these cationic polymerization initiators, from the viewpoint of safety, it is desirable to use a cationic polymerization initiator whose anionic species is phosphorus hexafluoride.
作為所述銨鹽系陽離子聚合起始劑的具體例,可列舉:K-PURE CXC-1612、K-PURE CXC-1613、K-PURE CXC-1615、K-PURE TAG2172、K-PURE TAG-2678、K-PURE TAG2713(均為商品名;王者工業(KING INDUSTRIES)股份有限公司)。Specific examples of the ammonium salt-based cationic polymerization initiator include: K-PURE CXC-1612, K-PURE CXC-1613, K-PURE CXC-1615, K-PURE TAG2172, K-PURE TAG-2678 , K-PURE TAG2713 (both trade names; KING INDUSTRIES Co., Ltd.).
作為所述鋶鹽系陽離子聚合起始劑的具體例,可列舉:桑艾德(Sun-aid)SI-110、桑艾德(Sun-aid)SI-150、桑艾德(Sun-aid)SI-300(均為商品名;三新化學工業股份有限公司);CPI-100P、CPI-200K(均為商品名;桑亞普羅(Sanapro)股份有限公司)。As specific examples of the cationic salt-based cationic polymerization initiators, Sun-aid SI-110, Sun-aid SI-150, Sun-aid SI-300 (all trade names; Sanxin Chemical Industry Co., Ltd.); CPI-100P, CPI-200K (all trade names; Sanapro Co., Ltd.).
作為所述碘鎓鹽系陽離子聚合起始劑的具體例,可列舉豔佳固(Irgacure)250、豔佳固(Irgacure)270(均為商品名;巴斯夫(BASF)歐洲公司)。Specific examples of the iodonium salt-based cationic polymerization initiator include Irgacure 250 and Irgacure 270 (both trade names; BASF Europe).
作為所述鏻鹽系陽離子聚合起始劑的具體例,可列舉:乙基三苯基鏻六氟磷酸鹽、乙基三苯基鏻六氟銻酸鹽、四丁基鏻六氟磷酸鹽、四丁基鏻六氟銻酸鹽。Specific examples of the phosphonium salt-based cationic polymerization initiator include ethyltriphenylphosphonium hexafluorophosphate, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluorophosphate, Tetrabutylphosphonium hexafluoroantimonate.
這些陽離子聚合起始劑(C)中,作為使用六氟化銻的鋶鹽系陽離子聚合起始劑的桑艾德(Sun-aid)SI-150顯現非常良好的平坦性及屏障性。另一方面,銻為毒性物質,就安全方面的觀點而言,較佳為向所述組成物中添加不含銻的陽離子聚合起始劑。若選自不含銻的陽離子聚合起始劑,就平坦性、屏障性、安全性及添加量的觀點而言,較佳為鋶鹽系陽離子聚合起始劑。Among these cationic polymerization initiators (C), Sun-aid SI-150, which is a cationic polymerization initiator using antimony hexafluoride, exhibits very good flatness and barrier properties. On the other hand, antimony is a toxic substance, and from the viewpoint of safety, it is preferable to add a cationic polymerization initiator containing no antimony to the composition. If it is selected from cationic polymerization initiators that do not contain antimony, from the viewpoint of flatness, barrier properties, safety, and added amount, it is preferably a cationic polymerization initiator of the saline salt type.
在使用陽離子聚合起始劑(C)的情況下,相對於環狀醚化合物的聚合物(B)100重量份,陽離子聚合起始劑(C)的比例為0.1重量份~60重量份。When the cationic polymerization initiator (C) is used, the ratio of the cationic polymerization initiator (C) is 0.1 to 60 parts by weight with respect to 100 parts by weight of the polymer (B) of the cyclic ether compound.
1-5.硬化劑 在本發明的熱硬化性組成物中,就進一步提高耐熱性、耐化學品性的觀點而言,也可包含酸酐系硬化劑、含羧酸的聚合物、咪唑系硬化劑、酚系硬化劑等硬化劑。1-5. Hardener The thermosetting composition of the present invention may include an acid anhydride-based hardener, a carboxylic acid-containing polymer, an imidazole-based hardener, and a phenol-based hardener from the viewpoint of further improving heat resistance and chemical resistance. Etc. hardener.
所述酸酐系硬化劑的具體例為:馬來酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、六氫偏苯三甲酸酐等脂肪族二羧酸酐;鄰苯二甲酸酐、偏苯三甲酸酐等芳香族多元羧酸酐;以及苯乙烯-馬來酸酐共聚物。這些酸酐系硬化劑中,較佳為耐熱性與對溶劑的溶解性的平衡良好的偏苯三甲酸酐及六氫偏苯三甲酸酐。Specific examples of the acid anhydride-based hardener are: maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrotrimellitic anhydride and other aliphatic Dicarboxylic anhydride; aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride; and styrene-maleic anhydride copolymers. Among these acid anhydride-based curing agents, preferred are trimellitic anhydride and hexahydrotrimellitic anhydride, which have a good balance between heat resistance and solubility in solvents.
作為所述含羧酸的聚合物的具體例,可列舉:阿魯豐(ARUFON)UC-3000、阿魯豐(ARUFON)UC-3090、阿魯豐(ARUFON)UC-3900(均為商品名;東亞合成股份有限公司)、馬普魯夫(Marproof)MA-0215Z、馬普魯夫(Marproof)MA-0217Z及馬普魯夫(Marproof)MA-0221Z(均為商品名;日油股份有限公司)。這些含羧酸的聚合物中,較佳為耐熱性與對溶劑的溶解性及平坦性良好的阿魯豐(ARUFON)UC-3900。Specific examples of the carboxylic acid-containing polymer include: ARUFON UC-3000, ARUFON UC-3090, ARUFON UC-3900 (all are trade names ; East Asia Synthetic Co., Ltd.), Marproof MA-0215Z, Marproof MA-0217Z and Marproof MA-0221Z (both trade names; Nippon Oil Co., Ltd. the company). Among these carboxylic acid-containing polymers, ARUFON UC-3900 having good heat resistance, solubility in solvents and flatness is preferred.
所述咪唑系硬化劑的具體例為:2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2,3-二氫-1H-吡咯并[1,2-a]苯并咪唑、1-氰基乙基-2-十一烷基咪唑鎓偏苯三酸鹽、1-苄基-2-甲基咪唑及1-苄基-2-苯基咪唑。這些咪唑系硬化劑中,較佳為硬化性與對溶劑的溶解性的平衡良好的2-十一烷基咪唑、2-苯基-4-甲基咪唑及1-苄基-2-苯基咪唑。Specific examples of the imidazole-based hardener are: 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro -1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-benzyl-2-methylimidazole and 1- Benzyl-2-phenylimidazole. Among these imidazole-based hardeners, 2-undecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenyl, which have a good balance of hardenability and solubility in solvents, are preferred Imidazole.
酚系硬化劑的具體例可列舉:α,α,α'-三(4-羥基苯基)-1-乙基-4-異丙基苯、1,1,1-三(4-羥基苯基)乙烷、9,9-雙(4-羥基-3-甲基苯基)茀、1,3-雙[2-(4-羥基苯基)-2-丙基]苯、4,4'-(3,3,5-三甲基-1,1-環己烷二基)雙(苯酚)及1,1,2,2-四(4-羥基苯基)乙烷。這些酚系硬化劑中,較佳為耐熱性及相容性的平衡良好的α,α,α'-三(4-羥基苯基)-1-乙基-4-異丙基苯、1,1,1-三(4-羥基苯基)乙烷及9,9-雙(4-羥基-3-甲基苯基)茀。Specific examples of phenolic hardeners include: α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1,1,1-tris(4-hydroxybenzene Group) ethane, 9,9-bis(4-hydroxy-3-methylphenyl) stilbene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 4,4 '-(3,3,5-trimethyl-1,1-cyclohexanediyl)bis(phenol) and 1,1,2,2-tetra(4-hydroxyphenyl)ethane. Among these phenolic hardeners, α,α,α'-tri(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, 1, which has a good balance of heat resistance and compatibility are preferred 1,1-tris(4-hydroxyphenyl)ethane and 9,9-bis(4-hydroxy-3-methylphenyl) stilbene.
在使用硬化劑的情況下,相對於環狀醚化合物的聚合物(B)100重量份,較佳為0.1重量份以上且40重量份以下。When a hardener is used, it is preferably 0.1 part by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polymer (B) of the cyclic ether compound.
1-6.其他成分 在本發明的熱硬化性組成物中,可添加各種添加劑以提高平坦性、耐劃傷性、塗佈均勻性、密著性等膜物性。添加劑主要可列舉:具有氧雜環丙基的化合物(b2)以外的環氧化合物,具有聚合性雙鍵的化合物,溶劑,陰離子系、陽離子系、非離子系、氟系或矽系的調平劑·界面活性劑,矽烷偶合劑等密著性提高劑,受阻酚系、受阻胺系、磷系、硫系化合物等抗氧化劑。1-6. Other ingredients In the thermosetting composition of the present invention, various additives may be added to improve film properties such as flatness, scratch resistance, coating uniformity, and adhesion. Additives mainly include: epoxy compounds other than oxetanyl compound (b2), compounds having polymerizable double bonds, solvents, anionic, cationic, nonionic, fluorine or silicon leveling Agents/surfactants, adhesion improvers such as silane coupling agents, antioxidants such as hindered phenols, hindered amines, phosphorus, and sulfur compounds.
1-6-1.環氧化合物 在本發明的熱硬化性組成物中,也可使用具有氧雜環丙基的化合物(b2)以外的環氧化合物。本發明的熱硬化性組成物中所任意使用的環氧化合物為每一分子中具有兩個以上的環氧基的化合物。環氧化合物可為一種,也可使用兩種以上。1-6-1. Epoxy compound In the thermosetting composition of the present invention, an epoxy compound other than the compound (b2) having an oxetanyl group can also be used. The epoxy compound used arbitrarily in the thermosetting composition of the present invention is a compound having two or more epoxy groups per molecule. The epoxy compound may be one kind, or two or more kinds may be used.
所述環氧化合物的例子為:雙酚A型環氧化合物、雙酚F型環氧化合物、縮水甘油醚型環氧化合物、縮水甘油酯型環氧化合物、聯苯型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、雙酚A酚醛清漆型環氧化合物、脂肪族聚縮水甘油醚化合物、環式脂肪族環氧化合物、具有環氧基的單體與其他單體的共聚物及具有矽氧烷鍵結部位的環氧化合物。Examples of the epoxy compound are: bisphenol A epoxy compound, bisphenol F epoxy compound, glycidyl ether epoxy compound, glycidyl ester epoxy compound, biphenyl epoxy compound, phenol novolac Varnish-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolac-type epoxy compounds, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy compounds, monomers with epoxy groups and others Copolymers of monomers and epoxy compounds with siloxane bond sites.
雙酚A型環氧化合物的市售品的具體例為jER 828、jER 1004、jER 1009(均為商品名;三菱化學股份有限公司);雙酚F型環氧化合物的市售品的具體例為jER 806、jER 4005P(均為商品名;三菱化學股份有限公司);縮水甘油醚型環氧化合物的市售品的具體例為特克莫(TECHMORE)VG3101L(商品名;普林泰科(Printec)股份有限公司),EHPE3150(商品名;大賽璐(Daicel)股份有限公司),EPPN-501H、EPPN-502H(均為商品名;日本化藥股份有限公司),及jER 1032H60(商品名;三菱化學股份有限公司);縮水甘油酯型環氧化合物的市售品的具體例為丹納考爾(Denacol)EX-721(商品名;長瀨化成(Nagase chemteX)股份有限公司),及1,2-環己烷二羧酸二縮水甘油酯(商品名;東京化成工業股份有限公司製造);聯苯型環氧化合物的市售品的具體例為jER YX4000、jER YX4000H、jER YL6121H(均為商品名;三菱化學股份有限公司),及NC-3000、NC-3000-L、NC-3000-H、NC-3100(均為商品名;日本化藥股份有限公司);苯酚酚醛清漆型環氧化合物的市售品的具體例為EPPN-201(商品名;日本化藥股份有限公司),及jER 152、jER 154(均為商品名;三菱化學股份有限公司)等;甲酚酚醛清漆型環氧化合物的市售品的具體例為EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1020(均為商品名;日本化藥股份有限公司)等;雙酚A酚醛清漆型環氧化合物的市售品的具體例為jER 157S65、jER 157S70(均為商品名;三菱化學股份有限公司);環式脂肪族環氧化合物的市售品的具體例為賽羅西德(Celloxide)2021P、賽羅西德(Celloxide)3000(均為商品名;大賽璐(Daicel)股份有限公司);具有矽氧烷鍵結部位的環氧化合物的市售品的具體例為1,3-雙[2-(3,4-環氧環己基)乙基]四甲基二矽氧烷(商品名;捷萊斯特股份有限公司(Gelest Incorporated)),TSL9906(商品名;日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司),考特奧斯陸(COATOSIL)MP200(商品名;日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司),空珀塞朗(Conpoceran)SQ506(商品名;荒川化學股份有限公司),ES-1023(商品名;信越化學工業股份有限公司)。Specific examples of commercially available products of bisphenol A type epoxy compounds are jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi Chemical Corporation); specific examples of commercially available products of bisphenol F type epoxy compounds JER 806, jER 4005P (both trade names; Mitsubishi Chemical Co., Ltd.); a specific example of a commercially available product of a glycidyl ether epoxy compound is TECHMORE VG3101L (trade name; Plintech ( Printec) Co., Ltd.), EHPE3150 (trade name; Daicel) Co., Ltd., EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), and jER 1032H60 (trade name; Mitsubishi Chemical Corporation); specific examples of commercially available products of glycidyl ester epoxy compounds are Denacol EX-721 (trade name; Nagase chemteX Co., Ltd.), and 1 ,2-Cyclohexanedicarboxylic acid diglycidyl ester (trade name; manufactured by Tokyo Chemical Industry Co., Ltd.); specific examples of commercially available products of biphenyl-type epoxy compounds are jER YX4000, jER YX4000H, and jER YL6121H (all Is a trade name; Mitsubishi Chemical Co., Ltd.), and NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.); phenol novolak type ring Specific examples of commercially available products of oxygen compounds are EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), and jER 152, jER 154 (both trade names; Mitsubishi Chemical Co., Ltd.), etc.; cresol novolac type Specific examples of commercially available products of epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all are trade names; Nippon Kayaku Co., Ltd.), etc.; bisphenol A novolac epoxy compound Specific examples of commercially available products are jER 157S65, jER 157S70 (both trade names; Mitsubishi Chemical Co., Ltd.); specific examples of commercially available products of cycloaliphatic epoxy compounds are Celloxide 2021P, Celloxide 3000 (both trade names; Daicel) Co., Ltd.; a specific example of a commercial product of an epoxy compound having a siloxane bond site is 1,3-bis[2 -(3,4-epoxycyclohexyl)ethyl]tetramethyldisilaxane (trade name; Gelest Incorporated), TSL9906 (trade name; Momentive, Japan) Performance Materials Japan) Co., Ltd., COATOSIL MP 200 (trade name; Momentive Performance Materials Japan), Conpoceran SQ506 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Industry) Co., Ltd.).
再者,特克莫(TECHMORE)VG3101L(商品名;普林泰科(Printec)股份有限公司)為2-[4-(2,3-環氧丙氧基)苯基]-2-[4-[1,1-雙[4-(2,3-環氧丙氧基)苯基]乙基]苯基]丙烷及1,3-雙[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-[4-[1-[4-(2,3-環氧丙氧基)苯基]-1-甲基乙基]苯基]乙基]苯氧基]-2-丙醇的混合物;EHPE3150(商品名;大賽璐(Daicel)股份有限公司)為2,2-雙(羥基甲基)-1-丁醇的1,2-環氧基-4-(2-環氧乙烷基(oxiranyl))環己烷加成物;賽羅西德(Celloxide)2021P(商品名;大賽璐(Daicel)股份有限公司)為3',4'-環氧環己基甲基-3,4-環氧環己烷羧酸酯;賽羅西德(Celloxide)3000(商品名;大賽璐(Daicel)股份有限公司)為1-甲基-4-(2-甲基環氧乙烷基)-7-氧雜雙環[4.1.0]庚烷;考特奧斯陸(COATOSIL)MP200(商品名;日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司)為3-縮水甘油氧基丙基三甲氧基矽烷的聚合物。Furthermore, TECHMORE VG3101L (trade name; Printec Co., Ltd.) is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4 -[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3 -Glycidoxy)phenyl]-1-[4-[1-[4-(2,3-glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl] Phenoxy]-2-propanol mixture; EHPE3150 (trade name; Daicel Corporation) is 1,2-epoxy of 2,2-bis(hydroxymethyl)-1-butanol -4-(2-oxiranyl) cyclohexane adduct; Celloxide 2021P (trade name; Daicel Corporation) is 3', 4'- Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; Celloxide 3000 (trade name; Daicel Corporation) is 1-methyl-4-( 2-methyloxirane)-7-oxabicyclo[4.1.0]heptane; COATOSIL MP200 (trade name; Momentive Performance Materials Japan Co., Ltd.) It is a polymer of 3-glycidoxypropyltrimethoxysilane.
所述環氧化合物可單獨使用所述化合物,也可混合使用兩種以上。The epoxy compound may be used alone or in combination of two or more.
1-6-2.具有氧雜環丙基的化合物(b2)以外的環氧化合物相對於聚酯醯胺酸(A)的比例 相對於本發明的熱硬化性組成物中的聚酯醯胺酸(A)100重量份,所述具有氧雜環丙基的化合物(b2)以外的環氧化合物的總量的比例為0重量份~100重量份。若具有氧雜環丙基的化合物(b2)以外的環氧化合物的總量的比例為所述範圍,則平坦性、耐熱性、耐化學品性、密著性、屏障性的平衡良好。在更重視屏障性的情況下,具有氧雜環丙基的化合物(b2)以外的環氧化合物的總量較佳為0重量份~50重量份的範圍。1-6-2. Ratio of epoxy compound other than oxetanyl compound (b2) to polyester amide (A) The ratio of the total amount of epoxy compounds other than the oxetanyl group-containing compound (b2) to 0 parts by weight of the polyester amidic acid (A) in the thermosetting composition of the present invention is 0 parts by weight Parts to 100 parts by weight. If the ratio of the total amount of epoxy compounds other than the oxetanyl compound (b2) is within the above range, the balance of flatness, heat resistance, chemical resistance, adhesion, and barrier properties is good. When the barrier property is more important, the total amount of epoxy compounds other than the oxetanyl-containing compound (b2) is preferably in the range of 0 parts by weight to 50 parts by weight.
1-6-3.具有聚合性雙鍵的化合物 在本發明的熱硬化性組成物中,也可使用具有聚合性雙鍵的化合物。本發明的熱硬化性組成物中所使用的具有聚合性雙鍵的化合物只要在每一分子中具有兩個以上的聚合性雙鍵,則並無特別限定。1-6-3. Compounds with polymerizable double bonds In the thermosetting composition of the present invention, a compound having a polymerizable double bond can also be used. The compound having a polymerizable double bond used in the thermosetting composition of the present invention is not particularly limited as long as it has two or more polymerizable double bonds per molecule.
所述具有聚合性雙鍵的化合物中的每一分子中具有兩個聚合性雙鍵的化合物的具體例為:乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、表氯醇改質乙二醇二(甲基)丙烯酸酯、表氯醇改質二乙二醇二(甲基)丙烯酸酯、表氯醇改質三乙二醇二(甲基)丙烯酸酯、表氯醇改質四乙二醇二(甲基)丙烯酸酯、表氯醇改質聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、四丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、表氯醇改質丙二醇二(甲基)丙烯酸酯、表氯醇改質二丙二醇二(甲基)丙烯酸酯、表氯醇改質三丙二醇二(甲基)丙烯酸酯、表氯醇改質四丙二醇二(甲基)丙烯酸酯、表氯醇改質聚丙二醇二(甲基)丙烯酸酯、丙三醇丙烯酸酯甲基丙烯酸酯、丙三醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、表氯醇改質1,6-己二醇二(甲基)丙烯酸酯、甲氧基化環己基二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、己內酯改質羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、硬脂酸改質季戊四醇二(甲基)丙烯酸酯、烯丙基化環己基二(甲基)丙烯酸酯、雙[(甲基)丙烯醯氧基新戊二醇]己二酸酯、雙酚A二(甲基)丙烯酸酯、環氧乙烷改質雙酚A二(甲基)丙烯酸酯、雙酚F二(甲基)丙烯酸酯、環氧乙烷改質雙酚F二(甲基)丙烯酸酯、雙酚S二(甲基)丙烯酸酯、環氧乙烷改質雙酚S二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二丙烯酸二環戊基酯、環氧乙烷改質磷酸二(甲基)丙烯酸酯、己內酯·環氧乙烷改質磷酸二(甲基)丙烯酸酯、表氯醇改質鄰苯二甲酸二(甲基)丙烯酸酯、四溴雙酚A二(甲基)丙烯酸酯、三丙三醇二(甲基)丙烯酸酯、新戊二醇改質三羥甲基丙烷二(甲基)丙烯酸酯及異氰脲酸環氧乙烷改質二丙烯酸酯。Specific examples of the compound having two polymerizable double bonds per molecule in the compound having a polymerizable double bond are: ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylic acid Ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol di(meth)acrylate ) Acrylic ester, epichlorohydrin modified diethylene glycol di(meth)acrylate, epichlorohydrin modified triethylene glycol di(meth)acrylate, epichlorohydrin modified tetraethylene glycol di(meth) Base) acrylate, epichlorohydrin modified polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate , Tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin modified propylene glycol di(meth)acrylate, epichlorohydrin modified dipropylene glycol di(meth)acrylate, Epichlorohydrin modified tripropylene glycol di(meth)acrylate, epichlorohydrin modified tetrapropylene glycol di(meth)acrylate, epichlorohydrin modified polypropylene glycol di(meth)acrylate, glycerol acrylate Methacrylate, glycerol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, epichlorohydrin modified 1,6-hexanediol di(meth)acrylate , Methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, caprolactone modified hydroxyl Trimethylacetic acid neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(methyl) Acryloyl neopentyl glycol] adipate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, bisphenol F di(methyl) Acrylate, ethylene oxide modified bisphenol F di(meth)acrylate, bisphenol S di(meth)acrylate, ethylene oxide modified bisphenol S di(meth)acrylate, 1, 4-Butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, dicyclopentyl diacrylate, ethylene oxide modified di(meth)acrylate , Caprolactone·ethylene oxide modified di(meth)acrylate, epichlorohydrin modified phthalate di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, Triglycerol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate and isocyanurate ethylene oxide modified diacrylate.
所述具有聚合性雙鍵的化合物中的每一分子中具有三個以上的聚合性雙鍵的化合物的具體例為:三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、表氯醇改質三羥甲基丙烷三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、表氯醇改質丙三醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、環氧乙烷改質磷酸三(甲基)丙烯酸酯、己內酯·環氧乙烷改質磷酸三(甲基)丙烯酸酯、己內酯改質三[(甲基)丙烯醯氧基乙基]異氰脲酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二甘油四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯及烷基改質二季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯及含羧基的多官能(甲基)丙烯酸酯。Specific examples of the compound having three or more polymerizable double bonds in each molecule of the compound having a polymerizable double bond are: trimethylolpropane tri(meth)acrylate, ethylene oxide modification Trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylolpropane tri(meth)acrylate, propylene Triol tri(meth)acrylate, epichlorohydrin modified glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, cyclic Oxyethane modified tri(meth)acrylate, caprolactone·ethylene oxide modified tri(meth)acrylate, caprolactone modified tri[(meth)acryloyloxyethyl ] Isocyanurate, di-trimethylolpropane tetra (meth) acrylate, diglycerol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and alkyl modified di pentaerythritol tetra (meth) Base) acrylate, dipentaerythritol penta(meth)acrylate, alkyl modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate ) Acrylic esters and polyfunctional (meth)acrylates containing carboxyl groups.
所述具有聚合性雙鍵的化合物可單獨使用所述化合物,也可混合使用兩種以上。The compound having a polymerizable double bond may be used alone or in combination of two or more.
在所述具有聚合性雙鍵的化合物100重量%中,就耐劃傷性的觀點而言,較佳為包含50重量%以上的每一分子中具有三個以上的聚合性雙鍵的化合物。From the viewpoint of scratch resistance, 100% by weight of the compound having a polymerizable double bond is preferably a compound containing 50% by weight or more of three or more polymerizable double bonds per molecule.
在所述具有聚合性雙鍵的化合物中,就平坦性及耐劃傷性的觀點而言,較佳為使用異氰脲酸環氧乙烷改質二丙烯酸酯、異氰脲酸環氧乙烷改質三丙烯酸酯、三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯及含羧基的多官能(甲基)丙烯酸酯。Among the compounds having a polymerizable double bond, from the viewpoint of flatness and scratch resistance, isocyanurate ethylene oxide is preferably used to modify diacrylate, isocyanurate ethylene oxide Alkane modified triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl group-containing multifunctional (meth)acrylate.
所述具有聚合性雙鍵的化合物可使用如下述般的市售品。異氰脲酸環氧乙烷改質二丙烯酸酯的具體例為亞羅尼斯(Aronix)M-215(商品名;東亞合成股份有限公司);異氰脲酸環氧乙烷改質二丙烯酸酯及異氰脲酸環氧乙烷改質三丙烯酸酯的混合物的具體例為亞羅尼斯(Aronix)M-313(30重量%~40重量%)及亞羅尼斯(Aronix)M-315(3重量%~13重量%,以下略記為“M-315”)(均為商品名;東亞合成股份有限公司,括號內的含有率為混合物中的異氰脲酸環氧乙烷改質二丙烯酸酯的含有率的目錄記載值);三羥甲基丙烷三丙烯酸酯的具體例為亞羅尼斯(Aronix)M-309(商品名;東亞合成股份有限公司);季戊四醇三丙烯酸酯及季戊四醇四丙烯酸酯的混合物的具體例為亞羅尼斯(Aronix)M-306(65重量%~70重量%)、亞羅尼斯(Aronix)M-305(55重量%~63重量%)、亞羅尼斯(Aronix)M-303(30重量%~60重量%)、亞羅尼斯(Aronix)M-452(25重量%~40重量%)及亞羅尼斯(Aronix)M-450(未滿10重量%)(均為商品名;東亞合成股份有限公司,括號內的含有率為混合物中的季戊四醇三丙烯酸酯的含有率的目錄記載值);二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯的混合物的具體例為亞羅尼斯(Aronix)M-403(50重量%~60重量%)、亞羅尼斯(Aronix)M-400(40重量%~50重量%)、亞羅尼斯(Aronix)M-402(30重量%~40重量%,以下略記為“M-402”)、亞羅尼斯(Aronix)M-404(30重量%~40重量%)、亞羅尼斯(Aronix)M-406(25重量%~35重量%)及亞羅尼斯(Aronix)M-405(10重量%~20重量%)(均為商品名;東亞合成股份有限公司,括號內的含有率為混合物中的二季戊四醇五丙烯酸酯的含有率的目錄記載值);含羧基的多官能(甲基)丙烯酸酯的具體例為亞羅尼斯(Aronix)M-510及亞羅尼斯(Aronix)M-520(以下略記為“M-520”)(均為商品名;東亞合成股份有限公司)。As the compound having a polymerizable double bond, commercially available products as described below can be used. A specific example of isocyanuric acid ethylene oxide modified diacrylate is Aronix (Aronix) M-215 (trade name; East Asia Synthetic Co., Ltd.); isocyanuric acid ethylene oxide modified diacrylate Specific examples of mixtures of isocyanuric acid ethylene oxide modified triacrylates are Aronix M-313 (30% by weight to 40% by weight) and Aronix M-315 (3 % By weight to 13% by weight, hereinafter abbreviated as "M-315") (all are trade names; East Asia Synthetic Co., Ltd., the content in parentheses is isocyanuric acid ethylene oxide modified diacrylate in the mixture Contents listed in the catalogue); the specific examples of trimethylolpropane triacrylate are Aronix M-309 (trade name; East Asia Synthetic Co., Ltd.); pentaerythritol triacrylate and pentaerythritol tetraacrylate Specific examples of the mixture of Aronix (Aronix) M-306 (65 wt% ~ 70 wt%), Aronix (Aronix) M-305 (55 wt% ~ 63 wt%), Aronix (Aronix) M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight) and Aronix M-450 (less than 10% by weight) (both It is a trade name; East Asia Synthetic Co., Ltd., the content rate in parentheses is the cataloged value of the content rate of pentaerythritol triacrylate in the mixture); the specific example of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is sub Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% to 50% by weight), Aronix M-402 (30% by weight) ~40% by weight, hereinafter abbreviated as “M-402”), Aronix M-404 (30%-40%), Aronix M-406 (25%~35% %) and Aronix (Aronix) M-405 (10% by weight to 20% by weight) (both trade names; East Asia Synthetic Co., Ltd., the content in parentheses is the content of dipentaerythritol pentaacrylate in the mixture Catalogue value); Specific examples of carboxyl-containing polyfunctional (meth)acrylates are Aronix (Aronix) M-510 and Aronix (Aronix) M-520 (hereinafter abbreviated as "M-520") (All are trade names; East Asia Synthetic Co., Ltd.).
1-6-4.具有聚合性雙鍵的化合物相對於聚酯醯胺酸(A)的比例 相對於本發明的熱硬化性組成物中的聚酯醯胺酸(A)100重量份,具有聚合性雙鍵的化合物的總量的比例為0重量份~100重量份。若具有聚合性雙鍵的化合物的總量的比例為所述範圍,則平坦性、耐熱性、耐劃傷性及屏障性的平衡良好。在更重視屏障性的情況下,具有聚合性雙鍵的化合物的總量較佳為0重量份~50重量份的範圍。1-6-4. Ratio of compound with polymerizable double bond to polyester amide (A) The ratio of the total amount of the compound having a polymerizable double bond is 100 parts by weight to 100 parts by weight with respect to 100 parts by weight of the polyester amide acid (A) in the thermosetting composition of the present invention. If the ratio of the total amount of the compound having a polymerizable double bond is within the above range, the balance of flatness, heat resistance, scratch resistance, and barrier properties is good. When the barrier property is more important, the total amount of the compound having a polymerizable double bond is preferably in the range of 0 parts by weight to 50 parts by weight.
1-6-5.溶劑(D) 在本發明的熱硬化性組成物中,也可使用溶劑(D)。本發明的熱硬化性組成物中所任意添加的溶劑(D)較佳為可溶解聚酯醯胺酸(A)、環狀醚化合物的聚合物(B)、陽離子聚合起始劑(C)等的溶劑。所述溶劑(D)的具體例為:甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、異丁醇、第三丁醇、丙酮、2-丁酮、乙酸乙酯、乙酸丁酯、乙酸丙酯、丙酸丁酯、乳酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧基丙酸甲酯、3-羥基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-羥基丙酸甲酯、2-羥基丙酸丙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-側氧丁酸甲酯、2-側氧丁酸乙酯、4-羥基-4-甲基-2-戊酮、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、乙二醇單甲醚、乙二醇單***、乙二醇單異丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、環戊酮、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單***、二乙二醇單***乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、四氫呋喃、乙腈、二噁烷、甲苯、二甲苯、γ-丁內酯、或N,N-二甲基乙醯胺及環己酮、乙二醇、二乙二醇、三乙二醇、四乙二醇、重量平均分子量1,000以下的聚乙二醇、丙二醇、二丙二醇、三丙二醇、四丙二醇、重量平均分子量1,000以下的聚丙二醇。溶劑可為這些溶劑的一種,也可為這些溶劑的兩種以上的混合物。1-6-5. Solvent (D) In the thermosetting composition of the present invention, a solvent (D) can also be used. The solvent (D) optionally added to the thermosetting composition of the present invention is preferably a polymer (B) capable of dissolving polyester amide acid (A), a cyclic ether compound, and a cationic polymerization initiator (C) And other solvents. Specific examples of the solvent (D) are: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, third butanol, acetone, 2-butanone , Ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate , Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2 -Methyl methyl propionate, ethyl 2-hydroxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, ethyl 2-ethoxy-2-methyl propionate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy- 4-methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol mono Butyl ether acetate, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, Xylene, γ-butyrolactone, or N,N-dimethylacetamide and cyclohexanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, weight average molecular weight of 1,000 or less Polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less. The solvent may be one of these solvents, or a mixture of two or more of these solvents.
相對於熱硬化性組成物總量,溶劑(D)的含量較佳為65重量%~95重量%。更佳為70重量%~90重量%。The content of the solvent (D) is preferably 65% by weight to 95% by weight relative to the total amount of the thermosetting composition. More preferably, it is 70% by weight to 90% by weight.
1-6-6.界面活性劑 在本發明的熱硬化性組成物中,也可添加界面活性劑以提高塗佈均勻性。界面活性劑的具體例為:波利弗洛(Polyflow)No.75、波利弗洛(Polyflow)No.90、波利弗洛(Polyflow)No.95(以上均為商品名;共榮社化學股份有限公司)、迪斯帕畢克(Disperbyk)-161、迪斯帕畢克(Disperbyk)-162、迪斯帕畢克(Disperbyk)-163、迪斯帕畢克(Disperbyk)-164、迪斯帕畢克(Disperbyk)-166、迪斯帕畢克(Disperbyk)-170、迪斯帕畢克(Disperbyk)-180、迪斯帕畢克(Disperbyk)-181、迪斯帕畢克(Disperbyk)-182、BYK-300、BYK-306、BYK-310、BYK-320、BYK-330、BYK-342、BYK-346、BYK-361N、BYK-UV3500、BYK-UV3570(以上均為商品名;日本畢克化學(BYK Chemie Japan)股份有限公司)、KP-341、KP-368、KF-96-50CS、KF-50-100CS(以上均為商品名;信越化學工業股份有限公司)、沙福隆(Surflon)S611(商品名;AGC清美化學(AGC Seimi Chemical)股份有限公司)、福吉特(Ftergent)222F、福吉特(Ftergent)208G、福吉特(Ftergent)251、福吉特(Ftergent)710FL、福吉特(Ftergent)710FM、福吉特(Ftergent)710FS、福吉特(Ftergent)601AD、福吉特(Ftergent)602A、福吉特(Ftergent)650A、FTX-218(以上均為商品名;尼奧斯(Neos)股份有限公司)、美佳法(Megafac)F-410、美佳法(Megafac)F-430、美佳法(Megafac)F-444、美佳法(Megafac)F-472SF、美佳法(Megafac)F-475、美佳法(Megafac)F-477、美佳法(Megafac)F-552、美佳法(Megafac)F-553、美佳法(Megafac)F-554、美佳法(Megafac)F-555、美佳法(Megafac)F-556、美佳法(Megafac)F-558、美佳法(Megafac)F-559、美佳法(Megafac)R-94、美佳法(Megafac)RS-75、美佳法(Megafac)RS-72-K、美佳法(Megafac)RS-76-NS、美佳法(Megafac)DS-21(以上均為商品名;迪愛生(DIC)股份有限公司)、迪高屯(TEGO Twin)4000、迪高屯(TEGO Twin)4100、迪高弗洛(TEGO Flow)370、迪高格萊德(TEGO Glide)440、迪高格萊德(TEGO Glide)450、迪高拉德(TEGO Rad)2200N(以上均為商品名;日本贏創(Evonik Japan)股份有限公司)、氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基碘化銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚、聚氧乙烯月桂基醚、聚氧乙烯油烯基醚、聚氧乙烯十三烷基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、聚氧乙烯月桂基胺、山梨醇酐月桂酸酯、山梨醇酐棕櫚酸酯、山梨醇酐硬脂酸酯、山梨醇酐油酸酯、山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐月桂酸酯、聚氧乙烯山梨醇酐棕櫚酸酯、聚氧乙烯山梨醇酐硬脂酸酯、聚氧乙烯山梨醇酐油酸酯、聚氧乙烯萘基醚、烷基苯磺酸鹽及烷基二苯基醚二磺酸鹽。較佳為使用選自這些化合物中的至少一種。1-6-6. Surfactant In the thermosetting composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of surfactants are: Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (the above are trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk -161, Disperbyk -162, Disperbyk -163, Disperbyk -164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk (Disperbyk)-181 Disperbyk)-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (the above are trade names ; BYK Chemie Japan Co., Ltd., KP-341, KP-368, KF-96-50CS, KF-50-100CS (the above are trade names; Shin-Etsu Chemical Industry Co., Ltd.), Sha Surflon S611 (trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL , Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 602A, Ftergent 650A, FTX-218 (the above are trade names; Nios ( Neos) Co., Ltd., Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-410 475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac ( Megafac) F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Mega(ac) fac) RS-72-K, Megafac RS-76-NS, Megafac DS-21 (the above are trade names; DIC Co., Ltd.), TEGO Twin ) 4000, TEGO Twin (4100), TEGO Flow (370), TEGO Glide (440), TEGO Glide (450), TEGO Glide (450), TEGO Glide (TEGO) Rad) 2200N (the above are trade names; Evonik Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl iodide Ammonium, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonyl Phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl wax Ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan Palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan Alkyd stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these compounds.
這些界面活性劑中,若為選自BYK-306、BYK-342、BYK-346、KP-341、KP-368、沙福隆(Surflon)S611、福吉特(Ftergent)710FL、福吉特(Ftergent)710FM、福吉特(Ftergent)710FS、福吉特(Ftergent)650A、美佳法(Megafac)F-477、美佳法(Megafac)F-556、美佳法(Megafac)RS-72-K、美佳法(Megafac)DS-21、迪高屯(TEGO Twin)4000、氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、氟烷基磺酸鹽、氟烷基三甲基銨鹽及氟烷基胺基磺酸鹽中的至少一種,則熱硬化性組成物的塗佈均勻性變高,因此較佳。If these surfactants are selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethylammonium At least one of a salt and a fluoroalkylamine sulfonate is preferable because the uniformity of coating of the thermosetting composition becomes high.
相對於熱硬化性組成物總量,本發明的熱硬化性組成物中的界面活性劑的含量較佳為0.01重量%~10重量%。The content of the surfactant in the thermosetting composition of the present invention is preferably 0.01% by weight to 10% by weight relative to the total amount of the thermosetting composition.
1-6-7.密著性提高劑 就使所形成的硬化膜與基板的密著性進一步提高的觀點而言,本發明的熱硬化性組成物也可還含有密著性提高劑。作為密著性提高劑的例子,可列舉矽烷系、鋁系或鈦酸酯系的偶合劑。具體而言為:3-縮水甘油氧基丙基二甲基乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷(例如,薩拉艾斯(Sila-Ace)S510;商品名;捷恩智(JNC)股份有限公司)、2-(3,4-環氧環己基)乙基三甲氧基矽烷(例如,薩拉艾斯(Sila-Ace)S530;商品名;捷恩智(JNC)股份有限公司)、3-巰基丙基三甲氧基矽烷(例如,薩拉艾斯(Sila-Ace)S810;商品名;捷恩智(JNC)股份有限公司)、3-縮水甘油氧基丙基三甲氧基矽烷的共聚物(例如,商品名;考特奧斯陸(COATOSIL)MP200,日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司)等矽烷系偶合劑,乙醯烷氧基二異丙醇鋁等鋁系偶合劑及四異丙基雙(二辛基亞磷酸酯)鈦酸酯等鈦酸酯系偶合劑。1-6-7. Adhesion improver From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent include silane-based, aluminum-based, or titanate-based coupling agents. Specifically: 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane ( For example, Sila-Ace S510; trade name; JNC (JNC) Co., Ltd.), 2-(3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, Sala-Ace) (Sila-Ace) S530; trade name; JNC (JNC) Co., Ltd., 3-mercaptopropyltrimethoxysilane (for example, Sila-Ace) S810; trade name; JNC) Co., Ltd.), a copolymer of 3-glycidoxypropyltrimethoxysilane (for example, trade name; COATOSIL MP200, Momentive Performance Materials Japan) Co., Ltd. ) And other silane-based coupling agents, aluminum acetyl diisopropoxide and other aluminum-based coupling agents, and tetraisopropyl bis (dioctyl phosphite) titanate and other titanate-based coupling agents.
這些密著性提高劑中,3-縮水甘油氧基丙基三甲氧基矽烷的提升密著性的效果大,因此較佳。Among these adhesion improving agents, 3-glycidoxypropyltrimethoxysilane has a large effect of improving adhesion and is therefore preferable.
相對於熱硬化性組成物總量,密著性提高劑的含量較佳為0.01重量%以上且10重量%以下。The content of the adhesion improving agent is preferably 0.01% by weight or more and 10% by weight or less relative to the total amount of the thermosetting composition.
1-6-8.抗氧化劑 就提高透明性、防止硬化膜暴露在高溫下的情況下的黃變的觀點而言,本發明的熱硬化性組成物也可還含有抗氧化劑。1-6-8. Antioxidants From the viewpoints of improving transparency and preventing yellowing when the cured film is exposed to high temperature, the thermosetting composition of the present invention may further contain an antioxidant.
在本發明的熱硬化性組成物中,也可添加受阻酚系、受阻胺系、磷系、硫系化合物等抗氧化劑。其中,就耐光性的觀點而言,較佳為受阻酚系。具體例為:易璐佳諾斯(Irganox)1010、易璐佳諾斯(Irganox)1010FF、易璐佳諾斯(Irganox)1035、易璐佳諾斯(Irganox)1035FF、易璐佳諾斯(Irganox)1076、易璐佳諾斯(Irganox)1076FD、易璐佳諾斯(Irganox)1098、易璐佳諾斯(Irganox)1135、易璐佳諾斯(Irganox)1330、易璐佳諾斯(Irganox)1726、易璐佳諾斯(Irganox)1425WL、易璐佳諾斯(Irganox)1520L、易璐佳諾斯(Irganox)245、易璐佳諾斯(Irganox)245FF、易璐佳諾斯(Irganox)259、易璐佳諾斯(Irganox)3114、易璐佳諾斯(Irganox)565、易璐佳諾斯(Irganox)565DD(均為商品名;日本巴斯夫(BASF Japan)股份有限公司)、艾迪科斯塔波(ADK STAB)AO-20、艾迪科斯塔波(ADK STAB)AO-30、艾迪科斯塔波(ADK STAB)AO-50、艾迪科斯塔波(ADK STAB)AO-60、艾迪科斯塔波(ADK STAB)AO-80(均為商品名;艾迪科(ADEKA)股份有限公司)。其中,更佳為易璐佳諾斯(Irganox)1010、艾迪科斯塔波(ADK STAB)AO-60。Antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added to the thermosetting composition of the present invention. Among these, from the viewpoint of light resistance, hindered phenols are preferred. Specific examples are: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, Irganox (Irganox) 1035FF Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1330, Irganox (Irganox) Irganox) 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox (Irganox) 245FF Irganox) 259, Irganox 3114, Irganox 565, Irganox 565DD (all trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO- 60. ADK STAB AO-80 (all trade names; ADEKA) Co., Ltd. Among them, the better ones are Irganox 1010 and ADK STAB AO-60.
相對於熱硬化性組成物總量,添加0.1重量份~5重量份的抗氧化劑而使用。The antioxidant is added in an amount of 0.1 to 5 parts by weight relative to the total amount of the thermosetting composition.
1-6-9.分子量調整劑 本發明的熱硬化性組成物也可還含有分子量調整劑,以抑制因聚合而分子量變高,且顯現優異的保存穩定性。作為分子量調整劑,可列舉:硫醇類、黃原酸類、醌類、氫醌類及2,4-二苯基-4-甲基-1-戊烯等。1-6-9. Molecular weight regulator The thermosetting composition of the present invention may further contain a molecular weight adjuster to suppress the increase in molecular weight due to polymerization and exhibit excellent storage stability. Examples of the molecular weight modifier include thiols, xanthogen acids, quinones, hydroquinones, 2,4-diphenyl-4-methyl-1-pentene, and the like.
作為分子量調整劑的具體例,可列舉:1,4-萘醌、1,2-苯醌、1,4-苯醌、甲基-對苯醌、蒽醌、氫醌、甲基氫醌、第三丁基氫醌、2,5-二-第三丁基氫醌、2,5-二-第三戊基氫醌、1,4-二羥基萘、3,6-二羥基苯并降冰片烷、4-甲氧基苯酚、2,2',6,6'-四-第三丁基-4,4'-二羥基聯苯、3-(3,5-二-第三丁基-4-羥基苯基)丙酸硬脂酯、2,2'-亞甲基雙(6-第三丁基-4-乙基苯酚)、2,4,6-三(3',5'-二-第三丁基-4'-羥基苄基)均三甲苯、季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、4-第三丁基鄰苯二酚、正己基硫醇、正辛基硫醇、正十二烷基硫醇、第三-十二烷基硫醇、硫代乙醇酸(thioglycolic acid)、二甲基黃原酸硫醚、二異丙基黃原酸二硫醚、2,6-二-第三丁基-對甲酚、4,4'-亞丁基雙(6-第三丁基-間甲酚)、4,4'-硫代雙(6-第三丁基-間甲酚)、2,4-二苯基-4-甲基-1-戊烯、吩噻嗪、2-羥基-1,4-萘醌等。Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, Third butyl hydroquinone, 2,5-di-third butyl hydroquinone, 2,5-di-third pentyl hydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzophenone Bornane, 4-methoxyphenol, 2,2',6,6'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3-(3,5-di-tert-butyl -4-hydroxyphenyl) stearyl propionate, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,4,6-tris(3',5' -Di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4- Tributylcatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, thioglycolic acid, dimethyl yellow Original acid sulfide, diisopropyl xanthogen acid disulfide, 2,6-di-t-butyl-p-cresol, 4,4'-butylene bis(6-t-butyl-m-cresol ), 4,4'-thiobis(6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, 2-hydroxy-1 , 4-naphthoquinone, etc.
分子量調整劑可單獨使用,也可組合使用兩種以上。分子量調整劑中,若為萘醌系分子量調整劑,則就顯現優異的保存穩定性的方面而言較佳。The molecular weight modifier may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred in terms of showing excellent storage stability.
分子量調整劑中,若為具有酚性羥基的2-羥基-1,4-萘醌,則就保存穩定性的觀點而言更佳。Among the molecular weight modifiers, if it is 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group, it is more preferable from the viewpoint of storage stability.
1-6-10.紫外線吸收劑 就進一步提高所形成的透明膜的劣化抑制能力的觀點而言,本發明的熱硬化性組成物也可含有紫外線吸收劑。1-6-10. Ultraviolet absorber From the viewpoint of further improving the deterioration suppression ability of the formed transparent film, the thermosetting composition of the present invention may contain an ultraviolet absorber.
紫外線吸收劑的具體例為:帝奴彬(TINUVIN)P、帝奴彬(TINUVIN)120、帝奴彬(TINUVIN)144、帝奴彬(TINUVIN)213、帝奴彬(TINUVIN)234、帝奴彬(TINUVIN)326、帝奴彬(TINUVIN)571、帝奴彬(TINUVIN)765(均為商品名;日本巴斯夫(BASF Japan)股份有限公司)。Specific examples of UV absorbers are: TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINU (TINUVIN) 326, TINUVIN 571, TINUVIN 765 (all trade names; BASF Japan Co., Ltd.).
相對於熱硬化性組成物總量,添加0.01重量份~10重量份的紫外線吸收劑而使用。The ultraviolet absorber is used by adding 0.01 to 10 parts by weight to the total amount of the thermosetting composition.
1-6-11.防凝聚劑 就不使具有聚合性雙鍵的聚酯醯胺酸(A)或環氧化合物(B)與溶劑融合、防止凝聚的觀點而言,本發明的熱硬化性組成物也可含有防凝聚劑。1-6-11. Anti-agglomerating agent The thermosetting composition of the present invention may contain an anti-agglomerating agent from the viewpoint of not fusing the polyester amidic acid (A) or epoxy compound (B) having a polymerizable double bond with a solvent and preventing aggregation.
防凝聚劑的具體例為:迪斯帕畢克(Disperbyk)-145、迪斯帕畢克(Disperbyk)-161、迪斯帕畢克(Disperbyk)-162、迪斯帕畢克(Disperbyk)-163、迪斯帕畢克(Disperbyk)-164、迪斯帕畢克(Disperbyk)-182、迪斯帕畢克(Disperbyk)-184、迪斯帕畢克(Disperbyk)-185、迪斯帕畢克(Disperbyk)-2163、迪斯帕畢克(Disperbyk)-2164、畢克(BYK)-220S、迪斯帕畢克(Disperbyk)-191、迪斯帕畢克(Disperbyk)-199、迪斯帕畢克(Disperbyk)-2015(均為商品名;日本畢克化學(BYK Chemie Japan)股份有限公司),FTX-218、福吉特(Ftergent)710FM、福吉特(Ftergent)710FS(均為商品名;尼奧斯(Neos)股份有限公司)、弗洛倫(Flowlen)G-600、弗洛倫(Flowlen)G-700(均為商品名;共榮社化學股份有限公司)。Specific examples of anti-agglomerating agents are: Disperbyk-145, Disperbyk-161, Disperbyk-162, Disperbyk- 163, Disperbyk-164, Disperbyk-182, Disperbyk-184, Disperbyk-185, Disperbyk (Disperbyk)-2163, Disperbyk-2164, BYK-220S, Disperbyk-191, Disperbyk-199, Dis Disperbyk-2015 (all trade names; BYK Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names ; Neos (Neos) Co., Ltd.), Floren (Flowlen) G-600, Floren (Flowlen) G-700 (both trade names; Gongrongshe Chemical Co., Ltd.).
相對於熱硬化性組成物總量,添加0.01重量份~10重量份的防凝聚劑而使用。The anti-agglomeration agent is used in an amount of 0.01 to 10 parts by weight relative to the total amount of the thermosetting composition.
1-6-12.熱交聯劑 就進一步提高耐熱性、耐化學品性、膜面內均勻性、可撓性、柔軟性、彈性的觀點而言,本發明的熱硬化性組成物也可含有熱交聯劑。1-6-12. Thermal crosslinking agent From the viewpoint of further improving heat resistance, chemical resistance, film surface uniformity, flexibility, flexibility, and elasticity, the thermosetting composition of the present invention may contain a thermal crosslinking agent.
熱交聯劑的具體例為:尼卡拉克(Nikalac)MW-30HM、尼卡拉克(Nikalac)MW-100LM、尼卡拉克(Nikalac)MX-270、尼卡拉克(Nikalac)MX-280、尼卡拉克(Nikalac)MX-290、尼卡拉克(Nikalac)MW-390、尼卡拉克(Nikalac)MW-750LM(均為商品名;三和化學股份有限公司)。Specific examples of the thermal cross-linking agent are: Nikalak (Nikalac) MW-30HM, Nikalak (MW) 100LM, Nikalak (MX) 270, Nikalak (MX-280), Nikalak (MX-280) Nikalac MX-290, Nikalac MW-390, Nikalac MW-750LM (all are trade names; Sanwa Chemical Co., Ltd.).
相對於熱硬化性組成物總量,添加0.1重量份~10重量份的熱交聯劑而使用。The thermal crosslinking agent is used in an amount of 0.1 to 10 parts by weight relative to the total amount of the thermosetting composition.
1-7.熱硬化性組成物的保存 本發明的熱硬化性組成物若在-30℃~25℃的範圍內保存,則組成物的經時穩定性變得良好而較佳。若保存溫度為-20℃~10℃,則也不會產生析出物而更佳。1-7. Preservation of thermosetting composition When the thermosetting composition of the present invention is stored in the range of -30°C to 25°C, the stability of the composition over time becomes good and preferable. If the storage temperature is -20°C to 10°C, no precipitates are generated, which is more preferable.
2.由熱硬化性組成物獲得的硬化膜 本發明的熱硬化性組成物可通過如下方式而獲得:視需要而選擇添加聚酯醯胺酸(A)、環狀醚化合物的聚合物(B)、陽離子聚合起始劑(C)、溶劑(D)、以及具有氧雜環丙基的化合物(b2)以外的環氧化合物、具有聚合性雙鍵的化合物、界面活性劑、密著性提高劑、抗氧化劑及其他添加劑,將這些化合物均勻地混合溶解。2. Hardened film obtained from thermosetting composition The thermosetting composition of the present invention can be obtained by optionally adding polyester amide (A), a polymer of a cyclic ether compound (B), a cationic polymerization initiator (C), a solvent (D), and epoxy compounds other than the oxetanyl compound (b2), compounds with polymerizable double bonds, surfactants, adhesion enhancers, antioxidants and other additives, to homogenize these compounds To mix and dissolve.
若將以所述方式製備的熱硬化性組成物(在無溶劑的固體狀態的情況下,溶解於溶劑中後)塗佈於基體表面上,通過例如加熱等而將溶劑除去,則可形成塗膜。對基體表面的熱硬化性組成物的塗佈可利用旋塗法、輥塗法、浸漬法及狹縫塗佈法等現有公知的方法形成塗膜。繼而,利用加熱板、或烘箱等將所述塗膜暫時煅燒。暫時煅燒條件視各成分的種類及調配比例而不同,通常在70℃~150℃下,若使用烘箱則為5分鐘~15分鐘,若使用加熱板則為1分鐘~5分鐘。其後,為了使塗膜硬化而進行正式煅燒。正式煅燒條件視各成分的種類及調配比例而不同,通常在180℃~250℃、較佳為200℃~250℃下,若使用烘箱則為30分鐘~90分鐘,若使用加熱板則為5分鐘~30分鐘,可通過進行加熱處理而獲得硬化膜。If the thermosetting composition prepared in the above manner (in the case of a solvent-free solid state, after being dissolved in a solvent) is applied to the surface of the substrate, and the solvent is removed by, for example, heating, the coating can be formed membrane. The coating of the thermosetting composition on the surface of the substrate can be formed by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. Then, the coating film is temporarily calcined using a hot plate, an oven, or the like. The temporary calcination conditions vary depending on the types of ingredients and the mixing ratio. Usually, at 70°C to 150°C, if an oven is used, it is 5 minutes to 15 minutes, and if a hot plate is used, it is 1 minute to 5 minutes. Thereafter, in order to harden the coating film, the main calcination is performed. The formal calcination conditions vary depending on the type of ingredients and the mixing ratio, usually at 180 ℃ ~ 250 ℃, preferably 200 ℃ ~ 250 ℃, if you use an oven, it is 30 minutes to 90 minutes, if you use a hot plate, it is 5 From minutes to 30 minutes, a cured film can be obtained by performing heat treatment.
以所述方式獲得的硬化膜在加熱時,1)聚酯醯胺酸的聚醯胺酸部分脫水環化而形成醯亞胺鍵,2)聚酯醯胺酸的羧酸與環氧化合物反應而高分子量化,及3)環氧化合物硬化而高分子量化,因此非常強韌,且透明性、耐熱性、耐化學品性、平坦性、密著性優異。另外,就相同的理由而言,也期待耐光性、耐濺鍍性、耐劃傷性、塗佈性優異。因此,本發明的硬化膜若用作彩色濾光片用的保護膜,則有效,可使用所述彩色濾光片來製造液晶顯示元件或固體攝像元件。另外,除彩色濾光片用的保護膜以外,本發明的硬化膜若用作形成於薄膜電晶體(Thin Film Transistor,TFT)與透明電極間的透明絕緣膜或形成於透明電極與配向膜間的透明絕緣膜,則有效。進而,本發明的硬化膜即便用作發光二極管(Light Emitting Diode,LED)發光體的保護膜,也有效。 [實施例]When the cured film obtained in the above manner is heated, 1) the polyamic acid of the polyester amide acid is partially dehydrated and cyclized to form an amide imine bond, and 2) the carboxylic acid of the polyester amide acid reacts with the epoxy compound The high molecular weight, and 3) the epoxy compound is hardened and the high molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness and adhesion. In addition, for the same reason, it is also expected to be excellent in light resistance, sputtering resistance, scratch resistance, and coating properties. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and the color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. In addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode or formed between a transparent electrode and an alignment film The transparent insulating film is effective. Furthermore, the cured film of the present invention is effective even as a protective film for a light emitting diode (LED) light emitter. [Example]
繼而,通過合成例、實施例及比較例對本發明加以具體的說明,但本發明並不受這些實施例的任何限定。Next, the present invention will be specifically described by the synthesis examples, examples, and comparative examples, but the present invention is not limited by these examples.
合成例、實施例及比較例中所使用的化合物的略稱表示以下原料。The abbreviations of the compounds used in Synthesis Examples, Examples, and Comparative Examples indicate the following raw materials.
[四羧酸酐] ODPA:3,3',4,4'-二苯基醚四羧酸二酐 BT-100:1,2,3,4-丁烷四羧酸二酐 理家德(Rikacid)BT-100(商品名;新日本理化股份有限公司)[Tetracarboxylic anhydride] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride BT-100: 1,2,3,4-butanetetracarboxylic dianhydride Rikacid BT-100 (trade name; New Japan Physical and Chemical Co., Ltd.)
[二胺] DDS:3,3'-二胺基二苯基碸[Diamine] DDS: 3,3'-diaminodiphenyl sulfone
[多元羥基化合物] Bis-A-2EOH:4,4'-亞異丙基雙(2-苯氧基乙醇) 70PA:環氧酯 70PA(商品名;共榮社化學股份有限公司)[Polyhydroxy compound] Bis-A-2EOH: 4,4'-isopropylidenebis(2-phenoxyethanol) 70PA: Epoxy ester 70PA (trade name; Kyoeisha Chemical Co., Ltd.)
[苯乙烯-馬來酸酐共聚物] SMA1000P(商品名;川原油化股份有限公司)[Styrene-maleic anhydride copolymer] SMA1000P (trade name; Sichuan Crude Oil Chemical Co., Ltd.)
[環狀醚化合物] OXE-30:甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯 OXE-10:丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯 GMA:甲基丙烯酸縮水甘油酯[Cyclic ether compound] OXE-30: (3-ethyloxetan-3-yl) methyl methacrylate OXE-10: (3-ethyloxetane-3-yl) methyl acrylate GMA: glycidyl methacrylate
[(b2)以外的環氧化合物] E1:特克莫(TECHMORE)VG3101L(商品名;普林泰科(Printec)股份有限公司)[Epoxy compounds other than (b2)] E1: TECHMORE VG3101L (trade name; Printec Co., Ltd.)
[熱聚合起始劑] V-601:二甲基2,2'-偶氮雙(2-甲基丙酸酯)[Thermal polymerization initiator] V-601: Dimethyl 2,2'-azobis(2-methylpropionate)
[陽離子聚合起始劑] CPI-100P(商品名;桑亞普羅(Sanapro)股份有限公司) CPI-200K(商品名;桑亞普羅(Sanapro)股份有限公司) 豔佳固(Irgacure)250(商品名;巴斯夫(BASF)歐洲公司)[Cationic polymerization initiator] CPI-100P (trade name; Sanapro Co., Ltd.) CPI-200K (trade name; Sanapro Co., Ltd.) Irgacure 250 (trade name; BASF Europe)
[硬化劑] TMA:偏苯三甲酸酐 UC-3900:阿魯豐(ARUFON)UC-3900(商品名;東亞合成股份有限公司)[hardener] TMA: trimellitic anhydride UC-3900: ARUFON UC-3900 (trade name; East Asia Synthetic Co., Ltd.)
[添加劑] S510:薩拉艾斯(Sila-Ace)S510(商品名;捷恩智(JNC)股份有限公司);密著性提高劑(偶合劑) AO-60:艾迪科斯塔波(ADK STAB)AO-60(商品名;艾迪科(ADEKA)股份有限公司);抗氧化劑 DS-21:美佳法(Megafac)DS-21(商品名;迪愛生(DIC)股份有限公司);界面活性劑[additive] S510: Sila-Ace S510 (trade name; JNC Co., Ltd.); adhesion improver (coupling agent) AO-60: ADK STAB AO-60 (trade name; ADEKA Co., Ltd.); antioxidant DS-21: Megafac DS-21 (trade name; DIC) Co., Ltd.; surfactant
[溶劑] MMP:3-甲氧基丙酸甲酯 PGMEA:丙二醇單甲醚乙酸酯[Solvent] MMP: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate
首先,如下所示地合成作為四羧酸二酐、二胺、單羥基化合物、多元羥基化合物等的反應產物的聚酯醯胺酸溶液(合成例1~合成例7)。First, a polyester amide acid solution (Synthesis Example 1 to Synthesis Example 7) as a reaction product of tetracarboxylic dianhydride, diamine, monohydroxy compound, polyhydroxy compound, or the like is synthesized as follows.
[合成例1]聚酯醯胺酸(A1)的合成 在帶有攪拌機的四口燒瓶中,以下述重量裝入進行了脫水純化的MMP、ODPA、1,4-丁二醇、苄醇,在乾燥氮氣流下且在125℃下進行2小時攪拌(合成第一階段)。 MMP 49.00 g ODPA 20.36 g 1,4-丁二醇 3.55 g 苄醇 2.84 g[Synthesis Example 1] Synthesis of polyester amide acid (A1) In a four-necked flask equipped with a stirrer, dehydrated and purified MMP, ODPA, 1,4-butanediol, and benzyl alcohol were charged at the following weights, and the mixture was stirred at 125°C for 2 hours under a stream of dry nitrogen (synthesis The first stage). MMP 49.00 g ODPA 20.36 g 1,4-butanediol 3.55 g Benzyl alcohol 2.84 g
其後,將反應後的溶液冷卻至室溫,以下述重量投入DDS、MMP,在20℃~30℃下進行2小時攪拌後,在125℃下進行1小時攪拌(合成第二階段)。 DDS 3.26 g MMP 21.00 g [Z/Y=3.0、(Y+Z)/X=0.8]Thereafter, the solution after the reaction was cooled to room temperature, and DDS and MMP were added at the following weights, and the mixture was stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 3.26 g MMP 21.00 g [Z/Y=3.0, (Y+Z)/X=0.8]
將溶液冷卻至室溫,獲得淡黃色透明的聚酯醯胺酸(A1)的30重量%溶液。對溶液的一部分進行取樣,利用GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,所獲得的聚酯醯胺酸(A1)的重量平均分子量為4,200。The solution was cooled to room temperature to obtain a 30% by weight solution of light yellow transparent polyester amide acid (A1). A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amide acid (A1) was 4,200.
[合成例2]聚酯醯胺酸(A2)的合成 在帶有攪拌機的四口燒瓶中,以下述重量依序裝入進行了脫水純化的PGMEA、BT-100、SMA1000P、1,4-丁二醇、苄醇,在乾燥氮氣流下且在125℃下進行2小時攪拌(合成第一階段)。 PGMEA 53.49 g BT-100 3.83 g SMA1000P 18.23 g 1,4-丁二醇 1.16 g 苄醇 5.57 g[Synthesis Example 2] Synthesis of polyester amide acid (A2) In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol were sequentially charged at the following weights, under a stream of dry nitrogen and at 125°C Stir for 2 hours (the first stage of synthesis). PGMEA 53.49 g BT-100 3.83 g SMA1000P 18.23 g 1,4-butanediol 1.16 g Benzyl alcohol 5.57 g
其後,將反應後的溶液冷卻至室溫,以下述重量投入DDS、PGMEA,在20℃~30℃下進行2小時攪拌後,在125℃下進行1小時攪拌(合成第二階段)。 DDS 1.20 g PGMEA 16.51 g [Z/Y=2.7、(Y+Z)/X=0.9]Thereafter, the solution after the reaction was cooled to room temperature, and DDS and PGMEA were added at the following weights, stirred at 20°C to 30°C for 2 hours, and then stirred at 125°C for 1 hour (second stage of synthesis). DDS 1.20 g PGMEA 16.51 g [Z/Y=2.7, (Y+Z)/X=0.9]
將溶液冷卻至室溫,獲得淡黃色透明的聚酯醯胺酸(A2)的30重量%溶液。對溶液的一部分進行取樣,利用GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,所獲得的聚酯醯胺酸(A2)的重量平均分子量為10,000。The solution was cooled to room temperature to obtain a 30% by weight solution of light yellow transparent polyester amide acid (A2). A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polyester amide acid (A2) was 10,000.
[合成例3~合成例7]聚酯醯胺酸(A3)~聚酯醯胺酸(A7)的合成 依據合成例1及合成例2的方法,以表1-1中記載的溫度、時間及比例(單位:g)使各成分反應,獲得聚酯醯胺酸(A3)~聚酯醯胺酸(A7)溶液。[Synthesis Example 3 to Synthesis Example 7] Synthesis of polyester amide acid (A3) to polyester amide acid (A7) According to the methods of Synthesis Example 1 and Synthesis Example 2, each component was reacted at the temperature, time and ratio (unit: g) described in Table 1-1 to obtain polyester amide acid (A3) to polyester amide acid (A3) A7) Solution.
表1-1
繼而,如下所示地合成環狀醚化合物的聚合物(B)的溶液(合成例8~合成例13)。Next, a solution of the polymer (B) of the cyclic ether compound (Synthesis Example 8 to Synthesis Example 13) was synthesized as follows.
[合成例8]環狀醚化合物的聚合物(B1)的合成 在帶有攪拌器的四口燒瓶中,以下述重量裝入作為聚合溶劑的進行了脫水純化的PGMEA、作為具有氧雜環丁基的化合物(b1)的OXE-30,進而以下述重量裝入作為聚合起始劑的V-601,在乾燥氮氣流下且在110℃下進行2小時攪拌。 PGMEA 31.50 g OXE-30 13.50 g V-601 1.35 g[Synthesis Example 8] Synthesis of polymer (B1) of cyclic ether compound In a four-necked flask equipped with a stirrer, dehydration-purified PGMEA as a polymerization solvent and OXE-30 as an oxetanyl-containing compound (b1) were charged with the following weight, and further charged with the following weight V-601 as a polymerization initiator was stirred at 110°C for 2 hours under a stream of dry nitrogen. PGMEA 31.50 g OXE-30 13.50 g V-601 1.35 g
將溶液冷卻至室溫,獲得環狀醚化合物的聚合物(B1)的30重量%溶液。對溶液的一部分進行取樣,利用GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,所獲得的環狀醚化合物的聚合物(B1)的重量平均分子量為7,200。The solution was cooled to room temperature to obtain a 30% by weight solution of the polymer (B1) of the cyclic ether compound. A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (B1) of the obtained cyclic ether compound was 7,200.
[合成例9]環狀醚化合物的聚合物(B2)的合成 在帶有攪拌器的四口燒瓶中,以下述重量裝入作為聚合溶劑的進行了脫水純化的PGMEA、作為具有氧雜環丁基的化合物(b1)的OXE-30、作為具有氧雜環丙基的化合物(b2)的GMA,進而以下述重量裝入作為聚合起始劑的V-601,在乾燥氮氣流下且在110℃下進行2小時攪拌。 PGMEA 31.500 g OXE-30 10.125 g GMA 3.375 g V-601 1.350 g[Synthesis Example 9] Synthesis of polymer (B2) of cyclic ether compound In a four-necked flask equipped with a stirrer, PGMEA as a polymerization solvent subjected to dehydration purification, OXE-30 as a compound (b1) having an oxetanyl group, and as a compound having an oxetane are charged at the following weights The GMA of the base compound (b2) was further charged into the polymerization initiator V-601 at the following weight, and stirred at 110° C. for 2 hours under a stream of dry nitrogen. PGMEA 31.500 g OXE-30 10.125 g GMA 3.375 g V-601 1.350 g
將溶液冷卻至室溫,獲得環狀醚化合物的聚合物(B2)的30重量%溶液。對溶液的一部分進行取樣,利用GPC分析(聚苯乙烯標準)測定重量平均分子量。其結果,所獲得的環狀醚化合物的聚合物(B2)的重量平均分子量為7,300。The solution was cooled to room temperature to obtain a 30% by weight solution of the polymer (B2) of the cyclic ether compound. A part of the solution was sampled, and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polymer (B2) of the obtained cyclic ether compound was 7,300.
[合成例10~合成例13]環狀醚化合物的聚合物(B3)~環狀醚化合物的聚合物(B6)的合成 依據合成例8及合成例9的方法,以表1-2中記載的溫度、時間及比例(單位:g)使各成分反應,獲得環狀醚化合物的聚合物(B3)~環狀醚化合物的聚合物(B6)溶液。[Synthesis Example 10 to Synthesis Example 13] Synthesis of cyclic ether compound polymer (B3) to cyclic ether compound polymer (B6) According to the methods of Synthesis Example 8 and Synthesis Example 9, each component was reacted at the temperature, time and ratio (unit: g) described in Table 1-2 to obtain polymers (B3) to cyclic ether compounds of cyclic ether compounds Polymer (B6) solution.
表1-2
[實施例1] 對帶有攪拌翼的500 ml的可分離式燒瓶進行氮氣置換,在所述燒瓶中裝入100.0 g的作為聚酯醯胺酸(A)的合成例1中所獲得的聚酯醯胺酸(A1)溶液、120.0 g的環狀醚化合物的聚合物(B1)、3.6 g的作為陽離子聚合起始劑(C)的CPI-100P、3.7 g的作為密著性提高劑的S510、0.4 g的作為抗氧化劑的AO-60、54.9 g的作為溶劑(D)的進行了脫水純化的MMP及100.8 g的PGMEA,在室溫下進行3小時攪拌,使其均勻地溶解。[Example 1] A 500 ml separable flask with a stirring wing was replaced with nitrogen, and the flask was charged with 100.0 g of the polyester amide acid obtained in Synthesis Example 1 as polyester amide acid (A) ( A1) Solution, 120.0 g of cyclic ether compound polymer (B1), 3.6 g of CPI-100P as a cationic polymerization initiator (C), 3.7 g of S510 as an adhesion improver, 0.4 g of AO-60 as an antioxidant, 54.9 g of dehydrated MMP as a solvent (D), and 100.8 g of PGMEA were stirred at room temperature for 3 hours to uniformly dissolve.
繼而,投入1.0 g的作為界面活性劑的美佳法(Megafac)DS-21(商品名;迪愛生(DIC)股份有限公司),在室溫下進行1小時攪拌,利用薄膜過濾器(孔徑0.2 μm)進行過濾而製備熱硬化性組成物。Then, 1.0 g of Megafac DS-21 (trade name; DIC) Co., Ltd. was added as a surfactant, and stirred at room temperature for 1 hour, using a membrane filter (pore size 0.2 μm ) It is filtered to prepare a thermosetting composition.
[屏障性的評價方法] 當利用紫外可見近紅外分光光度計(商品名;V-670,日本分光股份有限公司)進行測定時,以300 rpm歷時10秒將熱硬化性組成物旋塗於在560 nm附近具有吸收且具有包含R、G、B的像素的無硬化膜的彩色濾光片基板上,在90℃的加熱板上預烘烤2分鐘。繼而,在烘箱中以230℃後烘烤30分鐘,獲得保護膜的平均膜厚為2.0 μm的帶有硬化膜的彩色濾光片基板。[Barrier evaluation method] When measuring with a UV-Vis near-infrared spectrophotometer (trade name; V-670, Japan Spectroscopy Co., Ltd.), the thermosetting composition was spin-coated at 300 rpm for 10 seconds to have absorption near 560 nm and have On the color filter substrate including no R, G, and B pixels without a hardened film, pre-bake on a hot plate at 90°C for 2 minutes. Then, post-bake at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having a protective film with an average film thickness of 2.0 μm.
繼而,在切成為10 cm見方的帶有硬化膜的彩色濾光片基板上滴加0.5 mL的1-甲基-2-吡咯烷酮,將切成為9 cm見方的玻璃(以下稱為蓋玻璃)靜置於帶有硬化膜的彩色濾光片基板上,使用加熱板以180℃進行5分鐘加熱。加熱結束後,去除蓋玻璃,利用5 mL的1-甲基-2-吡咯烷酮來清洗蓋玻璃及帶有硬化膜的彩色濾光片基板,將清洗液移至10 mL的量瓶中。在加入有清洗液的量筒中添加1-甲基-2-吡咯烷酮而定容至10 mL,將所混合的溶液作為帶有硬化膜的彩色濾光片基板的溶出液。其後,利用所述紫外可見近紅外分光光度計,將1-甲基-2-吡咯烷酮作為參照樣品,測定溶出液的透射率。根據所測定的結果,將560 nm的透射率為90%以上的情況設為○,將未滿90%的情況設為×。Then, 0.5 mL of 1-methyl-2-pyrrolidone was added dropwise to the color filter substrate with a cured film cut into a 10 cm square, and the glass cut into a 9 cm square (hereinafter referred to as cover glass) was statically placed. It was placed on a color filter substrate with a cured film, and heated at 180°C for 5 minutes using a hot plate. After the heating is completed, the cover glass is removed, and 5 mL of 1-methyl-2-pyrrolidone is used to clean the cover glass and the color filter substrate with a hardened film, and the cleaning solution is transferred to a 10 mL measuring flask. 1-Methyl-2-pyrrolidone was added to a graduated cylinder with a cleaning solution and the volume was adjusted to 10 mL, and the mixed solution was used as the eluent of the color filter substrate with a hardened film. Thereafter, using the ultraviolet-visible-near infrared spectrophotometer, using 1-methyl-2-pyrrolidone as a reference sample, the transmittance of the eluate was measured. Based on the measured results, the case where the transmittance at 560 nm is 90% or more is set to ○, and the case where less than 90% is set to x.
[平坦性的評價方法] 以300 rpm歷時10秒將熱硬化性組成物旋塗於預先使用微細形狀測定裝置(商品名;P-17,科磊(KLA TENCOR)股份有限公司)測定了表面階差的具有包含R、G、B的像素的無硬化膜的彩色濾光片基板上,在90℃的加熱板上預烘烤2分鐘。繼而,在烘箱中以230℃後烘烤30分鐘,獲得保護膜的平均膜厚為2.0 μm的帶有硬化膜的彩色濾光片基板。其後,對所獲得的帶有硬化膜的彩色濾光片基板測定表面階差。[Evaluation method of flatness] The thermosetting composition was spin-coated at 300 rpm for 10 seconds on a micro-shape measuring device (trade name; P-17, KLA TENCOR) Co., Ltd. in advance. The surface level difference was measured with R and G. And B, the non-cured color filter substrate of the pixel is pre-baked on a hot plate at 90°C for 2 minutes. Then, post-bake at 230° C. for 30 minutes in an oven to obtain a color filter substrate with a cured film having a protective film with an average film thickness of 2.0 μm. After that, the obtained color filter substrate with a cured film was measured for the surface level difference.
根據無硬化膜的彩色濾光片基板及帶有硬化膜的彩色濾光片基板的表面階差的最大值(以下略記為“最大階差”),並使用下述計算式來算出平坦化率。將平坦化率為85%以上的情況評價為平坦性○,將未滿85%的情況評價為平坦性×。再者,無硬化膜的彩色濾光片基板使用最大階差為1.5 μm者。 平坦化率=[(無硬化膜的彩色濾光片基板的最大階差-帶有硬化膜的彩色濾光片基板的最大階差)/(無硬化膜的彩色濾光片基板的最大階差)]×100%Calculate the flattening rate based on the maximum value of the surface level difference of the color filter substrate without a cured film and the color filter substrate with a cured film (hereinafter abbreviated as "maximum level difference"), and use the following calculation formula . The case where the flattening rate was 85% or more was evaluated as flatness ○, and the case where less than 85% was evaluated as flatness ×. In addition, the color filter substrate without a cured film has a maximum step difference of 1.5 μm. Flattening rate = [(Maximum step difference of color filter substrate without cured film-Maximum step difference of color filter substrate with cured film)/(Maximum step difference of color filter substrate without cured film )]×100%
[密著性的評價方法] 繼而,以800 rpm歷時10秒將熱硬化性組成物旋塗於玻璃基板上,在90℃的加熱板上預烘烤2分鐘。繼而,在烘箱中以230℃後烘烤30分鐘,獲得保護膜的膜厚為1.0 μm的帶有硬化膜的玻璃基板。依據JIS K5600-5-6:1999對所獲得的帶有硬化膜的玻璃基板進行試驗。將試驗結果示出分類0~分類2的密著性的情況設為○,將示出分類3~分類5的密著性的情況設為×。[Evaluation method of adhesion] Then, the thermosetting composition was spin-coated on the glass substrate at 800 rpm for 10 seconds, and prebaked on a hot plate at 90°C for 2 minutes. Then, after baking at 230° C. for 30 minutes in an oven, a glass substrate with a cured film having a protective film thickness of 1.0 μm was obtained. The obtained glass substrate with a cured film was tested according to JIS K5600-5-6:1999. The case where the test result shows the adhesion of category 0 to category 2 is ○, and the case of showing the adhesion of categories 3 to 5 is ×.
[實施例2~實施例16] 依據實施例1的方法,以表2-1~表2-3中記載的比例(單位:g)將各成分混合溶解而獲得熱硬化性組成物。[Example 2 to Example 16] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 2-1 to Table 2-3 to obtain a thermosetting composition.
表2-1
表2-2
表2-3
[比較例1~比較例5] 依據實施例1的方法,以表3的比例(單位:g)將各成分混合溶解而獲得熱硬化性組成物。[Comparative Example 1 to Comparative Example 5] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 3 to obtain a thermosetting composition.
表3
根據表2-1~表2-3所示的結果而明確得知:實施例1~實施例16的使用了陽離子聚合起始劑的硬化膜的屏障性優異,在平坦性及密著性方面取得平衡。From the results shown in Tables 2-1 to 2-3, it is clear that the cured films using the cationic polymerization initiators of Examples 1 to 16 are excellent in barrier properties, and have flatness and adhesion Get a balance.
表3中記載的比較例1、比較例3中,使用偏苯三甲酸酐(Trimellitic Anhydride,TMA)作為硬化劑,其屏障性良好。另一方面,比較例3的平坦性差,比較例1除平坦性以外,密著性也不良。比較例2、比較例4及比較例5雖然密著性良好,但完全未顯現屏障性。In Comparative Example 1 and Comparative Example 3 described in Table 3, trimellitic anhydride (TMA) was used as a hardener, and its barrier properties were good. On the other hand, Comparative Example 3 has poor flatness, and Comparative Example 1 has poor adhesion in addition to flatness. Although Comparative Example 2, Comparative Example 4, and Comparative Example 5 had good adhesion, they did not exhibit barrier properties at all.
如上所述,僅在將聚酯醯胺酸(A)、環狀醚化合物的聚合物(B)及陽離子聚合起始劑(C)用作必需的成分的情況下,可滿足所有特性。 [產業上的可利用性]As described above, only when the polyester amide acid (A), the polymer (B) of the cyclic ether compound, and the cationic polymerization initiator (C) are used as essential components, all characteristics can be satisfied. [Industry availability]
由本發明的熱硬化性組成物獲得的硬化膜的屏障性高、平坦性高,就所述方面而言,可用作彩色濾光片、LED發光元件及光接收元件等各種光學材料等的保護膜,以及形成於TFT與透明電極間及透明電極與配向膜間的絕緣膜。The cured film obtained from the thermosetting composition of the present invention has high barrier properties and high flatness, and can be used as a protection for various optical materials such as color filters, LED light-emitting elements, and light-receiving elements. Film, and an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.
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