TW202110950A - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor - Google Patents
Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and polyimide or polyimide precursor Download PDFInfo
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Abstract
Description
本發明係有關一種硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法、半導體器件及聚醯亞胺或聚醯亞胺前驅物。The present invention relates to a curable resin composition, a cured film, a laminate, a method for manufacturing a cured film, a semiconductor device, and a polyimide or polyimide precursor.
聚醯亞胺的耐熱性及絕緣性優異,因此適用於各種用途。作為上述用途並無特別限定,若以實際安裝用半導體器件為例,則可列舉作為絕緣膜或密封材料的素材或保護膜的利用。又,亦用作撓性基板的基底膜或覆蓋膜(COVERLAY)等。Polyimide is excellent in heat resistance and insulation, so it is suitable for various applications. The use is not particularly limited, and if a semiconductor device for actual mounting is taken as an example, the use as a material of an insulating film or a sealing material or a protective film can be cited. It is also used as a base film or cover film (COVERLAY) for flexible substrates.
例如在上述用途中,聚醯亞胺有時以含有聚醯亞胺之硬化性樹脂組成物的形態使用,有時還以含有聚醯亞胺前驅物之硬化性樹脂組成物的形態使用。上述前驅物例如藉由加熱等環化而成為聚醯亞胺。 該等硬化性樹脂組成物能夠藉由公知的塗佈方法等而適用於基材等,因此,可以說例如所適用之硬化性樹脂組成物的形狀、大小、適用位置等設計的自由度高等製造上的適應性優異。 從不僅是聚醯亞胺所具有之高性能,而且這種製造上的適應性亦優異之觀點考慮,越來越期待拓展含有選自包括聚醯亞胺、聚醯亞胺前驅物之群組中之至少一種樹脂之硬化性樹脂組成物在產業上的應用。For example, in the above-mentioned applications, polyimine is sometimes used in the form of a curable resin composition containing polyimine, and sometimes is used in the form of a curable resin composition containing a polyimide precursor. The aforementioned precursor is cyclized by heating or the like to become polyimide. These curable resin compositions can be applied to substrates and the like by known coating methods. Therefore, it can be said that, for example, the shape, size, and application position of the applied curable resin composition can be manufactured with high degree of freedom in design. The adaptability is excellent. Considering not only the high performance of polyimide, but also the excellent adaptability in manufacturing, it is increasingly expected to expand the group containing polyimine and polyimine precursors. Industrial application of a curable resin composition of at least one of the resins.
例如,專利文獻1中記載有具有特定的聚合性基之結構的硬化性聚醯亞胺。For example,
[專利文獻1]國際公開第2018/237377號[Patent Document 1] International Publication No. 2018/237377
在含有選自包括聚醯亞胺或聚醯亞胺前驅物之群組中之至少一種樹脂之硬化性樹脂組成物中,希望提供一種組成物的塗佈性優異之硬化性樹脂組成物。In a curable resin composition containing at least one resin selected from the group consisting of polyimine or polyimide precursors, it is desirable to provide a curable resin composition having excellent coating properties of the composition.
本發明的一實施態樣的目的為,提供一種塗佈性優異之硬化性樹脂組成物、將上述硬化性樹脂組成物硬化而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。 又,本發明的另一實施態樣的目的為,提供一種新型的聚醯亞胺或聚醯亞胺前驅物。An object of one embodiment of the present invention is to provide a curable resin composition with excellent coatability, a cured film formed by curing the curable resin composition, a laminate including the cured film, and a composite of the cured film Manufacturing method and semiconductor device including the above-mentioned cured film or the above-mentioned laminate. In addition, the purpose of another aspect of the present invention is to provide a novel polyimide or polyimine precursor.
以下,記載本發明的代表性實施態樣的例子。 <1>一種硬化性樹脂組成物,其係含有: 具有聚伸烷氧基及聚合性基且選自包括聚醯亞胺及聚醯亞胺前驅物之群組中之至少一種樹脂;聚合起始劑; 聚合性化合物;及 溶劑。 <2>如<1>所述之硬化性樹脂組成物,其中作為具有上述聚伸烷氧基及上述聚合性基之結構包含以下述式(1-1)表示之結構。 [化學式1] 式(1-1)中,R1 分別獨立地表示氫原子或烷基,Z1 表示包含聚合性基之基團,n表示2以上的整數,m表示2以上的整數,*表示與其他結構的鍵結部位。 <3>如<2>所述之硬化性樹脂組成物,其中上述Z1 作為上述聚合性基包含選自包括乙烯性不飽和基、環狀醚基及羥甲基之群組中之至少一種基團。 <4>如<2>或<3>所述之硬化性樹脂組成物,其中上述樹脂作為包含以上述式(1-1)表示之結構之結構,包含以下述式(1-2)表示之結構。 [化學式2] 式(1-2)中,L1 表示b+2價連接基,X2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,L2 表示單鍵或a+1價連接基,X1 表示以上述式(1-1)表示之結構,a表示1以上的整數,b表示1以上的整數,存在複數個X2 、L2 、X1 或a時,複數個X2 、L2 、X1 或a可以相同,亦可以不同。 <5>如<2>至<4>之任一項所述之硬化性樹脂組成物,其中作為包含以上述式(1-1)表示之結構之重複單元,包含以下述式(1-3)表示之重複單元。 [化學式3] 式(1-3)中,L1 表示b+2價連接基,X2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,L2 表示單鍵或a+1價連接基,X1 表示以上述式(1-1)表示之結構,a表示1以上的整數,b表示1以上的整數,L4 表示以下述式(L4-1)或式(L4-2)表示之結構,存在複數個X2 、L2 、X1 或a時,複數個X2 、L2 、X1 或a可以相同,亦可以不同。 [化學式4] 式(L4-1)或式(L4-2)中,R115 表示4價有機基,A1 及A2 分別獨立地表示氧原子或-NH-,R113 及R114 分別獨立地表示氫原子或1價有機基。 <6>如<4>或<5>所述之硬化性樹脂組成物,其中上述L1 包含選自包括以下述式(A-1)~(A-5)表示之結構之群組中之至少一種所表示之結構。 [化學式5] 式(A-1)~(A-5)中,RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基、鹵素原子或與上述式(1-2)或上述式(1-3)中的X2 的鍵結部位,LA31 及LA41 分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基,RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中,b個分別為與上述式(1-2)或上述式(1-3)中的X2 的鍵結部位,*分別獨立地表示與其他結構的鍵結部位。 <7>如<1>至<6>之任一項所述之硬化性樹脂組成物,其係用於形成再配線層用層間絕緣膜。 <8>一種硬化膜,其係將<1>至<7>之任一項所述之硬化性樹脂組成物硬化而成。 <9>一種積層體,其係具有兩層以上的<8>所述之硬化膜,且在硬化膜之間具有金屬層。 <10>一種硬化膜的製造方法,其係包括將<1>至<7>之任一項所述之硬化性樹脂組成物適用於基材而形成膜之膜形成步驟。 <11>如<10>所述之硬化膜的製造方法,其係包括將上述膜曝光之曝光步驟及將上述膜顯影之顯影步驟。 <12>如<10>或<11>所述之硬化膜的製造方法,其係包括在50~450℃下加熱上述膜之步驟。 <13>一種半導體器件,其係包含<8>所述之硬化膜或<9>所述之積層體。 <14>一種聚醯亞胺或聚醯亞胺前驅物,其係包含以下述式(1-1)表示之結構。 [化學式6] 式(1-1)中,R1 分別獨立地表示氫原子或烷基,Z1 表示包含聚合性基之基團,n表示2以上的整數,m表示2以上的整數,*表示與其他結構的鍵結部位。 [發明效果]Hereinafter, examples of representative embodiments of the present invention will be described. <1> A curable resin composition containing: at least one resin having a polyalkyleneoxy group and a polymerizable group selected from the group consisting of polyimine and polyimide precursors; polymerized Starting agent; polymerizable compound; and solvent. <2> The curable resin composition according to <1>, in which the structure having the polyalkoxyl group and the polymerizable group includes a structure represented by the following formula (1-1). [Chemical formula 1] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group, Z 1 represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site. <3> The curable resin composition according to <2>, wherein the Z 1 as the polymerizable group includes at least one selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group Group. <4> The curable resin composition as described in <2> or <3>, wherein the resin includes a structure represented by the above formula (1-1) as a structure represented by the following formula (1-2) structure. [Chemical formula 2] In formula (1-2), L 1 represents a b+2 valent linking group, X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L 2 represents a single bond or a+1 valence Linking group, X 1 represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, when there are multiple X 2 , L 2 , X 1 or a, multiple X 2 , L 2 , X 1 or a may be the same or different. <5> The curable resin composition according to any one of <2> to <4>, which includes the following formula (1-3) as a repeating unit including the structure represented by the above formula (1-1) ) Represents the repeating unit. [Chemical formula 3] In formula (1-3), L 1 represents a b+2 valent linking group, X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L 2 represents a single bond or a+1 valence Linking group, X 1 represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L 4 represents the following formula (L4-1) or formula (L4-2) In the indicated structure, when there are a plurality of X 2 , L 2 , X 1 or a, the plurality of X 2 , L 2 , X 1 or a may be the same or different. [Chemical formula 4] In formula (L4-1) or formula (L4-2), R 115 represents a tetravalent organic group, A 1 and A 2 each independently represent an oxygen atom or -NH-, and R 113 and R 114 each independently represent a hydrogen atom Or monovalent organic group. <6> The curable resin composition as described in <4> or <5>, wherein the L 1 includes one selected from the group including the structures represented by the following formulas (A-1) to (A-5) At least one of the indicated structures. [Chemical formula 5] In formulas (A-1) to (A-5), R A11 to R A14 , R A21 to R A24 , R A31 to R A38 , R A41 to R A48 and R A51 to R A58 each independently represent a hydrogen atom, An alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, a halogen atom or the bonding site with X 2 in the above formula (1-2) or the above formula (1-3), L A31 and L A41 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group, or a halogenated alkylene group, R A11 to R A14 , R A21 to R In A24 , R A31 to R A38 , R A41 to R A48, and R A51 to R A58 , b is the bonding site with X 2 in the above formula (1-2) or the above formula (1-3), respectively, * Each independently indicates the bonding site with other structures. <7> The curable resin composition according to any one of <1> to <6>, which is used for forming an interlayer insulating film for a rewiring layer. <8> A cured film obtained by curing the curable resin composition described in any one of <1> to <7>. <9> A laminate having two or more layers of the cured film described in <8>, and a metal layer between the cured films. <10> A method for producing a cured film, which includes a film forming step of applying the curable resin composition described in any one of <1> to <7> to a substrate to form a film. <11> The method for producing a cured film as described in <10>, which includes an exposure step of exposing the above-mentioned film and a development step of developing the above-mentioned film. <12> The method for producing a cured film as described in <10> or <11>, which includes the step of heating the film at 50 to 450°C. <13> A semiconductor device comprising the cured film described in <8> or the laminated body described in <9>. <14> A polyimine or polyimine precursor, which contains a structure represented by the following formula (1-1). [Chemical formula 6] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group, Z 1 represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site. [Effects of the invention]
依本發明的一實施態樣,提供一種塗佈性優異之硬化性樹脂組成物、將上述硬化性樹脂組成物硬化而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。 又,依本發明的另一實施態樣,提供新型的聚醯亞胺或聚醯亞胺前驅物。According to an embodiment of the present invention, there is provided a curable resin composition with excellent coatability, a cured film formed by curing the curable resin composition, a laminate including the cured film, and a method for manufacturing the cured film And a semiconductor device including the above-mentioned cured film or the above-mentioned laminate. Furthermore, according to another aspect of the present invention, a novel polyimide or polyimide precursor is provided.
以下,對本發明的主要實施形態進行說明。然而,本發明並不限於所明示之實施形態。 本說明書中,用“~”記號表示之數值範圍表示將記載於“~”的前後之數值分別作為下限值及上限值包括之範圍。 本說明書中,“步驟”這一用語不僅表示獨立之步驟,只要能夠實現該步驟的所預期之作用,則亦表示包括無法與其他步驟明確區分之步驟。 關於本說明書中的基團(原子團)的標記,未標註經取代及未經取代的標記同時包括不具有取代基的基團(原子團)和具有取代基之基團(原子團)。例如,“烷基”不僅包括不具有取代基的烷基(未經取代的烷基),而且還包括具有取代基之烷基(取代烷基)。 本說明書中,除非另有指明,則“曝光”不僅包括利用光之曝光,而且還包括利用電子束、離子束等粒子束之曝光。又,作為用於曝光之光,可列舉水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線(EUV光)、X射線、電子束等光化射線或放射線。 本說明書中,“(甲基)丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一個,“(甲基)丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一個,“(甲基)丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一個。 本說明書中,結構式中的Me表示甲基,Et表示乙基,Bu表示丁基,Ph表示苯基。 本說明書中,總固體成分是指組成物的所有成分中除了溶劑以外之成分的總質量。又,本說明書中,固體成分濃度為除了溶劑以外之其他成分相對於組成物的總質量之質量百分率。 本說明書中,除非另有指明,則重量平均分子量(Mw)及數量平均分子量(Mn)按照凝膠滲透層析法(GPC測量),並以聚苯乙烯換算值來定義。本說明書中,重量平均分子量(Mw)及數量平均分子量(Mn)例如能夠使用HLC-8220GPC(TOSOH CORPORATION製),並作為管住使用保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(TOSOH CORPORATION製)而求出。除非另有指明,則該等分子量係使用THF(四氫呋喃)為洗滌液進行測量者。又,除非另有指明,則GPC測量中的檢測係使用UV線(紫外線)的波長254nm檢測器者。 本說明書中,關於構成積層體之各層的位置關係,記載為“上”或“下”時,只要在所關注之複數層中成為基準之層的上側或下側存在其他層即可。亦即,在成為基準之層與上述其他層之間亦可以進一步夾有第3層或第3要素,而成為基準之層與上述其他層無需接觸。又,除非另有指明,則將在基材上堆疊層之方向稱為“上”,或存在感光層時,將從基材朝向感光層之方向稱為“上”,將其相反方向稱為“下”。另外,這種上下方向的設定為的是便於說明本說明書,在實際態樣中,本說明書中的“上”方向亦可以與鉛垂上朝向不同。 本說明書中,除非另有指明,則作為組成物中所包含之各成分,組成物亦可以包含符合該成分之兩種以上的化合物。又,除非另有指明,則組成物中的各成分的含量表示符合該成分之所有化合物的合計含量。 本說明書中,除非另有指明,則溫度為23℃,氣壓為101,325Pa(1氣壓)。 本說明書中,較佳的態樣的組合為更佳態樣。Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiment. In this specification, the numerical range indicated by the symbol "~" means the range that includes the numerical values described before and after the "~" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only refers to an independent step, but as long as it can achieve the expected effect of the step, it also refers to a step that cannot be clearly distinguished from other steps. Regarding the label of the group (atomic group) in this specification, the label not labeling substituted and unsubstituted includes both a group (atomic group) without a substituent and a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, unless otherwise specified, "exposure" includes not only exposure using light, but also exposure using electron beams, ion beams, and other particle beams. In addition, as the light used for exposure, actinic rays or radiation such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all the components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of other components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined in accordance with gel permeation chromatography (GPC measurement) and in terms of polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION), and protection columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000 can be used as the tube housing. , TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the washing solution. Also, unless otherwise specified, the detection in GPC measurement uses a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting the layered body is described as "upper" or "lower", it is only necessary that another layer exists on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, a third layer or a third element may be further sandwiched between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. Also, unless otherwise specified, the direction in which the layers are stacked on the substrate is called "up", or when a photosensitive layer is present, the direction from the substrate to the photosensitive layer is called "up", and the opposite direction is called "under". In addition, the setting of this up-down direction is to facilitate the description of this specification. In an actual aspect, the "up" direction in this specification may also be different from the vertical up-direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may also include two or more compounds that conform to the component. In addition, unless otherwise specified, the content of each component in the composition indicates the total content of all the compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C and the pressure is 101,325Pa (1 atmosphere). In this specification, a combination of preferred aspects is a better aspect.
(硬化性樹脂組成物) 本發明的硬化性樹脂組成物(以下,亦簡稱為“本發明的組成物”。)含有具有聚伸烷氧基及聚合性基且選自包括聚醯亞胺及聚醯亞胺前驅物之群組中之至少一種樹脂(以下,亦稱為“特定樹脂”。)、聚合起始劑、聚合性化合物及溶劑。 本發明的硬化性樹脂組成物進一步含有後述熱鹼產生劑或鎓鹽為較佳。尤其,特定樹脂為聚醯亞胺前驅物時,本發明的硬化性樹脂組成物進一步含有後述熱鹼產生劑或鎓鹽為較佳。(Curable resin composition) The curable resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention".) contains a polyalkyleneoxy group and a polymerizable group selected from the group consisting of polyimine and polyimide precursors At least one resin in the group (hereinafter, also referred to as "specific resin"), polymerization initiator, polymerizable compound, and solvent. The curable resin composition of the present invention preferably further contains a thermal base generator or an onium salt described later. In particular, when the specific resin is a polyimide precursor, the curable resin composition of the present invention preferably further contains a thermal base generator or an onium salt described later.
本發明的硬化性樹脂組成物的塗佈性優異。 本說明書中,組成物的塗佈性是指,塗佈乾燥後形成之塗佈膜中膜厚差小,並且由氣泡、凹凸所致之塗佈不均等缺陷少。 可獲得上述效果之機制尚不確定,但認為藉由特定樹脂包含聚伸烷氧基及聚合性基而特定樹脂對溶劑的溶解性優異。 認為藉由使用這種溶解性優異之特定樹脂,即使在將組成物塗佈乾燥時溶劑漸漸揮發之階段,特定樹脂亦不易析出,因此塗佈之後形成之塗佈膜中不易產生膜厚差,並且不易產生缺陷。 又,認為例如即使將本發明的硬化性樹脂組成物使用於具有段差之基材,亦容易獲得平坦的膜。 又,認為將塗佈膜硬化之後獲得之硬化膜中,剛直的聚醯亞胺結構和柔軟的聚伸烷氧基結構共存,因此硬化膜的強度(例如,斷裂伸長率)容易提高。The curable resin composition of the present invention is excellent in coatability. In this specification, the coating property of the composition means that the coating film formed after coating and drying has a small film thickness difference, and there are few defects such as uneven coating caused by bubbles and unevenness. The mechanism by which the above-mentioned effects can be obtained is uncertain, but it is thought that the specific resin has excellent solubility in solvents because the specific resin contains a polyalkoxyl group and a polymerizable group. It is believed that by using such a specific resin with excellent solubility, the specific resin is not easy to precipitate even when the solvent is gradually volatilized when the composition is coated and dried. Therefore, the coating film formed after coating is less likely to have a film thickness difference. And it is not easy to produce defects. In addition, it is considered that, for example, even if the curable resin composition of the present invention is used for a substrate having a step, a flat film can be easily obtained. In addition, it is considered that in the cured film obtained after curing the coating film, a rigid polyimide structure and a soft polyalkoxyl structure coexist, and therefore the strength (for example, elongation at break) of the cured film is likely to be improved.
其中,專利文獻1中,關於包含聚伸烷氧基之樹脂,既無記載亦無啟示。又,專利文獻1中的硬化性樹脂組成物中,存在塗佈性低的問題。Among them, in
<特定樹脂> 本發明的硬化性樹脂組成物含有特定樹脂。 特定樹脂具有聚伸烷氧基及聚合性基。 特定樹脂亦可以在主鏈上具有聚伸烷氧基,但從所獲得之硬化膜的膜強度的觀點考慮,在特定樹脂的側鏈上具有為較佳。 本說明書中,“主鏈”是指構成樹脂之高分子化合物的分子中相對最長的鍵結鏈,“側鏈”是指除此以外的鍵結鏈。 又,特定樹脂作為側鏈具備具有聚伸烷氧基及聚合性基之側鏈之為較佳。<Specific resins> The curable resin composition of the present invention contains a specific resin. The specific resin has a polyalkoxyl group and a polymerizable group. The specific resin may have a polyalkoxyl group in the main chain, but from the viewpoint of the film strength of the cured film obtained, it is preferable to have it in the side chain of the specific resin. In this specification, the "main chain" refers to the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" refers to other bonding chains. Moreover, it is preferable that the specific resin has a side chain which has a polyalkoxyl group and a polymerizable group as a side chain.
[聚伸烷氧基] 本發明中,聚伸烷氧基是指直接鍵結兩個以上伸烷氧基之基團。聚伸烷氧基中所包含之複數個伸烷氧基中的伸烷基可以分別相同,亦可以不同。 聚伸烷氧基包含伸烷基不同之複數種伸烷氧基時,聚伸烷氧基中的伸烷氧基的排列可以為無規排列,亦可以為具有嵌段之排列,還可以為具有交替等圖案之排列。 上述伸烷基的碳數(伸烷基具有取代基時,包含取代基的碳數)為2以上為較佳,2~50為更佳,2~30為更佳,2~10為進一步較佳,2~6為再進一步較佳,2~4為特佳,2或3為最佳。 又,上述伸烷基亦可以具有取代基。作為較佳的取代基,可列舉烷基、芳基、鹵素原子等。 又,聚伸烷氧基中所包含之伸烷氧基的數(聚伸烷氧基的重複數)為2~100為較佳,2~50為更佳,2~30為進一步較佳,2~10為特佳,3~10為最佳。 作為聚伸烷氧基,從兼顧溶劑溶解性及耐藥品性的觀點考慮,聚乙烯氧基、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個伸丙氧基鍵結之基團為較佳,聚乙烯氧基或聚伸丙氧基為更佳。上述複數個乙烯氧基與複數個伸丙氧基鍵結之基團中,乙烯氧基與伸丙氧基可以無規排列,亦可以形成嵌段而排列,還可以排列成交替等圖案狀。該等基團中的乙烯氧基等的重複數的較佳的態樣如上所述。[Polyoxyalkylene] In the present invention, the polyalkoxyl group refers to a group directly bonding two or more alkoxyl groups. The alkylene groups in the plurality of alkylene groups contained in the polyalkoxy group may be the same or different. When the polyalkoxyl group contains a plurality of different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, a block arrangement, or Arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, the carbon number including the substituent) is preferably 2 or more, more preferably 2-50, more preferably 2-30, and more preferably 2-10 Preferably, 2 to 6 are further preferred, 2 to 4 are particularly preferred, and 2 or 3 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of alkoxyl groups (the number of repetitions of polyalkoxyl groups) contained in the polyalkoxyl group is preferably from 2 to 100, more preferably from 2 to 50, and even more preferably from 2 to 30, 2-10 is particularly good, and 3-10 is the best. As a polyoxyethylene group, from the viewpoint of both solvent solubility and chemical resistance, polyvinyloxy, polypropoxy, polytrimethylene, polytetramethylene, or multiple ethyleneoxy groups are combined with Groups to which a plurality of propoxyl groups are bonded are preferred, and polyvinyloxy or polypropoxyl groups are more preferred. Among the groups in which the plural ethyleneoxy groups and the plural propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferable aspect of the repeating number of the vinyloxy group etc. in these groups is as mentioned above.
[聚合性基] 作為特定樹脂中所包含之聚合性基,包含乙烯性不飽和基、環狀醚基或羥甲基之基團為較佳,乙烯基、(甲基)烯丙基、(甲基)丙烯醯胺基、(甲基)丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基或羥甲基為更佳,(甲基)丙烯醯氧基、環氧基或羥甲基為更佳。 作為本發明的較佳的一態樣,可列舉特定樹脂中所包含之聚合性基直接鍵結於上述聚伸烷氧基的一個末端之態樣。亦即,特定樹脂具有上述聚伸烷氧基的一個末端與聚合性基所鍵結之側鏈為較佳。[Polymerizing group] As the polymerizable group contained in the specific resin, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferred, and a vinyl group, (meth)allyl group, (meth)acrylic acid group are preferred. Amino group, (meth)acryloxy group, maleimino group, vinyl phenyl group, epoxy group, oxetanyl group or methylol group are more preferable, (meth)acryloxy group Group, epoxy group or hydroxymethyl group are more preferable. As a preferable aspect of the present invention, an aspect in which a polymerizable group contained in a specific resin is directly bonded to one terminal of the above-mentioned polyalkyleneoxy group can be cited. That is, it is preferable that the specific resin has a side chain to which one end of the above-mentioned polyalkyleneoxy group is bonded to the polymerizable group.
[以式(1-1)表示之結構] 特定樹脂作為具有上述聚伸烷氧基及上述聚合性基之結構,包含以下述式(1-1)表示之結構為較佳。 特定樹脂包含複數個以下述式(1-1)表示之結構為較佳。特定樹脂包含複數個以式(1-1)表示之結構時,複數個以式(1-1)表示之結構可以相同,亦可以不同。 [化學式7] 式(1-1)中,R1 分別獨立地表示氫原子或烷基,Z1 表示包含聚合性基之基團,n表示2以上的整數,m表示2以上的整數,*表示與其他結構的鍵結部位。[Structure represented by formula (1-1)] As the structure having the above-mentioned polyalkoxyl group and the above-mentioned polymerizable group, the specific resin preferably includes a structure represented by the following formula (1-1). The specific resin preferably contains a plurality of structures represented by the following formula (1-1). When the specific resin contains a plurality of structures represented by formula (1-1), the plurality of structures represented by formula (1-1) may be the same or different. [Chemical formula 7] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group, Z 1 represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site.
-R1 - 式(1-1)中,R1 分別獨立地表示氫原子或碳數1~10的烷基為較佳,氫原子或碳數1~4的烷基為更佳,氫原子或甲基為進一步較佳。-R 1 -In the formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbons, preferably a hydrogen atom or an alkyl group having 1 to 4 carbons, and a hydrogen atom Or methyl is more preferred.
-Z1 - 式(1-1)中,Z1 表示包含聚合性基之基團。 Z1 作為上述聚合性基包含選自包括乙烯性不飽和基、環狀醚基及羥甲基之群組中之至少一種基團為較佳,包含乙烯基、(甲基)烯丙基、(甲基)丙烯醯胺基、(甲基)丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基或羥甲基為更佳,包含(甲基)丙烯醯氧基、環氧基或羥甲基為更佳。 又,Z1 為以下述式(Z-1)表示之基團為較佳。 [化學式8] 式(Z-1)中,L表示單鍵或nz+1價連接基,nz表示1以上的整數,Z2 表示聚合性基,*表示與式(1-1)中的氧原子的鍵結部位。 式(Z-1)中,L為單鍵或脂肪族烴基、芳香族烴基、醚鍵(-O-)、羰基(-C(=O)-)、硫醚鍵(-O-)、磺醯基(-S(=O)2 -)、-NRN -、或者將該等鍵結兩個以上之基團為較佳,單鍵、脂肪族烴基或芳香族烴基為更佳。上述RN 表示氫原子或烴基,氫原子、烷基或芳基為更佳,氫原子或烷基為進一步較佳,氫原子為特佳。 作為上述脂肪族烴基,碳數1~20的烴基為較佳,碳數1~10的烴基為更佳。又,作為上述脂肪族烴基,飽和脂肪族烴基為更佳。 作為上述芳香族烴基,碳數6~20的芳香族烴基為更佳,碳數6~12的芳香族烴基為更佳,碳數6的芳香族烴基為更佳。 式(Z-1)中,nz為1~10的整數為較佳,1~4的整數為較佳,1或2為進一步較佳,1為特佳。 式(Z-1)中,nz為1,並且L為單鍵或伸烷基、伸芳基、醚鍵(-O-)、羰基(-C(=O)-)、硫醚鍵(-O-)、磺醯基(-S(=O)2 -)、-NRN -、或者將該等鍵結兩個以上之基團為較佳,nz為1,並且L為單鍵或碳數1~10的伸烷基、伸苯基、醚鍵(-O-)、羰基(-C(=O)-)、硫醚鍵(-O-)、磺醯基(-S(=O)2 -)、-NRN -、或者將該等鍵結兩個以上之基團為更佳。 式(Z-1)中,Z2 為乙烯基、(甲基)烯丙基、(甲基)丙烯醯胺基、(甲基)丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基或羥甲基為更佳,(甲基)丙烯醯氧基、環氧基或羥甲基為進一步較佳。-Z 1 -In the formula (1-1), Z 1 represents a group containing a polymerizable group. Z 1 as the above-mentioned polymerizable group preferably includes at least one group selected from the group consisting of ethylenically unsaturated groups, cyclic ether groups, and methylol groups, including vinyl groups, (meth)allyl groups, (Meth)acrylamido, (meth)acrylamido, maleimido, vinylphenyl, epoxy, oxetanyl or methylol is more preferred, including The (meth)acryloxy group, epoxy group or hydroxymethyl group is more preferable. In addition, Z 1 is preferably a group represented by the following formula (Z-1). [Chemical formula 8] In formula (Z-1), L represents a single bond or nz+1 valent linking group, nz represents an integer of 1 or more, Z 2 represents a polymerizable group, and * represents a bond with the oxygen atom in formula (1-1) Location. In formula (Z-1), L is a single bond or aliphatic hydrocarbon group, aromatic hydrocarbon group, ether bond (-O-), carbonyl group (-C(=O)-), thioether bond (-O-), sulfur An acyl group (-S(=O) 2 -), -NR N -, or a group bonding two or more of these groups is preferable, and a single bond, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is more preferable. The above-mentioned R N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable. As the aliphatic hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrocarbon group having 1 to 10 carbon atoms is more preferred. In addition, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. In formula (Z-1), nz is preferably an integer of 1 to 10, preferably an integer of 1 to 4, 1 or 2 is more preferred, and 1 is particularly preferred. In the formula (Z-1), nz is 1, and L is a single bond or an alkylene group, an arylene group, an ether bond (-O-), a carbonyl group (-C(=O)-), a thioether bond (- O-), sulfonyl (-S(=O) 2 -), -NR N -, or a group that bonds two or more of these groups is preferred, nz is 1, and L is a single bond or carbon Number of 1-10 alkylene, phenylene, ether bond (-O-), carbonyl (-C(=O)-), thioether bond (-O-), sulfonyl (-S(=O) ) 2 -), -NR N -, or it is more preferable to bond these two or more groups. In formula (Z-1), Z 2 is vinyl, (meth)allyl, (meth)acrylamido, (meth)acrylamido, maleimido, ethylene A phenyl group, an epoxy group, an oxetanyl group, or a hydroxymethyl group is more preferable, and a (meth)acryloxy group, an epoxy group or a hydroxymethyl group is more preferable.
-n- 式(1-1)中,n分別獨立地為2~100的整數為較佳,2~50的整數為更佳,2~30的整數為進一步較佳,2~10的整數為特佳,3~10的整數為最佳。-n- In formula (1-1), n each independently is preferably an integer of 2 to 100, more preferably an integer of 2 to 50, more preferably an integer of 2 to 30, and particularly preferably an integer of 2 to 10, The integer of 3-10 is the best.
-m- 式(1-1)中,m分別獨立地為2~50的整數為較佳,2~30的整數為更佳,2~10的整數為進一步較佳,2~6的整數為更進一步較佳,2~4的整數為特佳,2或3為最佳。-m- In the formula (1-1), it is preferable that m is independently an integer of 2-50, an integer of 2-30 is more preferable, an integer of 2-10 is more preferable, and an integer of 2-6 is more preferable. Preferably, an integer of 2 to 4 is particularly preferred, and 2 or 3 is most preferred.
特定樹脂作為以式(1-1)表示之結構,包含選自包括以下述式(1-1-1)表示之結構、以下述式(1-1-2)表示之結構及以下述式(1-1-3)表示之結構之群組中之至少一種結構為較佳。 [化學式9] 式(1-1-1)~式(1-1-3)中,n及Z1 的含義分別與式(1-1)中的n及Z1 相同,且較佳的態樣亦相同。 式(1-1-1)~式(1-1-3)中,*表示與其他結構的鍵結部位。The specific resin as the structure represented by the formula (1-1) includes a structure selected from the structure represented by the following formula (1-1-1), the structure represented by the following formula (1-1-2), and the following formula ( 1-1-3) At least one structure in the group of the indicated structures is preferable. [Chemical formula 9] The same as in the formula (1-1-1) to (1-1-3), n and Z 1 are the meaning of the formula (1-1) n and Z 1, and preferred aspects are also the same. In formulas (1-1-1) to (1-1-3), * represents the bonding site with other structures.
[以式(1-2)表示之結構] 特定樹脂作為包含以上述式(1-1)表示之結構之結構,包含以下述式(1-2)表示之結構為較佳。 特定樹脂在主鏈上包含以式(1-2)表示之結構為較佳。亦即,以式(1-2)中的L1 表示之結構包含在特定樹脂的主鏈中為較佳。 特定樹脂包含複數個以式(1-2)表示之結構為較佳。特定樹脂包含複數個以式(1-2)表示之結構時,複數個以式(1-2)表示之結構可以相同,亦可以不同。 [化學式10] 式(1-2)中,L1 表示b+2價連接基,X2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,L2 表示單鍵或a+1價連接基,X1 表示以上述式(1-1)表示之結構,a表示1以上的整數,b表示1以上的整數,存在複數個X2 、L2 、X1 或a時,複數個X2 、L2 、X1 或a可以相同,亦可以不同。[Structure represented by formula (1-2)] As the structure including the structure represented by the above formula (1-1), the specific resin preferably includes the structure represented by the following formula (1-2). The specific resin preferably contains a structure represented by formula (1-2) in the main chain. That is, it is preferable that the structure represented by L 1 in the formula (1-2) is contained in the main chain of the specific resin. The specific resin preferably contains a plurality of structures represented by formula (1-2). When the specific resin contains a plurality of structures represented by formula (1-2), the plurality of structures represented by formula (1-2) may be the same or different. [Chemical formula 10] In formula (1-2), L 1 represents a b+2 valent linking group, X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L 2 represents a single bond or a+1 valence Linking group, X 1 represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, when there are multiple X 2 , L 2 , X 1 or a, multiple X 2 , L 2 , X 1 or a may be the same or different.
-L1 - L1 表示b+2價連接基,為脂肪族烴基、芳香族烴基或該等基團中的至少一個與醚鍵、羰基、硫醚鍵、磺醯基及-NRN -中的至少一個鍵結之基團為較佳。上述RN 表示氫原子或烴基,氫原子、烷基或芳基為更佳,氫原子或烷基為進一步較佳,氫原子為特佳。 作為上述脂肪族烴基,碳數2~30的脂肪族飽和烴基為較佳,碳數2~10的脂肪族飽和烴基為更佳。 又,作為上述脂肪族烴基,環員數為6~20的飽和脂肪族烴環基為較佳。 作為上述芳香族烴基,碳數6~20的芳香族烴基為較佳,碳數6~12的脂肪族烴基為較佳,碳數6的芳香族烴基為更佳。 該等中,從溶劑溶解性的觀點考慮,L1 為包含脂肪族烴環基或芳香族烴環基之基團為較佳,包含芳香族烴環基之基團為更佳。 又,L1 包含選自包括以下述式(A-1)~下述式(A-5)中的任一個表示之結構之群組中之至少一種結構為較佳,以下述式(A-1)~下述式(A-5)中的任一個表示之結構為更佳。-L 1 -L 1 represents a b+2 valent linking group, which is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR N- At least one bonded group of is preferred. The above-mentioned R N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable. As the aliphatic hydrocarbon group, an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms is preferable, and an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms is more preferable. Furthermore, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aliphatic hydrocarbon group having 6 to 12 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. Among these, from the viewpoint of solvent solubility, L 1 is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and a group containing an aromatic hydrocarbon ring group is more preferable. In addition, L 1 preferably includes at least one structure selected from the group consisting of structures represented by any one of the following formula (A-1) to the following formula (A-5), and the following formula (A- 1) The structure represented by any one of the following formulas (A-5) is more preferable.
[化學式11] 式(A-1)~(A-5)中,RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基、鹵素原子或與上述式(1-2)或上述式(1-3)中的X2 的鍵結部位,LA31 及LA41 分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基,RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中,b個分別為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,*分別獨立地表示與其他結構的鍵結部位。[Chemical formula 11] In formulas (A-1) to (A-5), R A11 to R A14 , R A21 to R A24 , R A31 to R A38 , R A41 to R A48 and R A51 to R A58 each independently represent a hydrogen atom, An alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, a halogen atom or the bonding site with X 2 in the above formula (1-2) or the above formula (1-3), L A31 and L A41 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a heteroatom, a heterocyclic group, or a halogenated alkylene group, R A11 to R A14 , R A21 to R Among A24 , R A31 to R A38 , R A41 to R A48, and R A51 to R A58 , b is the bonding site to X 2 in formula (1-2) or formula (1-3) described later, * Each independently indicates the bonding site with other structures.
從耐藥品性的觀點考慮,該等中,L1 為以式(A-1)、式(A-2)、式(A-3)或式(A-4)表示之結構為較佳。From the viewpoint of chemical resistance, among these, L 1 is preferably a structure represented by formula (A-1), formula (A-2), formula (A-3), or formula (A-4).
式(A-1)中,RA11 ~RA14 分別獨立地表示氫原子、碳數1~6的烷基、碳數3~12的環狀烷基、碳數1~6的烷氧基、羥基、氰基、碳數1~3的鹵化烷基或鹵素原子為較佳,從溶劑溶解性的觀點考慮,氫原子、碳數1~6的烷基、碳數1~6的烷氧基或碳數1~3的鹵化烷基為更佳,氫原子或碳數1~6的烷基為更佳。 又,RA11 ~RA14 中b個為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,為RA13 與X2 的鍵結部位或RA12 及RA14 與X2 的鍵結部位為較佳。 作為上述RA11 ~RA14 中的上述鹵化烷基中的鹵素原子或上述鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子等,氯原子或溴原子為較佳。In the formula (A-1), R A11 to R A14 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a cyclic alkyl group having 3 to 12 carbons, an alkoxy group having 1 to 6 carbons, Hydroxyl group, cyano group, halogenated alkyl group having 1 to 3 carbons or halogen atom are preferred. From the viewpoint of solvent solubility, hydrogen atom, alkyl group having 1 to 6 carbons, alkoxy group having 1 to 6 carbons Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. Further, in the R A11 ~ R A14 is one and b in the formula (1-2) or the above formula (1-3) X 2 bonded portion, the A13 R is bonded to X or R 2 portion A12 and R The bonding site of A14 and X 2 is preferable. Examples of the halogen atom or the halogen atom in the halogenated alkyl group in the above R A11 to R A14 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred.
式(A-2)中,RA21 ~RA24 的含義分別與式(A-1)中的RA11 ~RA14 相同,且較佳的態樣亦相同。 又,RA21 ~RA24 中b個為與式(1-2)或後述式(1-3)中的X2 的鍵結部位。In the formula (A-2), the meanings of R A21 to R A24 are the same as those of R A11 to R A14 in the formula (A-1), and preferred aspects are also the same. In addition, b among R A21 to R A24 is a bonding site to X 2 in formula (1-2) or formula (1-3) described later.
式(A-3)中,RA31 ~RA38 分別獨立地表示氫原子、碳數1~6的烷基、碳數3~12的環狀烷基、碳數1~6的烷氧基、羥基、氰基、碳數1~3的鹵化烷基或鹵素原子為較佳,從溶劑溶解性的觀點考慮,氫原子、碳數1~6的烷基、碳數1~6的烷氧基或碳數1~3的鹵化烷基為更佳,氫原子或碳數1~6的烷基為更佳。 作為上述RA31 ~RA38 中的上述鹵化烷基中的鹵素原子或上述鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子等,氯原子或溴原子為較佳。 又,RA31 ~RA38 中b個為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,RA31 及RA36 與X2 的鍵結部位為較佳。 式(A-3)中,LA31 表示單鍵、碳數1~6的2價飽和烴基、碳數5~24的2價不飽和烴基、-O-、-S-、-NRN -、雜環基或碳數1~6的鹵化伸烷基為較佳,表示單鍵、碳數1~6的飽和烴基、-O-或雜環基為較佳,表示單鍵或-O-為進一步較佳。 上述RN 表示氫原子或烴基,氫原子、烷基或芳基為更佳,氫原子或烷基為進一步較佳,氫原子為特佳。 上述2價不飽和烴基可以為2價脂肪族不飽和烴基,亦可以為2價芳香族烴基,2價芳香族烴基為較佳。 作為上述雜環基,例如從脂肪族或芳香族雜環去除兩個氫原子之基團為較佳,從脂肪族或芳香族雜環去除兩個氫原子之基團為較佳,從吡咯啶環、四氫呋喃環、四氫噻吩環、吡咯環、呋喃環、噻吩環、哌啶環、四氫哌喃環、吡啶環、口末啉環等的環結構去除兩個氫原子之基團為更佳。該等雜環亦可以進一步與其他雜環或烴環具有縮合環。 上述雜環的環員數為5~10為較佳,5或6為更佳。 又,作為上述雜環基中的雜原子,氧原子、氮原子或硫原子為較佳。 作為上述鹵化伸烷基中的鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子等,氯原子或溴原子為較佳。In the formula (A-3), R A31 to R A38 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, a cyclic alkyl group having 3 to 12 carbons, an alkoxy group having 1 to 6 carbons, Hydroxyl group, cyano group, halogenated alkyl group having 1 to 3 carbons or halogen atom are preferred. From the viewpoint of solvent solubility, hydrogen atom, alkyl group having 1 to 6 carbons, alkoxy group having 1 to 6 carbons Or a halogenated alkyl group having 1 to 3 carbons is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbons is more preferable. Examples of the halogen atom or the halogen atom in the halogenated alkyl group in the above R A31 to R A38 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred. And, X is bonded portion after the R A31 ~ R A38 is a b formula (1-2) or the following formula (1-3) 2, R A31 and R A36 and the bonded portion of X 2 is preferably . In formula (A-3), L A31 represents a single bond, a divalent saturated hydrocarbon group with 1 to 6 carbons, a divalent unsaturated hydrocarbon group with 5 to 24 carbons, -O-, -S-, -NR N -, A heterocyclic group or a halogenated alkylene group having 1 to 6 carbon atoms is preferred, which represents a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group is preferred, and represents a single bond or -O- is Further better. The above-mentioned R N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable. The above-mentioned divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, and a divalent aromatic hydrocarbon group is preferred. As the above-mentioned heterocyclic group, for example, a group in which two hydrogen atoms are removed from an aliphatic or aromatic heterocyclic ring is preferable, and a group in which two hydrogen atoms are removed from an aliphatic or aromatic heterocyclic ring is preferable. The ring structure of ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, ormoline ring, etc. The ring structure removes two hydrogen atoms. good. These heterocyclic rings may further have a condensed ring with other heterocyclic rings or hydrocarbon rings. The number of ring members of the above heterocyclic ring is preferably 5-10, more preferably 5 or 6. In addition, as the hetero atom in the above heterocyclic group, an oxygen atom, a nitrogen atom or a sulfur atom is preferred. Examples of the halogen atom in the above-mentioned halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom or a bromine atom is preferred.
式(A-4)中,RA41 ~RA48 的含義分別與式(A-3)中的RA31 ~RA38 相同,且較佳的態樣亦相同。 又,RA41 ~RA48 中b個為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,RA41 及RA48 與X2 的鍵結部位為較佳。 式(A-4)中,LA41 的含義與式(A-3)中的LA31 相同,且較佳的態樣亦相同。In formula (A-4), R A41 to R A48 have the same meanings as R A31 to R A38 in formula (A-3), and preferred aspects are also the same. And, X is bonded portion after the R A41 ~ R A48 is a b formula (1-2) or the following formula (1-3) 2, R A41 and R A48 and the bonded portion of X 2 is preferably . In formula (A-4), L A41 has the same meaning as L A31 in formula (A-3), and preferred aspects are also the same.
式(A-5)中,RA51 ~RA58 的含義分別與式(A-1)中的RA11 ~RA14 相同,且較佳的態樣亦相同。In the formula (A-5), the meanings of R A51 to R A58 are the same as those of R A11 to R A14 in the formula (A-1), and preferred aspects are also the same.
又,式(A-1)~式(A-5)中,*分別獨立地為與樹脂中的主鏈的鍵結部位為較佳。In addition, in formulas (A-1) to (A-5), * is preferably a bonding site to the main chain in the resin independently.
-X2 - 式(1-2)中,X2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,酯鍵或醚鍵為較佳。 又,X2 在考慮合成方法等之基礎上決定即可。 X2 為酯鍵時,可以為酯鍵的碳原子與L1 鍵結,亦可以為氧原子與L1 鍵結。 X2 為胺甲酸乙酯鍵時,胺甲酸乙酯鍵的氧原子與L1 鍵結為較佳。 X2 為醯胺鍵時,醯胺鍵的碳原子與L1 鍵結為較佳。-X 2 -In the formula (1-2), X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and an ester bond or an ether bond is preferred. In addition, X 2 may be determined in consideration of the synthesis method and the like. When X 2 is an ester bond, the carbon atom of the ester bond may be bonded to L 1 or the oxygen atom may be bonded to L 1 . When X 2 is a urethane bond, the oxygen atom of the urethane bond is preferably bonded to L 1. When X 2 is an amide bond, the carbon atom of the amide bond is preferably bonded to L 1.
-L2 - 式(1-2)中,L2 表示單鍵或a+1價連接基,單鍵或脂肪族烴基、芳香族烴基、醚鍵、羰基、硫醚鍵、磺醯基、-NRN -、或者將該等鍵結兩個以上之基團為較佳,單鍵、脂肪族烴基或芳香族烴基為更佳。上述RN 表示氫原子或烴基,氫原子、烷基或芳基為更佳,氫原子或烷基為進一步較佳,氫原子為特佳。 作為上述脂肪族烴基,碳數1~20的烴基為較佳,碳數1~10的烴基為更佳。又,作為上述脂肪族烴基,飽和脂肪族烴基為更佳。 作為上述芳香族烴基,碳數6~20的芳香族烴基為更佳,碳數6~12的芳香族烴基為更佳,碳數6的芳香族烴基為更佳。-L 2 -In the formula (1-2), L 2 represents a single bond or a + 1 valent linking group, a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group,- NR N -, or a group that bonds two or more of these groups is preferable, and a single bond, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is more preferable. The above-mentioned R N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable. As the aliphatic hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrocarbon group having 1 to 10 carbon atoms is more preferred. In addition, as the above-mentioned aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is more preferable. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.
-X1 - 式(1-2)中,X1 表示以上述式(1-1)表示之結構,較佳的態樣如式(1-1)的說明中所記載。-X 1 -In the formula (1-2), X 1 represents the structure represented by the above formula (1-1), and a preferable aspect is as described in the description of the formula (1-1).
-a- 式(1-2)中,a表示1以上的整數,1~10的整數為較佳,1~4為更佳,1或2為進一步較佳,1為特佳。-a- In the formula (1-2), a represents an integer of 1 or more, and an integer of 1 to 10 is preferred, 1 to 4 is more preferred, 1 or 2 is more preferred, and 1 is particularly preferred.
-b- 式(1-2)中,b表示1以上的整數,1~10的整數為較佳,1~4為更佳,1或2為進一步較佳,1為特佳。-b- In the formula (1-2), b represents an integer of 1 or more, and an integer of 1 to 10 is preferred, 1 to 4 is more preferred, 1 or 2 is more preferred, and 1 is particularly preferred.
[以式(1-3)表示之重複單元] 特定樹脂作為包含以式(1-1)表示之結構之重複單元,包含以下述式(1-3)表示之重複單元為較佳。 又,特定樹脂在主鏈上具有以式(1-3)表示之重複單元為較佳。 [化學式12] 式(1-3)中,L1 表示b+2價連接基,X2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,L2 表示單鍵或a+1價連接基,X1 表示以上述式(1-1)表示之結構,a表示1以上的整數,b表示1以上的整數,L4 表示以下述式(L4-1)或式(L4-2)表示之結構,存在複數個X2 、L2 、X1 或a時,複數個X2 、L2 、X1 或a可以相同,亦可以不同。 [化學式13] 式(L4-1)或式(L4-2)中,R115 表示4價有機基,A1 及A2 分別獨立地表示氧原子或-NH-,R113 及R114 分別獨立地表示氫原子或1價有機基。[Repeating unit represented by formula (1-3)] As a repeating unit including a structure represented by formula (1-1), the specific resin preferably includes a repeating unit represented by the following formula (1-3). In addition, the specific resin preferably has a repeating unit represented by formula (1-3) in the main chain. [Chemical formula 12] In formula (1-3), L 1 represents a b+2 valent linking group, X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and L 2 represents a single bond or a+1 valence Linking group, X 1 represents the structure represented by the above formula (1-1), a represents an integer of 1 or more, b represents an integer of 1 or more, and L 4 represents the following formula (L4-1) or formula (L4-2) In the indicated structure, when there are a plurality of X 2 , L 2 , X 1 or a, the plurality of X 2 , L 2 , X 1 or a may be the same or different. [Chemical formula 13] In formula (L4-1) or formula (L4-2), R 115 represents a tetravalent organic group, A 1 and A 2 each independently represent an oxygen atom or -NH-, and R 113 and R 114 each independently represent a hydrogen atom Or monovalent organic group.
-L1 、X2 、L2 、X1 、a及b- 式(1-3)中,L1 、X2 、L2 、X1 、a及b的含義分別與式(1-2)中的L1 、X2 、L2 、X1 、a及b相同,且較佳的態樣亦相同。-L 1 , X 2 , L 2 , X 1 , a and b- In formula (1-3), L 1 , X 2 , L 2 , X 1 , a and b have the same meaning as formula (1-2) L 1 , X 2 , L 2 , X 1 , a and b are the same, and preferred aspects are also the same.
-L4 - <<式(L4-1)>> 式(L4-1)中,R115 為包含芳香環之4價有機基為較佳,以下述式(5)或式(6)表示之基團為更佳。-L 4 -<<Formula (L4-1)>> In the formula (L4-1), R 115 is preferably a tetravalent organic group containing an aromatic ring, which is represented by the following formula (5) or formula (6) The group is more preferable.
[化學式14] [Chemical formula 14]
R112 為2價連接基,單鍵或者可以被氟原子取代的碳數1~10的脂肪族烴基、-O-、-C(=O)-、-S-、-S(=O)2 -、-NHC(=O)-或將該等組合兩個以上之基團為較佳,單鍵或者選自可以被氟原子取代的碳數1~3的伸烷基、-O-、-C(=O)-、-S-及-S(=O)2 -中之基團為更佳,選自包括-CH2 -、-O-、-S-、-S(=O)2 -、-C(CF3 )2 -及-C(CH3 )2 -之群組中之2價基團為進一步較佳。*分別獨立地表示與其他結構的鍵結部位。R 112 is a divalent linking group, a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NHC(=O)- or a combination of two or more of these groups is preferred, a single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-,- The group in C(=O)-, -S- and -S(=O) 2 -is more preferably selected from the group including -CH 2 -, -O-, -S-, -S(=O) 2 The divalent group in the group of -, -C(CF 3 ) 2 -and -C(CH 3 ) 2-is further preferred. * Each independently indicates the bonding site with other structures.
關於式(L4-1)中的R115 所表示之4價有機基,具體而言,可列舉從四羧酸二酐去除酸二酐基之後殘存之四羧酸殘基等。四羧酸二酐可以僅使用一種,亦可以使用兩種以上。四羧酸二酐為以下述式(7)表示之化合物為較佳。 The tetravalent organic group represented by R 115 in the formula (L4-1) specifically includes a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
[化學式15] [Chemical formula 15]
R115 表示4價有機基。R115 的含義與式(L4-1)的R115 相同。R 115 represents a tetravalent organic group. R 115 is the same meaning as in formula (L4-1) of the R 115.
作為四羧酸二酐的具體例,可例示選自均苯四甲酸、均苯四甲酸二酐(PMDA)、3,3’,4,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯硫醚四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯基甲烷四羧酸二酐、2,2’,3,3’-二苯基甲烷四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,3,3’,4’-二苯甲酮四羧酸二酐、4,4’-氧代二鄰苯二甲酸二酐、4,4’-(六氟亞異丙基)二鄰苯二甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,7-萘四羧酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、2,2-雙(3,4-二羧基苯基)六氟丙烷二酐、1,3-二苯基六氟丙烷-3,3,4,4-四羧酸二酐、1,4,5,6-萘四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、3,4,9,10-苝四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,8,9,10-菲四羧酸二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、1,2,3,4-苯四羧酸二酐及該等的碳數1~6的烷基衍生物及碳數1~6的烷氧基衍生物中之至少一種。As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride , 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-di Carboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-Diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1 ,4,5,8-Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1 ,1-Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl derivatives with 1 to 6 carbon atoms and carbon numbers At least one of 1 to 6 alkoxy derivatives.
又,作為較佳例子,還可列舉下述中所示出之四羧酸二酐(DAA-1)~(DAA-5)。Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below can also be mentioned.
[化學式16] [Chemical formula 16]
<<式(L4-2)>> 式(L4-2)中,A1 及A2 分別獨立地表示氧原子或-NH-,氧原子為較佳。 式(L4-2)中,R113 及R114 分別獨立地表示氫原子或1價有機基,R113 及R114 中的至少一者包含聚合性基為較佳,兩者包含聚合性基為更佳。 作為R113 或R114 中的聚合性基,可列舉與上述式(1-1)中的Z1 中的聚合性基相同的基團。<<Formula (L4-2)>> In the formula (L4-2), A 1 and A 2 each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred. In the formula (L4-2), R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R 113 and R 114 contains a polymerizable group, and both of them contain a polymerizable group. Better. Examples of the polymerizable group in R 113 or R 114 include the same groups as the polymerizable group in Z 1 in the above formula (1-1).
R113 或R114 為乙烯基、烯丙基、(甲基)丙烯醯基或以下述式(III)表示之基團亦較佳。R 113 or R 114 is also preferably a vinyl group, an allyl group, a (meth)acryloyl group, or a group represented by the following formula (III).
[化學式17] [Chemical formula 17]
式(III)中,R200 表示氫原子或甲基,甲基為較佳。In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is preferred.
式(III)中,R201 表示碳數2~12的伸烷基、-CH2 CH(OH)CH2 -或碳數4~30的(聚)伸烷氧基(作為伸烷基,碳數1~12為較佳,1~6為更佳,1~3為特佳;重複數為1~12為較佳,1~6為更佳,1~3為特佳)。另外,(聚)伸烷氧基表示伸烷氧基或聚伸烷氧基。 關於較佳的R201 的例子,可列舉伸乙基、伸丙基、三亞甲基、四亞甲基、1,2-丁二基、1,3-丁二基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基、-CH2 CH(OH)CH2 -,伸乙基、伸丙基、三亞甲基、-CH2 CH(OH)CH2 -為更佳。 特佳為R200 為甲基,R201 為伸乙基。 式(III)中,*表示與其他結構的鍵結部位。 作為較佳的實施形態,可列舉作為式(L4-2)中的R113 或R114 的1價有機基具有一個、兩個或三個(較佳為一個)酸基之、脂肪族基、芳香族基及芳烷基等。具體而言,可列舉具有酸基之碳數6~20的芳香族基、具有酸基之碳數7~25的芳烷基。更具體而言,可列舉具有酸基之苯基及具有酸基之苄基。酸基為羥基為較佳。亦即,R113 或R114 為具有羥基之基團為較佳。 作為R113 或R114 所表示之1價有機基,可較佳地使用提高顯影液的溶解度之取代基。In formula (III), R 201 represents an alkylene group having 2 to 12 carbons, -CH 2 CH(OH)CH 2 -or a (poly) alkoxy group having 4 to 30 carbons (as an alkylene group, carbon The number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3; the repetitive number is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 to 3). In addition, (poly)alkoxyl group means an alkoxyl group or a polyalkoxyl group. Examples of preferred R 201 include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. Methylene, octamethylene, dodecamethylene, -CH 2 CH(OH)CH 2 -, ethylene, propylene, trimethylene, -CH 2 CH(OH)CH 2 -are more good. Particularly preferably, R 200 is a methyl group, and R 201 is an ethylene group. In formula (III), * represents the bonding site with other structures. As a preferred embodiment, the monovalent organic group of R 113 or R 114 in formula (L4-2) has one, two or three (preferably one) acid groups, aliphatic groups, Aromatic groups and aralkyl groups, etc. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an aralkyl group having 7 to 25 carbon atoms having an acid group can be cited. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group. As the monovalent organic group represented by R 113 or R 114 , a substituent that improves the solubility of the developer can be preferably used.
從對水性顯影液之溶解性的觀點考慮,R113 或R114 為氫原子、2-羥基芐基、3-羥基芐基及4-羥基芐基為更佳。From the viewpoint of solubility in an aqueous developer, R 113 or R 114 is a hydrogen atom, and it is more preferable that a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group are used.
從對有機溶劑之溶解度的觀點考慮,R113 或R114 為1價有機基為較佳。作為1價有機基,直鏈或支鏈的烷基、環狀烷基、芳香族基為較佳,被芳香族基取代之烷基為更佳。From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group are preferable, and an alkyl group substituted with an aromatic group is more preferable.
烷基的碳數為1~30為較佳(環狀時為3以上)。烷基可以為直鏈、支鏈、環狀中的任一個。作為直鏈或支鏈烷基,例如可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基,十八烷基、異丙基、異丁基、第二丁基、第三丁基、1-乙基戊基及2-乙基己基。環狀烷基可以為單環環狀烷基,亦可以為多環環狀烷基。作為單環環狀烷基,例如可列舉環丙基、環丁基、環戊基、環己基、環庚基及環辛基。作為多環環狀烷基,例如可列舉金剛烷基、降莰基、莰基、莰烯基(camphenyl)、十氫萘基、三環癸烷基、四環癸烷基、莰二醯基、二環己基及蒎烯基(pinenyl)。又,作為被芳香族基取代之烷基,被以下所述之芳香族基取代之直鏈烷基為較佳。The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic ring). The alkyl group may be any of linear, branched, and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl. , Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and camphenyl , Dicyclohexyl and pinenyl (pinenyl). In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.
作為芳香族基,具體而言為經取代或未經取代的芳香族烴基(作為構成基團之環狀結構,可列舉苯環、萘環、聯苯環、茀環、戊搭烯環、茚環、薁環、庚搭烯環、茚烯環、苝環、稠五苯環、苊烯環、菲環、蒽環、稠四苯環、䓛環、三伸苯環等)或經取代或未經取代的芳香族雜環基(作為構成基團之環狀結構,茀環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡啶環、吡𠯤環、嘧啶環、嗒𠯤環、吲口巾環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹口巾環、喹啉環、呔𠯤環、萘啶環、喹㗁啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、口山口星環、啡㗁噻環、啡噻𠯤環或啡𠯤環)。The aromatic group is specifically a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a sulphur ring, a pentene ring, and an indene ring. Ring, azulene ring, heptene ring, indenene ring, perylene ring, fused pentaphenyl ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, chrysene ring, terphenylene ring, etc.) or substituted or Unsubstituted aromatic heterocyclic group (as the cyclic structure of the constituent group, pyrrole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyridine ring, pyridine ring, pyrimidine ring) , Scalp ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, quinoline ring, naphthyridine ring, quinoline Ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thiaxanthene ring, chromene ring, Kouyamaguchi ring, phenanthrene ring, phenanthrene ring Or brown 𠯤 ring).
又,聚醯亞胺前驅物在重複單元中具有氟原子亦較佳。聚醯亞胺前驅物中的氟原子含量為10質量%以上為較佳,20質量%以上為更佳。上限並無特別限制,實際上為50質量%以下。Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the repeating unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is actually 50% by mass or less.
又,亦可以以提高與基材的密接性之目的,使具有矽氧烷結構之脂肪族基與特定樹脂共聚。具體而言,作為二胺成分,可列舉雙(3-胺基丙基)四甲基二矽氧烷、雙(對胺基苯基)八甲基五矽氧烷等。In addition, for the purpose of improving the adhesion to the substrate, the aliphatic group having a silicone structure can be copolymerized with a specific resin. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.
式(L4-2)中,R115 的含義與式(L4-1)中的R115 相同,且較佳的態樣亦相同。In formula (L4-2), R 115 is the same meaning as in formula (L4-1) R 115, and preferably also of the same aspect.
-樹脂種類- 式(1-3)中,L4 為以式(L4-1)表示之基團所表示之結構時,特定樹脂為聚醯亞胺為較佳。 式(1-3)中,L4 為以式(L4-2)表示之基團所表示之結構時,特定樹脂為聚醯亞胺前驅物為較佳。-Resin Type-In the formula (1-3), when L 4 is a structure represented by a group represented by the formula (L4-1), the specific resin is preferably polyimide. In formula (1-3), when L 4 is a structure represented by a group represented by formula (L4-2), it is preferable that the specific resin is a polyimide precursor.
-含量- 特定樹脂包含以式(1-3)表示之重複單元時,以式(1-3)表示之重複單元的含量相對於特定樹脂的總質量為0.1~80質量%為較佳,0.5~70質量%為更佳,1~60質量%為進一步較佳。 特定樹脂可以僅包含一種以式(1-3)表示之重複單元,亦可以包含兩種以上。-content- When the specific resin contains the repeating unit represented by the formula (1-3), the content of the repeating unit represented by the formula (1-3) relative to the total mass of the specific resin is preferably 0.1-80 mass%, 0.5-70 mass % Is more preferable, and 1 to 60% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-3), or may include two or more types.
[以式(1-1B)表示之結構] 特定樹脂亦可以為包含以下述式(1-1B)表示之結構,並且在特定樹脂的其他部位具有聚合性基之態樣。 特定樹脂可以在主鏈上具有以下述式(1-1B)表示之結構,亦可以在側鏈上具有,從膜強度的觀點考慮,在主鏈上具有為較佳。又,從塗佈性的觀點考慮,在側鏈上具有為較佳。 [化學式18] 式(1-1B)中,RB1 分別獨立地表示氫原子或烷基,nB表示2以上的整數,mB表示2以上的整數,*分別獨立地表示與其他結構的鍵結部位。[Structure represented by formula (1-1B)] The specific resin may include a structure represented by the following formula (1-1B) and have a polymerizable group in another part of the specific resin. The specific resin may have a structure represented by the following formula (1-1B) in the main chain, or may have it in a side chain. From the viewpoint of film strength, it is preferable to have it in the main chain. In addition, from the viewpoint of coatability, it is preferable to have it in the side chain. [Chemical formula 18] In formula (1-1B), R B1 each independently represents a hydrogen atom or an alkyl group, nB represents an integer of 2 or more, mB represents an integer of 2 or more, and * each independently represents a bonding site with another structure.
-RB1 - 式(1-1B)中,RB1 分別獨立地為氫原子或碳數1~10的烷基為較佳,氫原子或碳數1~4的烷基為更佳,氫原子或甲基為進一步較佳。-R B1 -In the formula (1-1B), R B1 is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom Or methyl is more preferred.
-nB- 式(1-1B)中,nB分別獨立地為2~100的整數為較佳,2~50的整數為更佳,2~30的整數為進一步較佳,2~10的整數為特佳,3~10的整數為最佳。-nB- In formula (1-1B), nB each independently is preferably an integer of 2-100, more preferably an integer of 2-50, more preferably an integer of 2-30, and particularly preferably an integer of 2-10. The integer of 3-10 is the best.
-mB- 式(1-1B)中,m分別獨立地為2~50的整數為較佳,2~30的整數為更佳,2~10的整數為進一步較佳,2~6的整數為更進一步較佳,2~4的整數為特佳,2或3為最佳。-mB- In the formula (1-1B), it is preferable that m is independently an integer of 2-50, an integer of 2-30 is more preferable, an integer of 2-10 is more preferable, and an integer of 2-6 is more preferable. Preferably, an integer of 2 to 4 is particularly preferred, and 2 or 3 is most preferred.
特定樹脂作為以式(1-1B)表示之結構,包含選自包括以下述式(1-1B-1)表示之結構、以下述式(1-1B-2)表示之結構及以下述式(1-1B-3)表示之結構之群組中之至少一種結構為較佳。 [化學式19] 式(1-1B-1)~式(1-1B-3)中,nB的含義分別與式(1-1B)中的nB相同,且較佳的態樣亦相同。 式(1-1B-1)~式(1-1B-3)中,*分別獨立地表示與其他結構的鍵結部位。As the structure represented by the formula (1-1B), the specific resin includes a structure selected from the structure represented by the following formula (1-1B-1), the structure represented by the following formula (1-1B-2), and the structure represented by the following formula ( 1-1B-3) At least one structure in the group of structures indicated is preferable. [Chemical formula 19] In formulas (1-1B-1) to (1-1B-3), nB has the same meaning as nB in formula (1-1B), and preferred aspects are also the same. In formulas (1-1B-1) to (1-1B-3), * each independently represents a bonding site with other structures.
[式(1-2B)或式(1-2C)] 特定樹脂作為包含式(1-1B)之結構,包含以下述式(1-2B)表示之結構或以下述式(1-2C)表示之結構為較佳。 特定樹脂包含以下述式(1-2B)表示之結構時,特定樹脂在主鏈上包含以下述式(1-2B)表示之結構為較佳。 特定樹脂包含以下述式(1-2C)表示之結構時,特定樹脂在主鏈末端或側鏈上包含以下述式(1-2C)表示之結構為較佳,在側鏈上包含為更佳。 特定樹脂包含複數個以式(1-2B)表示之結構或以式(1-2C)表示之結構為較佳。特定樹脂包含複數個以式(1-2B)表示之結構或以式(1-2C)表示之結構時,複數個以式(1-2B)表示之結構或以式(1-2C)表示之結構可以相同,亦可以不同。 [化學式20] 式(1-2B)中,LB1 及LB2 分別獨立地表示單鍵或2價連接基,LX 表示以上述式(1-1B)表示之結構。 式(1-2C)中,LB3 表示單鍵或2價連接基,LX 表示以上述式(1-1B)表示之結構,RB2 表示氫原子或表示不具有聚合性基的取代基。[Formula (1-2B) or Formula (1-2C)] The specific resin as a structure including formula (1-1B) includes a structure represented by the following formula (1-2B) or a structure represented by the following formula (1-2C) The structure is better. When the specific resin includes a structure represented by the following formula (1-2B), the specific resin preferably includes a structure represented by the following formula (1-2B) in the main chain. When the specific resin contains the structure represented by the following formula (1-2C), the specific resin preferably contains the structure represented by the following formula (1-2C) at the end of the main chain or on the side chain, and more preferably contains the structure on the side chain . The specific resin preferably contains a plurality of structures represented by formula (1-2B) or structures represented by formula (1-2C). When the specific resin contains multiple structures represented by formula (1-2B) or structures represented by formula (1-2C), multiple structures represented by formula (1-2B) or structures represented by formula (1-2C) The structure can be the same or different. [Chemical formula 20] In the formula (1-2B), L B1 and L B2 each independently represent a single bond or a divalent linking group, and L X represents a structure represented by the above formula (1-1B). In the formula (1-2C), L B3 represents a single bond or a divalent linking group, L X represents a structure represented by the above formula (1-1B), and R B2 represents a hydrogen atom or a substituent that does not have a polymerizable group.
式(1-2B)中,LB1 及LB2 分別獨立地為單鍵或伸烷基、伸芳基、醚鍵、羰基、硫醚鍵、磺醯基、-NRN -、或者將該等鍵結兩個以上之基團為較佳,單鍵、伸烷基或伸芳基為更佳,單鍵或伸烷基為更佳。上述RN 表示氫原子或烴基,氫原子、烷基或芳基為更佳,氫原子或烷基為進一步較佳,氫原子為特佳。 作為上述伸烷基,碳數2~10的伸烷基為較佳,碳數2~4的伸烷基為更佳,伸乙基或伸丙基為更佳。 式(1-2B)中,LX 表示以上述式(1-1B)表示之結構,較佳的態樣如上述式(1-1B)中的說明中所記載。In the formula (1-2B), L B1 and L B2 are each independently a single bond or an alkylene group, an aryl group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N -, or the like It is preferable to bond two or more groups, a single bond, an alkylene group or an arylene group is more preferable, and a single bond or an alkylene group is more preferable. The above-mentioned R N represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, and a hydrogen atom is particularly preferable. As the above-mentioned alkylene group, an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, and an ethylene group or a propylene group is more preferable. In the formula (1-2B), L X represents the structure represented by the above formula (1-1B), and a preferable aspect is as described in the description of the above formula (1-1B).
式(1-2C)中,LB3 的含義與上述式(1-2B)中的LB1 或LB2 相同,且較佳的態樣亦相同。 式(1-2C)中,LX 表示以上述式(1-1B)表示之結構,較佳的態樣如上述式(1-1B)中的說明中所記載。 式(1-2C)中,RB2 只要為氫原子或烷基、芳基、鹵素原子等公知的取代基即可,氫原子、烷基或芳基為較佳,氫原子或烷基為更佳,烷基為進一步較佳。 作為上述烷基,碳數1~20的烷基為較佳,碳數1~10的烷基為更佳,碳數1~4的烷基為進一步較佳。 作為上述芳基,碳數6~20的烷基為較佳,碳數6~12的烷基為更佳,碳數1~4的烷基為進一步較佳。In formula (1-2C), L B3 has the same meaning as L B1 or L B2 in the above formula (1-2B), and preferred aspects are also the same. In the formula (1-2C), L X represents the structure represented by the above formula (1-1B), and a preferable aspect is as described in the description of the above formula (1-1B). In the formula (1-2C), R B2 only needs to be a hydrogen atom or a known substituent such as an alkyl group, an aryl group, and a halogen atom. A hydrogen atom, an alkyl group or an aryl group is preferred, and a hydrogen atom or an alkyl group is more preferred. Preferably, the alkyl group is further preferred. As the above-mentioned alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. As the above-mentioned aryl group, an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 6 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
[以式(1-3B)表示之重複單元] 特定樹脂包含以式(1-2B)表示之結構時,特定樹脂包含以下述式(1-3B)表示之重複單元為較佳。 [化學式21] 式(1-3B)中,LB1 及LB2 分別獨立地表示單鍵或2價連接基,LX 表示以上述式(1-1B)表示之結構,LB4 表示以上述式(1-3)中的式(L4-1)或式(L4-2)表示之結構。[Repeating unit represented by formula (1-3B)] When the specific resin includes a structure represented by formula (1-2B), it is preferable that the specific resin includes a repeating unit represented by the following formula (1-3B). [Chemical formula 21] In the formula (1-3B), L B1 and L B2 each independently represent a single bond or a divalent linking group, L X represents the structure represented by the above formula (1-1B), and L B4 represents the above formula (1-3 The structure represented by the formula (L4-1) or formula (L4-2) in ).
式(1-3B)中,LB1 、LB2 及LX 的含義分別與式(1-2B)中的LB1 、LB2 及LX 相同,且較佳的態樣亦相同。 式(1-3B)中,LB4 的含義與上述式(1-3)中的L4 相同,且較佳的態樣亦相同。In the formula (1-3B), the meaning of L B1, L B2 and L X, respectively of formula (1-2B) L B1, L B2 and L X identical, and preferred aspects are also the same. In the formula (1-3B), L B4 has the same meaning as L 4 in the above formula (1-3), and preferred aspects are also the same.
-樹脂種類- 式(1-3B)中,LB4 為以式(L4-1)表示之基團所表示之結構時,特定樹脂為聚醯亞胺為較佳。 式(1-3B)中,LB4 為以式(L4-2)表示之基團所表示之結構時,特定樹脂為聚醯亞胺前驅物為較佳。- the type of resin - when the formula (1-3B), L B4 is a group represented by the formula (L4-1) represented by the structure, the specific resin is a polyimide is preferred. When the formula (1-3B), L B4 is a group represented by the formula (L4-2) represented by the structure, the specific resin is a polyimide precursor is preferred.
-含量- 特定樹脂包含以式(1-3B)表示之重複單元時,以式(1-3B)表示之重複單元的含量相對於特定樹脂的總質量為0.1~80質量%為較佳,10~70質量%為更佳,20~60質量%為進一步較佳。 特定樹脂可以僅包含一種以式(1-3B)表示之重複單元,亦可以包含兩種以上。-content- When the specific resin contains the repeating unit represented by the formula (1-3B), the content of the repeating unit represented by the formula (1-3B) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 70 mass% % Is more preferable, and 20 to 60% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-3B), or may include two or more types.
[以式(1-3C)表示之結構] 特定樹脂包含以式(1-2C)表示之結構時,特定樹脂作為包含以式(1-2C)表示之結構之結構,包含以下述式(1-3C)表示之結構為較佳。 特定樹脂在主鏈上包含以式(1-3C)表示之結構為較佳。亦即,以式(1-3C)中的LB5 表示之結構包含在特定樹脂的主鏈中為較佳。 特定樹脂包含複數個以式(1-3C)表示之結構為較佳。特定樹脂包含複數個以式(1-3C)表示之結構時,複數個以式(1-3C)表示之結構可以相同,亦可以不同。 [化學式22] 式(1-3C)中,LB5 表示nB2+2價連接基,XB2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,XB1 表示以上述式(1-2C)表示之結構,nB2表示1以上的整數,存在複數個XB1 或XB2 時,複數個XB1 或XB2 可以相同,亦可以不同。[Structure represented by formula (1-3C)] When the specific resin includes the structure represented by formula (1-2C), the specific resin as the structure including the structure represented by formula (1-2C) includes the following formula (1 -3C) The structure indicated is better. The specific resin preferably contains a structure represented by formula (1-3C) in the main chain. That is, in the formula (1-3C) L B5 is preferably represented by the structures contained in the main chain of the specific resin. The specific resin preferably contains a plurality of structures represented by formula (1-3C). When the specific resin contains a plurality of structures represented by formula (1-3C), the plurality of structures represented by formula (1-3C) may be the same or different. [Chemical formula 22] In formula (1-3C), L B5 represents nB2+divalent linking group, X B2 represents ester bond, urethane bond, urea bond, amide bond or ether bond, X B1 represents the formula (1-2C ) Represents the structure, nB2 represents an integer of 1 or more. When there are multiple X B1 or X B2 , the multiple X B1 or X B2 may be the same or different.
式(1-3C)中,LB5 的含義與上述式(1-2)中的L1 相同,且較佳的態樣亦相同。 式LB5 包含以式(A-1)~(A-5)表示之結構中的任一個時,式(A-1)~(A-5)的說明中的“RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中b個分別為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,”可替換為“RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中nB2個分別為與式(2-1)中的XB2 的鍵結部位,”。 式(1-3C)中,XB2 的含義與上述式(1-2)中的X2 相同,且較佳的態樣亦相同。 式(1-3C)中,XB1 表示以上述式(1-2C)表示之結構,較佳的態樣如上述式(1-2C)的說明中所記載。 式(1-3C)中,nB2的含義與上述式(1-2)中的b相同,且較佳的態樣亦相同。In the formula (1-3C), L B5 has the same meaning as L 1 in the above formula (1-2), and preferred aspects are also the same. When the formula L B5 includes any of the structures represented by the formulas (A-1) to (A-5), "R A11 to R A14 , R in the description of the formulas (A-1) to (A-5) A21 to R A24 , R A31 to R A38 , R A41 to R A48, and R A51 to R A58 are the bonding sites of X 2 in formula (1-2) or formula (1-3) described later, respectively , "may be replaced by" the R A11 ~ R A14, R A21 ~ R A24, R A31 ~ R A38, R A41 ~ R A48 and R A51 ~ R A58 are in a nB2 formula (2-1) X The bonding part of B2,". In the formula (1-3C), X B2 has the same meaning as X 2 in the above formula (1-2), and preferred aspects are also the same. In the formula (1-3C), X B1 represents the structure represented by the above formula (1-2C), and a preferable aspect is as described in the description of the above formula (1-2C). In the formula (1-3C), nB2 has the same meaning as b in the above formula (1-2), and preferred aspects are also the same.
[以式(1-4C)表示之重複單元] 特定樹脂包含以式(1-2C)表示之結構或以式(1-3C)表示之結構時,特定樹脂包含以下述式(1-4C)表示之重複單元為較佳。 [化學式23] 式(1-4C)中,LB5 表示nB2+2價連接基,XB2 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,XB1 表示以上述式(1-2C)表示之結構,nB2表示1以上的整數,LB4 表示以上述式(1-3)中的式(L4-1)或式(L4-2)表示之結構,存在複數個XB1 或XB2 時,複數個XB1 或XB2 可以相同,亦可以不同。[Repeating unit represented by formula (1-4C)] When the specific resin contains the structure represented by the formula (1-2C) or the structure represented by the formula (1-3C), the specific resin contains the following formula (1-4C) The repeating unit shown is preferred. [Chemical formula 23] In formula (1-4C), L B5 represents nB2+divalent linking group, X B2 represents ester bond, urethane bond, urea bond, amide bond or ether bond, X B1 represents the formula (1-2C ) Represents the structure, nB2 represents an integer of 1 or more, L B4 represents the structure represented by the formula (L4-1) or the formula (L4-2) in the above formula (1-3), there are plural X B1 or X B2 At the time, a plurality of X B1 or X B2 may be the same or different.
式(1-4C)中,LB5 、XB2 、XB1 及nB2的含義分別與上述式(1-3C)中的LB5 、XB2 、XB1 及nB2相同,且較佳的態樣亦相同。 式(1-4C)中,LB4 的含義與上述式(1-3)中的L4 相同,且較佳的態樣亦相同。In the formula (1-4C), L B5, X B2, X B1 and nB2 meaning as in the formula (1-3C) L B5, X B2 , X B1 and nB2 are the same, and preferably also the aspect of the same. In formula (1-4C), L B4 has the same meaning as L 4 in the above formula (1-3), and preferred aspects are also the same.
-樹脂種類- 式(1-4C)中,LB4 為以式(L4-1)表示之基團所表示之結構時,特定樹脂為聚醯亞胺為較佳。 式(1-4C)中,LB4 為以式(L4-2)表示之基團所表示之結構時,特定樹脂為聚醯亞胺前驅物為較佳。- the type of resin - when the formula (1-4C), L B4 is a group represented by the formula (L4-1) represented by the structure, the specific resin is a polyimide is preferred. When the formula (1-4C), L B4 is a group represented by the formula (L4-2) represented by the structure, the specific resin is a polyimide precursor is preferred.
-含量- 特定樹脂包含以式(1-4C)表示之重複單元時,以式(1-4C)表示之重複單元的含量相對於特定樹脂的總質量為0.1~80質量%為較佳,10~80質量%為更佳,20~75質量%為進一步較佳。 特定樹脂可以僅包含一種以式(1-4C)表示之重複單元,亦可以包含兩種以上。-content- When the specific resin contains the repeating unit represented by the formula (1-4C), the content of the repeating unit represented by the formula (1-4C) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 80 mass% % Is more preferable, and 20 to 75% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (1-4C), or may include two or more types.
[以式(2-1)表示之重複單元] 特定樹脂亦可以進一步包含以下述式(2-1)表示之重複單元。 又,特定樹脂包含以式(1-2B)或式(1-2C)表示之結構時,特定樹脂在以式(1-2B)或式(1-2C)表示之結構以外的其他結構包含聚合性基。 特定樹脂為聚醯亞胺時,特定樹脂作為具有聚合性基之重複單元,進一步包含以下述式(2-1)表示且L21 為式(L4-1)之重複單元為較佳。 特定樹脂為聚醯亞胺前驅物時,特定樹脂在以式(1-3B)表示之重複單元中的LB4 或以式(1-4C)表示之重複單元中的LB4 包含聚合性基、或進一步包含以下述式(2-1)表示且L21 為式(L4-2)之重複單元為較佳。在以式(1-3B)表示之重複單元中的LB4 或以式(1-4C)表示之重複單元中的LB4 包含聚合性基時,上述LB4 為式(L4-2)且式(L4-2)中的R113 及R114 中的至少一者包含聚合性基為較佳。 [化學式24] 式(2-1)中,L21 表示b2+2價連接基,X22 表示酯鍵、胺甲酸乙酯鍵、脲鍵、醯胺鍵或醚鍵,X21 表示包含聚合性基之基團,X21 及X22 為不包含聚伸烷氧基的基團,b2表示1以上的整數,L4 表示以上述式(1-3)中的式(L4-1)或式(L4-2)表示之結構,存在複數個X22 或X21 時,複數個X22 或X21 可以相同,亦可以不同。[Repeating unit represented by formula (2-1)] The specific resin may further include a repeating unit represented by the following formula (2-1). In addition, when the specific resin includes a structure represented by formula (1-2B) or formula (1-2C), the specific resin includes polymerization in a structure other than the structure represented by formula (1-2B) or formula (1-2C) Sex-based. When the specific resin is a polyimide, it is preferable that the specific resin further includes a repeating unit represented by the following formula (2-1) and L 21 is a formula (L4-1) as a repeating unit having a polymerizable group. Specific resin is polyimide precursor, L B4 specific resin of the repeating unit represented by the formula (1-3B) or the repeating unit represented by the formula (1-4C) L B4 is a polymerizable group, Or it is preferable to further include the repeating unit represented by the following formula (2-1) and L 21 is a formula (L4-2). When the repeating unit represented by the repeating unit represented by the formula (1-3B) of formula L B4 or (1-4C) L B4 is a polymerizable group, L B4 above formula (L4-2) and formula It is preferable that at least one of R 113 and R 114 in (L4-2) contains a polymerizable group. [Chemical formula 24] In formula (2-1), L 21 represents a b2+divalent linking group, X 22 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and X 21 represents a group containing a polymerizable group , X 21 and X 22 are groups that do not contain a polyalkyleneoxy group, b2 represents an integer of 1 or more, and L 4 represents the formula (L4-1) or the formula (L4-2) in the above formula (1-3) ) Indicates the structure. When there are multiple X 22 or X 21 , the multiple X 22 or X 21 may be the same or different.
式(2-1)中,L21 、X22 、b2及L4 的含義分別與上述式(1-3)中的L1 、X2 、b及L4 相同,且較佳的態樣亦相同。 式L21 包含以式(A-1)~(A-5)表示之結構中的任一個時,式(A-1)~(A-5)的說明中的“RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中b個分別為與式(1-2)或後述式(1-3)中的X2 的鍵結部位,”可替換為“RA11 ~RA14 、RA21 ~RA24 、RA31 ~RA38 、RA41 ~RA48 及RA51 ~RA58 中b2個分別為與式(2-1)中的X22 的鍵結部位,”。 式(2-1)中,X21 表示包含聚合性基之基團,上述以式(Z-1)表示之基團為較佳。In formula (2-1), the meanings of L 21 , X 22 , b2 and L 4 are the same as those of L 1 , X 2 , b and L 4 in the above formula (1-3), and preferred aspects are also the same. When formula L 21 includes any one of the structures represented by formulas (A-1) to (A-5), "R A11 to R A14 , R in the description of formulas (A-1) to (A-5) A21 to R A24 , R A31 to R A38 , R A41 to R A48, and R A51 to R A58 are the bonding sites of X 2 in formula (1-2) or formula (1-3) described later, respectively ," can be replaced with "R A11 ~R A14 , RA21 ~ RA24 , RA31 ~ RA38 , RA41 ~ RA48 and RA51 ~R A58 where b2 is the same as X in formula (2-1) The bonding part of 22,". In the formula (2-1), X 21 represents a group containing a polymerizable group, and the group represented by the above formula (Z-1) is preferred.
-樹脂種類- 式(2-1)中,L4 為以式(L4-1)表示之基團所表示之結構時,特定樹脂為聚醯亞胺為較佳。 式(2-1)中,L4 為以式(L4-2)表示之基團所表示之結構時,特定樹脂為聚醯亞胺前驅物為較佳。-Resin Type-In the formula (2-1), when L 4 is a structure represented by a group represented by the formula (L4-1), the specific resin is preferably a polyimide. In formula (2-1), when L 4 is a structure represented by a group represented by formula (L4-2), it is preferable that the specific resin is a polyimide precursor.
-含量- 特定樹脂包含以式(2-1)表示之重複單元時,以式(1-4C)表示之重複單元的含量相對於特定樹脂的總質量為0.1~80質量%為較佳,10~80質量%為更佳,20~75質量%為進一步較佳。 特定樹脂可以僅包含一種以式(2-1)表示之重複單元,亦可以包含兩種以上。-content- When the specific resin contains the repeating unit represented by the formula (2-1), the content of the repeating unit represented by the formula (1-4C) relative to the total mass of the specific resin is preferably 0.1 to 80% by mass, and 10 to 80 mass% % Is more preferable, and 20 to 75% by mass is still more preferable. The specific resin may include only one type of repeating unit represented by formula (2-1), or may include two or more types.
[其他重複單元] -以式(4)表示之重複單元- 特定樹脂亦可以進一步包含以下述式(4)表示之重複單元。 特定樹脂包含以下述式(4)表示之重複單元時,特定樹脂為聚醯亞胺為較佳。 特定樹脂包含以下述式(4)表示之重複單元時,特定樹脂在主鏈上包含以下述式(4)表示之重複單元為較佳。 [化學式25] 式(4)中,R131 表示2價有機基,R132 表示4價有機基。[Other repeating units] -Repeating units represented by the formula (4)- The specific resin may further include a repeating unit represented by the following formula (4). When the specific resin contains a repeating unit represented by the following formula (4), the specific resin is preferably polyimide. When the specific resin includes a repeating unit represented by the following formula (4), the specific resin preferably includes a repeating unit represented by the following formula (4) in the main chain. [Chemical formula 25] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.
作為R131 所表示之2價有機基,可例示與後述式(1)中的R111 相同的基團,且較佳的範圍亦相同。作為R132 所表示之4價有機基,可例示與上述式(L4-1)中的R115 相同的基團,且較佳的範圍亦相同。As the divalent organic group represented by R 131 , the same group as R 111 in the formula (1) described later can be exemplified, and the preferable range is also the same. As the tetravalent organic group represented by R 132 , the same group as R 115 in the above formula (L4-1) can be exemplified, and the preferred range is also the same.
特定樹脂中的以式(1-1)表示之結構中的R1 為不包含聚合性基的取代基時,R131 及R132 中的至少一者可以包含聚合性基,亦可以在聚醯亞胺的末端具有包含聚合性基之結構。 When R 1 in the structure represented by formula (1-1) in the specific resin is a substituent that does not include a polymerizable group, at least one of R 131 and R 132 may include a polymerizable group, or may be in the polyamide The terminal of the imine has a structure containing a polymerizable group.
特定樹脂包含以式(4)表示之重複單元時(例如,特定樹脂為聚醯亞胺時),特定樹脂中,相對於特定樹脂的總質量包含1~80質量%以式(4)表示之重複單元為較佳,包含10~70質量%為更佳,包含20~60質量%為進一步較佳。 又,特定樹脂為聚醯亞胺時,還能夠設為特定樹脂實質上不包含以式(4)表示之重複單元之態樣,這種態樣中,以式(4)表示之重複單元的含量相對於特定樹脂的總質量為5質量%以下為較佳,1質量%以下為更佳。 又,特定樹脂為聚醯亞胺時,特定樹脂中所包含之以式(1-3)表示之重複單元、以式(1-3B)表示之重複單元、以式(1-4C)表示之重複單元、以式(2-1)表示之重複單元、以式(4)表示之重複單元的合計含量(上述重複單元中,亦可以存在不包含之重複單元)相對於特定樹脂的總質量為50~100質量%為較佳,60~99質量%為更佳,70~95質量%為進一步較佳。When the specific resin contains the repeating unit represented by formula (4) (for example, when the specific resin is polyimide), the specific resin contains 1 to 80% by mass relative to the total mass of the specific resin expressed by formula (4) The repeating unit is preferable, and it is more preferable to contain 10 to 70% by mass, and it is still more preferable to contain 20 to 60% by mass. In addition, when the specific resin is polyimide, it can also be set to a state where the specific resin does not substantially contain the repeating unit represented by the formula (4). In this aspect, the repeating unit represented by the formula (4) is The content is preferably 5% by mass or less with respect to the total mass of the specific resin, and more preferably 1% by mass or less. In addition, when the specific resin is polyimide, the repeating unit represented by formula (1-3), the repeating unit represented by formula (1-3B), and the repeating unit represented by formula (1-4C) contained in the specific resin The total content of the repeating unit, the repeating unit represented by formula (2-1), and the repeating unit represented by formula (4) (in the above repeating unit, there may be repeating units not included) relative to the total mass of the specific resin 50 to 100% by mass is preferable, 60 to 99% by mass is more preferable, and 70 to 95% by mass is still more preferable.
-以式(1)表示之重複單元- 特定樹脂亦可以進一步包含以下述式(1)表示之重複單元。 特定樹脂包含以下述式(1)表示之重複單元時,特定樹脂為聚醯亞胺前驅物為較佳。 特定樹脂包含以下述式(1)表示之重複單元時,特定樹脂在主鏈上具有以下述式(1)表示之重複單元為較佳。 [化學式26] A1 及A2 分別獨立地表示氧原子或NH,R111 表示2價有機基,R115 表示4價有機基,R113 及R114 分別獨立地表示氫原子或1價有機基。-Repeating unit represented by formula (1)- The specific resin may further include a repeating unit represented by the following formula (1). When the specific resin contains a repeating unit represented by the following formula (1), the specific resin is preferably a polyimide precursor. When the specific resin contains a repeating unit represented by the following formula (1), the specific resin preferably has a repeating unit represented by the following formula (1) in the main chain. [Chemical formula 26] A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
式(1)中,A1 、A2 、R113 、R114 及R115 的含義分別獨立地與上述式(L4-2)中的A1 、A2 、R113 、R114 及R115 相同,且較佳的態樣亦相同。 式(1)中,R111 表示2價有機基。作為2價有機基,可例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基及芳香族基、雜芳香族基或將該等組合兩個以上之基團,碳數2~20的直鏈的脂肪族基、碳數3~20的支鏈的脂肪族基、碳數3~20的環狀的脂肪族基、碳數6~20的芳香族基或將該等組合兩個以上之基團為較佳,碳數6~20的芳香族基為更佳。(1) In the formula, A 1, A 2, R 113, R 114, and the meanings of R 115 each independently have the above formula (L4-2) A 1, A 2 , R 113, R 114 and R 115 identical , And the preferred aspect is also the same. In formula (1), R 111 represents a divalent organic group. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or a combination of two or more of these groups, with a carbon number of 2 -20 linear aliphatic groups, branched aliphatic groups with 3-20 carbons, cyclic aliphatic groups with 3-20 carbons, aromatic groups with 6-20 carbons, or a combination of these Two or more groups are preferred, and an aromatic group having 6 to 20 carbon atoms is more preferred.
式(1)中的R111 衍生自二胺為較佳。作為聚醯亞胺前驅物的製造中所使用之二胺,可列舉直鏈狀或支鏈狀脂肪族、環狀脂肪族或芳香族二胺等。二胺可以僅使用一種,亦可以使用兩種以上。 Preferably, R 111 in the formula (1) is derived from a diamine. Examples of diamines used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
具體而言,二胺為包含碳數2~20的直鏈脂肪族基、碳數3~20的支鏈狀或環狀脂肪族基、碳數6~20的芳香族基或將該等組合兩個以上之基團之二胺為較佳,包含碳數6~20的芳香族基之二胺為更佳。作為芳香族基的例子,可列舉下述芳香族基。Specifically, the diamine contains a linear aliphatic group having 2 to 20 carbons, a branched or cyclic aliphatic group having 3 to 20 carbons, an aromatic group having 6 to 20 carbons, or a combination of these Diamines with two or more groups are preferred, and diamines containing aromatic groups with 6 to 20 carbon atoms are more preferred. As an example of an aromatic group, the following aromatic groups can be mentioned.
[化學式27] [Chemical formula 27]
式中,A為單鍵或者可以被氟原子取代的碳數1~10的脂肪族烴基、-O-、-C(=O)-、-S-、-S(=O)2 -、-NHC(=O)-或將該等組合兩個以上之基團為較佳,單鍵或者選自可以被氟原子取代的碳數1~3的伸烷基、-O-、-C(=O)-、-S-及-S(=O)2 -中之基團為更佳,選自包括-CH2 -、-O-、-S-、-S(=O)2 -、-C(CF3 )2 -及-C(CH3 )2 -之群組中之2價基團為進一步較佳。In the formula, A is a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) 2 -,- NHC (=O)-or a combination of two or more of these groups is preferred, a single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- and -S(=O) 2 -is more preferably selected from the group including -CH 2 -, -O-, -S-, -S(=O) 2 -,- The divalent group in the group of C(CF 3 ) 2 -and -C(CH 3 ) 2-is further preferred.
作為二胺,具體而言,可列舉選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,6-二胺基己烷;1,2-二胺基環戊烷或1,3-二胺基環戊烷、1,2-二胺基環己烷、1,3-二胺基環己烷或1,4-二胺基環己烷、1,2-雙(胺基甲基)環己烷、1,3-雙(胺基甲基)環己烷或1,4-雙(胺基甲基)環己烷、雙-(4-胺基環己基)甲烷、雙-(3-胺基環己基)甲烷、4,4’-二胺基-3,3’-二甲基環己基甲烷或異佛爾酮二胺;間苯二胺或對苯二胺、二胺基甲苯、4,4’-二胺基聯苯或3,3’-二胺基聯苯、4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、4,4’-二胺基二苯基甲烷或3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸或3,3-二胺基二苯基碸、4,4’-二胺基二苯硫醚或3,3’-二胺基二苯硫醚、4,4’-二胺基二苯甲酮或3,3’-二胺基二苯甲酮、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯(4,4’-二胺基-2,2’-二甲基聯苯)、3,3’-二甲氧基-4,4’-二胺基聯苯、雙(4-胺基-3-羧基苯基)甲烷、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-胺基苯基)六氟丙烷、2,2-雙(3-羥基-4-胺基苯基)丙烷、2,2-雙(3-羥基-4-胺基苯基)六氟丙烷、2,2-雙(3-胺基-4-羥基苯基)丙烷、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、雙(3-胺基-4-羥基苯基)碸、雙(4-胺基-3-羥基苯基)碸、4,4’-二胺基對聯三苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(2-胺基苯氧基)苯基]碸、1,4-雙(4-胺基苯氧基)苯、9,10-雙(4-胺基苯基)蒽、3,3’-二甲基-4,4’-二胺基二苯基碸、1,3-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯基)苯、3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’-二甲基-4,4’-二胺基二苯基甲烷、4,4’-二胺基八氟聯苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、9,9-雙(4-胺基苯基)-10-氫蒽、3,3’,4,4’-四胺基聯苯、3,3’,4,4’-四胺基二苯醚、1,4-二胺基蒽醌、1,5-二胺基蒽醌、3,3-二羥基-4,4’-二胺基聯苯、9,9’-雙(4-胺基苯基)茀、4,4’-二甲基-3,3’-二胺基二苯基碸、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、2-(3’,5’-二胺基苯甲醯氧基)甲基丙烯酸乙酯、2,4-二胺基枯烯或2,5-二胺基枯烯、2,5-二甲基-對苯二胺、乙醯胍胺、2,3,5,6-四甲基-對苯二胺、2,4,6-三甲基-間苯二胺、4,6-二羥基-1,3-苯二胺、雙(3-胺基丙基)四甲基二矽氧烷、2,7-二胺基茀、2,5-二胺基吡啶、1,2-雙(4-胺基苯基)乙烷、二胺基苯甲醯苯胺、二胺苯甲酸、二胺苯甲酸的酯、1,5-二胺基萘、二胺基三氟甲苯、1,3-雙(4-胺基苯基)六氟丙烷、1,4-雙(4-胺基苯基)八氟丁烷、1,5-雙(4-胺基苯基)十氟戊烷、1,7-雙(4-胺基苯基)十四氟庚烷、2,2-雙[4-(3-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(2-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)-3,5-二甲基苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)-3,5-雙(三氟甲基)苯基]六氟丙烷、對雙(4-胺基-2-三氟甲基苯氧基)苯、4,4’-雙(4-胺基-2-三氟甲基苯氧基)聯苯、4,4’-雙(4-胺基-3-三氟甲基苯氧基)聯苯、4,4’-雙(4-胺基-2-三氟甲基苯氧基)二苯基碸、4,4’-雙(3-胺基-5-三氟甲基苯氧基)二苯基碸、2,2-雙[4-(4-胺基-3-三氟甲基苯氧基)苯基]六氟丙烷、3,3’,5,5’-四甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、2,2’,5,5’,6,6’-六氟聯甲苯胺及4,4’-二胺基四聯苯中之至少一種二胺。As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4 , 4'-diaminodiphenyl sulfide or 3,3-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, bis(4-amino-3-carboxyphenyl)methane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis (3-Amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, Bis(4-amino-3-hydroxyphenyl), 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-( 4-aminophenoxy) phenyl] ash, bis[4-(3-aminophenoxy) phenyl] ash, bis[4-(2-aminophenoxy) phenyl] ash, 1 ,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl Supplement, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3 ,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diamine Octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraamino Diphenyl ether, 1,4-diaminoanthraquinone, 1 ,5-Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl) stilbene, 4,4'-dimethyl -3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5' -Diaminobenzyloxy) ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, ethyl Guanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,6-dihydroxy-1,3-phenylenediamine , Bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethyl Alkyl, diaminobenzaniline, diaminobenzoic acid, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl) ) Hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-amine Phenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy) )Phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4 -Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4' -Bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4' -Bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfide, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfide, 2,2-Bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine And at least one diamine in 4,4'-diaminotetrabiphenyl.
又,以下所示之二胺(DA-1)~(DA-18)亦較佳。In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.
[化學式28] [Chemical formula 28]
[化學式29] [Chemical formula 29]
又,作為較佳例,亦可列舉在主鏈上具有至少兩個伸烷基二醇單元之二胺。較佳為在一個分子中合計包含兩個以上的乙二醇鏈、丙二醇鏈中的任一者或兩者之二胺,更佳為不包含芳香環的二胺。作為具體例,可列舉JEFFAMINE(註冊商標)KH-511、JEFFAMINE(註冊商標)ED-600、JEFFAMINE(註冊商標)ED-900、JEFFAMINE(註冊商標)ED-2003、JEFFAMINE(註冊商標)EDR-148、JEFFAMINE(註冊商標)EDR-176、D-200、D-400、D-2000、D-4000(以上為商品名,HUNTSMAN公司製)、1-(2-(2-(2-胺基丙氧基)乙氧基)丙氧基)丙烷-2-胺、1-(1-(1-(2-胺基丙氧基)丙烷-2-基)氧基)丙烷-2-胺等,但並不限定於該等。Moreover, as a preferable example, the diamine which has at least two alkylene glycol units in the main chain can also be mentioned. Preferably, a diamine containing two or more of ethylene glycol chains and propylene glycol chains or both in total is preferable in one molecule, and a diamine that does not contain an aromatic ring is more preferable. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148 , JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropyl) (Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., But it is not limited to these.
以下示出JEFFAMINE(註冊商標)KH-511、JEFFAMINE(註冊商標)ED-600、JEFFAMINE(註冊商標)ED-900、JEFFAMINE(註冊商標)ED-2003、JEFFAMINE(註冊商標)EDR-148、JEFFAMINE(註冊商標)EDR-176的結構。The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.
[化學式30] [Chemical formula 30]
上述中,x、y、z為算術平均值。In the above, x, y, and z are the arithmetic averages.
從所獲得之硬化膜的柔軟性的觀點考慮,式(1)中的R111 以-Ar0 -L0 -Ar0 -表示為較佳。Ar0 分別獨立地為芳香族烴基(碳數6~22為較佳,6~18為更佳,6~10為特佳),伸苯基為較佳。L0 表示單鍵或者可以被氟原子取代的碳數1~10的脂肪族烴基、-O-、-C(=O)-、-S-、-S(=O)2 -、-NHCO-或將該等組合兩個以上之基團。L0 的較佳範圍的含義與上述A相同。From the viewpoint of the flexibility of the cured film obtained, R 111 in the formula (1) is preferably represented by -Ar 0 -L 0 -Ar 0 -. Ar 0 is each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, more preferably 6-18, particularly preferably 6-10), and phenylene is preferred. L 0 represents a single bond or an aliphatic hydrocarbon group of 1 to 10 carbons which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NHCO- Or these groups can be combined with two or more groups. The meaning of the preferable range of L 0 is the same as the above-mentioned A.
從i射線透過率的觀點考慮,式(1)中的R111 為以下述式(51)或式(61)表示之2價有機基為較佳。尤其,從i射線透過率、易獲得的觀點考慮,以式(61)表示之2價有機基為更佳。From the viewpoint of i-ray transmittance, R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by the formula (61) is more preferable.
[化學式31] [Chemical formula 31]
式(51)中,R50 ~R57 分別獨立地為氫原子、氟原子或1價有機基,R50 ~R57 中的至少一個氟原子、甲基、氟甲基、二氟甲基或三氟甲基,*分別獨立地表示與其他結構的鍵結部位。In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or Trifluoromethyl, * each independently represents a bonding site with other structures.
作為R50 ~R57 的1價有機基,可列舉碳數1~10(較佳為碳數1~6)的未經取代的烷基、碳數1~10(較佳為碳數1~6)的氟化烷基等。Examples of the monovalent organic group of R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably 1 to 6 carbons). 6) The fluorinated alkyl group and so on.
[化學式32] [Chemical formula 32]
式(61)中,R58 及R59 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。In the formula (61), R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
作為賦予式(51)或(61)的結構之二胺化合物,可列舉二甲基-4,4’-二胺基聯苯、2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、2,2’-雙(氟)-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。可以使用該等中的一種,亦可以組合使用兩種以上。Examples of the diamine compound imparting the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4 '-Diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.
特定樹脂包含以式(1)表示之重複單元時(例如,特定樹脂為聚醯亞胺前驅物時),特定樹脂中,相對於特定樹脂的總質量包含1~90質量%以式(1)表示之重複單元為較佳,包含10~80質量%為更佳,包含20~70質量%為進一步較佳。 又,特定樹脂為聚醯亞胺前驅物時,還能夠設為特定樹脂實質上不包含以式(1)表示之重複單元的態樣,這種態樣中,以式(1)表示之重複單元的含量相對於特定樹脂的總質量為5質量%以下為較佳,1質量%以下為更佳。 又,特定樹脂為聚醯亞胺前驅物時,特定樹脂中所包含之以式(1-3)表示之重複單元、以式(1-3B)表示之重複單元、以式(1-4C)表示之重複單元、以式(2-1)表示之重複單元、以式(1)表示之重複單元的合計含量(上述重複單元中,亦可以存在不包含之重複單元)相對於特定樹脂的總質量為50~100質量%為較佳,60~99質量%為更佳,70~95質量%為進一步較佳。When the specific resin contains the repeating unit represented by the formula (1) (for example, when the specific resin is a polyimide precursor), the specific resin contains 1 to 90% by mass relative to the total mass of the specific resin in accordance with formula (1) The indicated repeating unit is preferable, and it is more preferable to contain 10 to 80% by mass, and it is more preferable to contain 20 to 70% by mass. In addition, when the specific resin is a polyimide precursor, it can also be set to a state in which the specific resin does not substantially contain the repeating unit represented by formula (1). In this aspect, the repeating unit represented by formula (1) The content of the unit relative to the total mass of the specific resin is preferably 5% by mass or less, and more preferably 1% by mass or less. In addition, when the specific resin is a polyimide precursor, the repeating unit represented by the formula (1-3), the repeating unit represented by the formula (1-3B), and the repeating unit represented by the formula (1-4C) contained in the specific resin The total content of the repeating unit represented, the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (1) (in the above repeating units, there may be repeating units not included) relative to the total content of the specific resin The mass is preferably from 50 to 100% by mass, more preferably from 60 to 99% by mass, and even more preferably from 70 to 95% by mass.
[含量] 從提高所獲得之硬化膜的斷裂伸長率之觀點考慮,本發明的硬化性樹脂組成物中的特定樹脂的含量相對於硬化性樹脂組成物的總固體成分為20質量%以上為較佳,30質量%以上為更佳,40質量%以上為進一步較佳。 作為上述含量的上限,從提高硬化性樹脂組成物的解析度的觀點考慮,99.5質量%以下為較佳,99質量%以下為更佳,98質量%以下為進一步較佳,97質量%以下為更進一步較佳,95質量%以下為更進一步較佳。[content] From the viewpoint of increasing the elongation at break of the cured film obtained, the content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more with respect to the total solid content of the curable resin composition. The mass% or more is more preferable, and 40 mass% or more is more preferable. As the upper limit of the above content, from the viewpoint of improving the resolution of the curable resin composition, 99.5% by mass or less is preferable, 99% by mass or less is more preferable, 98% by mass or less is more preferable, and 97% by mass or less is It is still more preferable, and 95% by mass or less is still more preferable.
[特定樹脂的物理性質] -分子量- 特定樹脂的重量平均分子量(Mw)為2,000~500,000為較佳,5,000~100,000為更佳,10,000~50,000為進一步較佳。 特定樹脂的數量平均分子量(Mn)為800~250,000為較佳,2,000~50,000為更佳,4,000~25,000為進一步較佳。 特定樹脂的分子量的分散度為1.5~3.5為較佳,2~3為更佳。 本說明書中,分子量的分散度表示重量平均分子量除以數量平均分子量而得之值(重量平均分子量/數量平均分子量)。[Physical properties of specific resin] -Molecular weight- The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) of the specific resin is preferably 800-250,000, more preferably 2,000-50,000, and still more preferably 4,000-25,000. The molecular weight dispersion of the specific resin is preferably 1.5 to 3.5, and more preferably 2 to 3. In this specification, the degree of molecular weight dispersion means the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).
-酸值- 將硬化性樹脂組成物使用於後述溶劑顯影中時,特定樹脂的酸值為1mmol/g以下為較佳,0.5mmol/g以下為更佳,0.3mmol/g為進一步較佳。上述酸值的下限並無特別限定,只要為0mmol/g以上即可。 將硬化性樹脂組成物使用於後述鹼性顯影時,特定樹脂的酸值為1.2~7mmol/g為較佳,1.5~6mmol/g為更佳,2~5mmol/g為進一步較佳。 本發明中,酸值是指特定樹脂1g中所包含之酸基的量(mmol)。 上述酸基表示被pH12以上的鹼(例如氫氧化鈉)中和之基團。又,上述酸基為pKa為10以下的基團為較佳。 上述酸值藉由公知的方法測量,例如藉由JIS K 0070:1992中所記載的方法測量。-Acid value- When the curable resin composition is used in the solvent development described below, the acid value of the specific resin is preferably 1 mmol/g or less, more preferably 0.5 mmol/g or less, and more preferably 0.3 mmol/g. The lower limit of the above acid value is not particularly limited, as long as it is 0 mmol/g or more. When the curable resin composition is used for alkaline development described later, the acid value of the specific resin is preferably 1.2 to 7 mmol/g, more preferably 1.5 to 6 mmol/g, and even more preferably 2 to 5 mmol/g. In the present invention, the acid value refers to the amount (mmol) of acid groups contained in 1 g of the specific resin. The aforementioned acid group means a group neutralized by a base having a pH of 12 or higher (for example, sodium hydroxide). Moreover, it is preferable that the said acid group is a group with a pKa of 10 or less. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
[特定樹脂的較佳的態樣] 特定樹脂為選自包括聚醯亞胺及聚醯亞胺前驅物之群組中之至少一種樹脂。 以下說明中,將以式(1-3)表示且L4 為式(L4-1)之重複單元稱為重複單元PI-1。 將以式(1-3B)表示且LB4 為式(L4-1)之重複單元稱為重複單元PI-2。 將以式(1-4C)表示且LB4 為式(L4-1)之重複單元稱為重複單元PI-3。 將以式(2-1)表示且L4 為式(L4-1)之重複單元稱為重複單元PI-4。 將以式(1-3)表示且L4 為式(L4-2)之重複單元稱為重複單元PIP-1。 將以式(1-3B)表示且LB4 為式(L4-2)之重複單元稱為重複單元PIP-2。 將以式(1-4C)表示且LB4 為式(L4-2)之重複單元稱為重複單元PIP-3。 將以式(2-1)表示且L4 為式(L4-2)之重複單元稱為重複單元PIP-4。[Preferred Aspects of Specific Resin] The specific resin is at least one resin selected from the group consisting of polyimine and polyimide precursors. In the following description, the repeating unit represented by the formula (1-3) and L 4 is the formula (L4-1) is referred to as repeating unit PI-1. It will be represented by the formula (1-3B) and L B4 repeating units of formula (L4-1) of the repeating units called PI-2. It will be represented by the formula (1-4C) and repeating units of the formula L B4 (L4-1) of the repeating units called PI-3. The repeating unit represented by formula (2-1) and L 4 of formula (L4-1) is referred to as repeating unit PI-4. The repeating unit represented by formula (1-3) and L 4 of formula (L4-2) is referred to as repeating unit PIP-1. The repeating unit represented by formula (1-3B) and L B4 of formula (L4-2) is referred to as repeating unit PIP-2. The repeating unit represented by formula (1-4C) and L B4 of formula (L4-2) is referred to as repeating unit PIP-3. The repeating unit represented by formula (2-1) and L 4 of formula (L4-2) is referred to as repeating unit PIP-4.
-聚醯亞胺- 特定樹脂為聚醯亞胺時,特定樹脂為下述PI1~下述PI3中的任一個中所記載的聚醯亞胺為較佳。 PI1:包含重複單元PI-1之聚醯亞胺 PI2:包含重複單元PI-2及重複單元PI-4之聚醯亞胺 PI3:包含重複單元PI-3及重複單元PI-4之聚醯亞胺 上述PI1中所記載的聚醯亞胺亦可以進一步包含重複單元PIP-1。 上述PI2中所記載的聚醯亞胺亦可以進一步包含選自包括重複單元PIP-2及重複單元PIP-4之群組中之至少一種。 上述PI3中所記載的聚醯亞胺亦可以進一步包含選自包括重複單元PIP-3及重複單元PIP-4之群組中之至少一種。 上述PI1中所記載的聚醯亞胺亦可以進一步包含重複單元PI-4。上述PI1中所記載的聚醯亞胺亦可以進一步包含重複單元PI-4。 上述PI1~PI3中所記載的聚醯亞胺亦可以進一步包含以式(4)表示之重複單元等其他重複單元。上述PI1~PI3中所記載的聚醯亞胺包含以式(4)表示之重複單元時,亦可以進一步包含以式(1)表示之重複單元。-Polyimide- When the specific resin is a polyimide, the specific resin is preferably the polyimide described in any one of the following PI1 to the following PI3. PI1: Polyimine containing repeating unit PI-1 PI2: Polyimide containing repeating unit PI-2 and repeating unit PI-4 PI3: Polyimide containing repeating unit PI-3 and repeating unit PI-4 The polyimide described in PI1 may further include the repeating unit PIP-1. The polyimide described in PI2 may further include at least one selected from the group consisting of the repeating unit PIP-2 and the repeating unit PIP-4. The polyimide described in PI3 may further include at least one selected from the group consisting of the repeating unit PIP-3 and the repeating unit PIP-4. The polyimide described in PI1 may further include a repeating unit PI-4. The polyimide described in PI1 may further include a repeating unit PI-4. The polyimide described in the above PI1 to PI3 may further include other repeating units such as the repeating unit represented by formula (4). When the polyimide described in PI1 to PI3 includes a repeating unit represented by formula (4), it may further include a repeating unit represented by formula (1).
又,特定樹脂為聚醯亞胺時,特定樹脂的閉環率為70%以上為較佳,80%以上為更佳,90%以上為更佳。 特定樹脂為聚醯亞胺時的特定樹脂的閉環率為藉由下述式CR(PI)表示之值。 式CR(PI): 特定樹脂的閉環率(%)=(特定樹脂中的醯亞胺環的莫耳量)/(特定樹脂中的醯亞胺環的莫耳量+特定樹脂中的經閉環而能夠形成醯亞胺環的結構的莫耳量)×100 例如,特定樹脂為包括重複單元PI-1、重複單元PIP-1、以式(4)表示之重複單元及以式(1)表示之重複單元之樹脂時,閉環率為藉由下述式CR(PI)1表示之值。 式CR(PI)1: 特定樹脂的閉環率(%)=(重複單元PI-1的莫耳量+以式(4)表示之重複單元的莫耳量)/(重複單元PI-1的莫耳量+重複單元PIP-1的莫耳量+以式(4)表示之重複單元的莫耳量+以式(1)表示之重複單元的莫耳量)In addition, when the specific resin is polyimide, the ring closure rate of the specific resin is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. When the specific resin is polyimide, the ring closure rate of the specific resin is a value represented by the following formula CR (PI). Type CR (PI): Ring-closure rate of specific resin (%)=(mole amount of imidine ring in specific resin)/(mole amount of iminium ring in specific resin + ring-closure in specific resin to form imines The molar amount of the structure of the ring)×100 For example, when the specific resin is a resin including the repeating unit PI-1, the repeating unit PIP-1, the repeating unit represented by formula (4), and the repeating unit represented by formula (1), the ring closure rate is determined by the following formula CR (PI) Value represented by 1. Formula CR (PI) 1: The ring-closure rate of the specific resin (%)=(mole amount of repeating unit PI-1+mole amount of repeating unit represented by formula (4))/(mole amount of repeating unit PI-1+repeat unit PIP- The molar amount of 1 + the molar amount of the repeating unit represented by formula (4) + the molar amount of the repeating unit represented by formula (1))
-聚醯亞胺前驅物- 特定樹脂為聚醯亞胺前驅物時,特定樹脂為下述PIP1~下述PIP5中的任一個中所記載的聚醯亞胺為較佳。 PIP1:包含重複單元PIP-1之聚醯亞胺前驅物 PIP2:包含重複單元PIP-2,式(1-3B)中的LB4 為式(L4-2),式(L4-2)中的R113 及R114 中的至少一者包含聚合性基之聚醯亞胺前驅物 PIP3:包含重複單元PIP-2及重複單元PIP-4之聚醯亞胺前驅物 PIP4:包含重複單元PIP-3,式(1-3B)中的LB4 為式(L4-2),式(L4-2)中的R113 及R114 中的至少一者包含聚合性基之聚醯亞胺前驅物 PIP5:包含重複單元PIP-3及重複單元PIP-4之聚醯亞胺前驅物-Polyimine precursor- When the specific resin is a polyimide precursor, the specific resin is preferably the polyimide described in any one of PIP1 to PIP5 below. PIP1: including a repeating unit of the polyimide precursor PIP1 PIP2: comprising repeating units PIP2, formula (1-3B) L B4 of formula (L4-2), the formula (L4-2) in At least one of R 113 and R 114 includes a polyimide precursor PIP3 of a polymerizable group: a polyimide precursor PIP4 that includes a repeating unit PIP-2 and a repeating unit PIP-4: includes a repeating unit PIP-3 , L B4 in formula (1-3B) is formula (L4-2), and at least one of R 113 and R 114 in formula (L4-2) contains a polyimide precursor PIP5 of a polymerizable group: Polyimide precursor containing repeating unit PIP-3 and repeating unit PIP-4
[具體例] 作為特定樹脂的具體例,可列舉後述實施例中使用之特定樹脂。[Specific example] As a specific example of a specific resin, the specific resin used in the Example mentioned later can be mentioned.
[合成方法] 特定樹脂例如藉由後述實施例中的合成例所示之合成方法合成。[resolve resolution] The specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the below-mentioned examples.
特定樹脂為上述PI1中所記載之聚醯亞胺時,特定樹脂藉由依序進行例如下述(1)~(2)中所記載的步驟來合成。 (1)使具有羧基、羥基、胺基等官能基之二胺與二羧酸或二羧酸衍生物反應,反應之後藉由熱醯亞胺化、化學醯亞胺化(例如,藉由藉助觸媒的作用來促進環化反應)等方法來形成醯亞胺環,以獲得聚醯亞胺之步驟 (2)使具有能夠與上述官能基鍵結的基團(例如,羥基、可以被鹵化的羧基、異氰酸酯基等)、聚伸烷氧基及聚合性基之化合物(例如,聚伸烷基二醇單甲基丙烯酸酯等)與上述(1)中所獲得之聚醯亞胺中的上述官能基反應之步驟 作為具有能夠與上述官能基鍵結的基團、聚伸烷氧基、聚合性基之化合物,可以使用市售品,作為市售品,可列舉BLEMMER PE-90、PE-200、PE-350、PP-1000、PP-500、PP-800、AE-90U、AE-200、AE-400、AP-200、AP-400、AP-550、AP-800(均為NOF CORPORATION製)等。When the specific resin is the polyimide described in PI1, the specific resin is synthesized by sequentially performing, for example, the steps described in (1) to (2) below. (1) Reacting a diamine having a functional group such as a carboxyl group, a hydroxyl group, and an amino group with a dicarboxylic acid or a dicarboxylic acid derivative. After the reaction, thermal imidization or chemical imidization (for example, by using The role of catalyst to promote the cyclization reaction) and other methods to form the imine ring to obtain the step of polyimine (2) Making a compound having a group capable of bonding to the above functional group (for example, a hydroxyl group, a carboxyl group that can be halogenated, an isocyanate group, etc.), a polyalkyleneoxy group, and a polymerizable group (for example, polyalkylene two The step of reacting alcohol monomethacrylate, etc.) with the above functional group in the polyimide obtained in (1) above As a compound having a group capable of bonding to the above functional group, a polyalkyleneoxy group, and a polymerizable group, commercially available products can be used. Examples of commercially available products include BLEMMER PE-90, PE-200, and PE-350 , PP-1000, PP-500, PP-800, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800 (all manufactured by NOF CORPORATION), etc.
特定樹脂為上述PI2中所記載之聚醯亞胺時,特定樹脂藉由依序進行例如下述(3)~(4)中所記載的步驟來合成。 (3)使具有聚伸烷氧基之二胺(例如,雙(2-(3-胺基丙氧基)乙基)醚等)、具有羧基、羥基、胺基等官能基之二胺及二羧酸或二羧酸衍生物反應,反應之後藉由熱醯亞胺化、化學醯亞胺化(例如,藉由藉助觸媒的作用來促進環化反應)等方法來形成醯亞胺環,以獲得聚醯亞胺之步驟 (4)使具有能夠與上述官能基鍵結的基團(例如,羥基、可以被鹵化的羧基、異氰酸酯基等)及聚合性基之化合物(例如,甲基丙烯醯氯等)與上述(1)中所獲得之聚醯亞胺中的上述官能基反應之步驟When the specific resin is the polyimide described in PI2, the specific resin is synthesized by sequentially performing, for example, the steps described in (3) to (4) below. (3) Diamines with polyalkyleneoxy groups (for example, bis(2-(3-aminopropoxy)ethyl)ether, etc.), diamines with functional groups such as carboxyl, hydroxyl, and amino groups, and The reaction of dicarboxylic acid or dicarboxylic acid derivative, followed by thermal imidization, chemical imidization (for example, by using a catalyst to promote the cyclization reaction) to form an imide ring , The steps to obtain polyimide (4) A compound having a group capable of bonding to the above functional group (for example, a hydroxyl group, a halogenated carboxyl group, an isocyanate group, etc.) and a polymerizable group (for example, methacrylic acid chloride, etc.) are combined with the above (1 Steps of reacting the above functional groups in the polyimine obtained in)
特定樹脂為上述PI3中所記載之聚醯亞胺時,特定樹脂藉由依序進行例如下述(5)~(6)中所記載的步驟來合成。 (5)使具有羧基、羥基、胺基等官能基之二胺與二羧酸或二羧酸衍生物反應,反應之後藉由熱醯亞胺化、化學醯亞胺化(例如,藉由藉助觸媒的作用來促進環化反應)等方法來形成醯亞胺環,以獲得聚醯亞胺之步驟 (6)使具有能夠與上述官能基鍵結的基團(例如,羥基、可以被鹵化的羧基、異氰酸酯基等)及聚伸烷氧基之化合物(例如,聚伸烷基二醇單烷基醚等)、以及具有能夠與上述官能性基鍵結的基團(例如,羥基、可以被鹵化的羧基、異氰酸酯基等)及聚合性基之化合物(例如,羥乙基甲基丙烯酸酯等)與上述(1)中所獲得之聚醯亞胺中的上述官能基反應之步驟When the specific resin is the polyimide described in PI3, the specific resin is synthesized by sequentially performing, for example, the steps described in (5) to (6) below. (5) Reacting diamines with functional groups such as carboxyl groups, hydroxyl groups, and amino groups with dicarboxylic acids or dicarboxylic acid derivatives, followed by thermal imidization and chemical imidization (for example, by using The role of catalyst to promote the cyclization reaction) and other methods to form the imine ring to obtain the step of polyimine (6) Making a compound having a group capable of bonding to the above-mentioned functional group (for example, a hydroxyl group, a carboxyl group that can be halogenated, an isocyanate group, etc.) and a polyalkyleneoxy compound (for example, a polyalkylene glycol monoalkyl group) Ether, etc.), and compounds having a group capable of bonding to the above-mentioned functional group (for example, a hydroxyl group, a halogenated carboxyl group, an isocyanate group, etc.) and a polymerizable group (for example, hydroxyethyl methacrylate, etc.) The step of reacting with the above functional group in the polyimide obtained in (1) above
作為特定樹脂為聚醯亞胺前驅物時的合成方法,例如可列舉使二胺與在羧酸的一部分導入有聚伸烷氧基及聚合性基中的至少一者之二羧酸衍生物反應之方法。 作為上述二胺,亦可以使用具有聚伸烷氧基之二胺。As a synthesis method when the specific resin is a polyimide precursor, for example, the reaction of a diamine and a dicarboxylic acid derivative in which at least one of a polyalkyleneoxy group and a polymerizable group is introduced into a part of the carboxylic acid can be mentioned.的方法。 The method. As the above-mentioned diamine, a diamine having a polyalkoxy group can also be used.
<其他樹脂> 本發明的硬化性樹脂組成物亦可以包含與上述特定樹脂不同之其他樹脂(以下,亦簡稱為“其他樹脂”。)。 作為其他樹脂,可列舉與特定樹脂不同種類的聚醯亞胺或聚醯亞胺前驅物等。 特定樹脂為聚醯亞胺時,其他樹脂為聚醯亞胺為較佳。 特定樹脂為聚醯亞胺前驅物時,其他樹脂為聚醯亞胺前驅物為較佳。<Other resins> The curable resin composition of the present invention may also include other resins different from the above-mentioned specific resins (hereinafter, also simply referred to as "other resins"). Examples of other resins include polyimide or polyimide precursors that are different from the specific resin. When the specific resin is polyimide, the other resin is preferably polyimide. When the specific resin is a polyimide precursor, the other resin is preferably a polyimide precursor.
[聚醯亞胺(其他樹脂)] 從所獲得之硬化膜的膜強度的觀點考慮,作為其他樹脂之聚醯亞胺具有上述以式(4)表示之重複單元為較佳。 聚醯亞胺中,以式(4)表示之重複單元可以為一種,亦可以為兩種以上。又,除了上述式(4)的重複單元以外,聚醯亞胺還可以包含其他種類的重複單元。[Polyimide (other resin)] From the viewpoint of the film strength of the cured film obtained, it is preferable that the polyimide, which is another resin, has the repeating unit represented by the above formula (4). In the polyimide, the repeating unit represented by the formula (4) may be one type or two or more types. Moreover, in addition to the repeating unit of the above formula (4), the polyimide may also include other types of repeating units.
作為本發明的聚醯亞胺的一實施形態,可例示總重複單元的50莫耳%以上,進而為70莫耳%以上,尤其90莫耳%以上為以式(4)表示之重複單元之聚醯亞胺前驅物。作為上限,實際為100莫耳%以下。As an embodiment of the polyimide of the present invention, 50 mol% or more of the total repeating unit can be exemplified, further 70 mol% or more, especially 90 mol% or more of the repeating unit represented by formula (4) Polyimide precursor. As the upper limit, it is actually 100 mol% or less.
聚醯亞胺的重量平均分子量(Mw)較佳為2,000~500,000,更佳為5,000~100,000,進一步較佳為10,000~50,000。又,數量平均分子量(Mn)較佳為800~250,000,更佳為2,000~50,000,進一步較佳為4,000~25,000。The weight average molecular weight (Mw) of the polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.
聚醯亞胺的分子量的分散度為1.5~3.5為較佳,2~3為更佳。The molecular weight dispersion of the polyimide is preferably 1.5 to 3.5, and more preferably 2 to 3.
聚醯亞胺例如藉由對作為後述其他樹脂之聚醯亞胺前驅物進行加熱等來環化而獲得。Polyimine is obtained, for example, by heating or cyclizing a polyimide precursor which is another resin described later.
[聚醯亞胺前驅物(其他樹脂)] 從所獲得之硬化膜的膜強度的觀點考慮,聚醯亞胺前驅物具有上述以式(1)表示之重複單元為較佳。[Polyimide precursors (other resins)] From the viewpoint of the film strength of the cured film obtained, the polyimide precursor preferably has the repeating unit represented by the above formula (1).
聚醯亞胺前驅物中,以式(1)表示之重複單元可以為一種,亦可以為兩種以上。又,亦可以包含以式(1)表示之重複單元的結構異構物。又,除了上述式(1)的重複單元以外,聚醯亞胺前驅物還可以包含其他種類的重複單元。In the polyimide precursor, the repeating unit represented by the formula (1) may be one type or two or more types. In addition, the structural isomer of the repeating unit represented by formula (1) may also be included. In addition to the repeating unit of the above formula (1), the polyimide precursor may also include other types of repeating units.
作為本發明中的聚醯亞胺前驅物的一實施形態,可例示總重複單元的50莫耳%以上,進而為70莫耳%以上,尤其90莫耳%以上為以式(1)表示之重複單元之聚醯亞胺前驅物。作為上限,實際為100莫耳%以下。As an embodiment of the polyimide precursor in the present invention, 50 mol% or more of the total repeating unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, represented by formula (1) Polyimide precursor of repeating unit. As the upper limit, it is actually 100 mol% or less.
聚醯亞胺前驅物的重量平均分子量(Mw)較佳為2,000~500,000,更佳為5,000~100,000,進一步較佳為10,000~50,000。又,數量平均分子量(Mn)較佳為800~250,000,更佳為2,000~50,000,進一步較佳為4,000~25,000。The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.
聚醯亞胺前驅物的分子量的分散度為1.5~3.5為較佳,2~3為更佳。The molecular weight dispersion of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3.
聚醯亞胺前驅物可藉由使二羧酸或二羧酸衍生物與二胺反應而獲得。較佳為使用鹵化劑將二羧酸或二羧酸衍生物鹵化之後,使其與二胺反應而獲得。The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative using a halogenating agent, and then reacting it with a diamine.
聚醯亞胺前驅物的製造方法中,反應中使用有機溶劑為較佳。有機溶劑可以為一種,亦可以為兩種以上。In the production method of the polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one type or two or more types.
作為有機溶劑,能夠依原料適當設定,可例示吡啶、二乙二醇二甲醚(二甘二甲醚)、N-甲基吡咯啶酮及N-乙基吡咯啶酮。The organic solvent can be appropriately set according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be exemplified.
製造聚醯亞胺前驅物時,包括析出固體之步驟為較佳。具體而言,使反應液中的聚醯亞胺前驅物沉澱於水中並使其溶解於四氫呋喃等可溶解聚醯亞胺前驅物之溶劑,藉此能夠析出固體。When manufacturing the polyimide precursor, it is preferable to include a step of separating out solids. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent capable of dissolving the polyimide precursor, such as tetrahydrofuran, so that a solid can be precipitated.
本發明的硬化性樹脂組成物包含其他樹脂時,其他樹脂的含量相對於硬化性樹脂組成物的總固體成分為0.01質量%以上為較佳,0.05質量%以上為更佳,1質量%以上為進一步較佳,2質量%以上為更進一步較佳,5質量%以上為更進一步較佳,10質量%以上為更進一步較佳。又,本發明的硬化性樹脂組成物中的其他樹脂的含量相對於硬化性樹脂組成物的總固體成分為80質量%以下為較佳,75質量%以下為更佳,70質量%以下為進一步較佳,60質量%以下為更進一步較佳,50質量%以下為更進一步較佳。When the curable resin composition of the present invention contains other resins, the content of the other resin relative to the total solid content of the curable resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 1% by mass or more More preferably, 2% by mass or more is more preferable, 5% by mass or more is still more preferable, and 10% by mass or more is still more preferable. In addition, the content of other resins in the curable resin composition of the present invention relative to the total solid content of the curable resin composition is preferably 80% by mass or less, more preferably 75% by mass or less, and more preferably 70% by mass or less. Preferably, 60% by mass or less is more preferable, and 50% by mass or less is still more preferable.
本發明的硬化性樹脂組成物可以僅包含一種其他樹脂,亦可以包含兩種以上。包含兩種以上時,合計量成為上述範圍為較佳。The curable resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds. When two or more types are contained, the total amount is preferably in the above-mentioned range.
<聚合起始劑> 本發明的硬化性樹脂組成物含有聚合起始劑。 作為聚合起始劑,光聚合起始劑為較佳。<Polymerization initiator> The curable resin composition of the present invention contains a polymerization initiator. As the polymerization initiator, a photopolymerization initiator is preferred.
[光聚合起始劑] 本發明的硬化性樹脂組成物包含光聚合起始劑為較佳。 光聚合起始劑為光自由基聚合起始劑為較佳。作為光自由基聚合起始劑,並無特別限制,能夠從公知的光自由基聚合起始劑中適當選擇。例如,對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又,亦可以為與光激勵之敏化劑產生某些作用,並產生活性自由基之活性劑。[Photopolymerization initiator] The curable resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator is not particularly limited, and it can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can also be an active agent that interacts with a light-excited sensitizer and generates active free radicals.
光自由基聚合起始劑至少含有一種在約300~800nm(較佳為330~500nm)的範圍內至少具有約50L・mol-1 ・cm-1 莫耳吸光係數之化合物為較佳。化合物的莫耳吸光係數能夠利用公知的方法測量。例如,藉由紫外可見分光光度計(Varian Medical Systems, Inc.製Cary-5 spectrophotometer),並使用乙酸乙酯溶劑在0.01g/L的濃度下測量為較佳。The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50L・mol-1 ・cm -1 in the range of about 300-800nm (preferably 330-500nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) and use an ethyl acetate solvent to measure at a concentration of 0.01 g/L.
作為光自由基聚合起始劑,能夠任意使用公知的化合物。例如,可列舉鹵化烴衍生物(例如具有三𠯤骨架之化合物、具有㗁二唑骨架之化合物、具有三鹵甲基之化合物等)、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等,具體能夠參閱日本特開2016-027357號公報的0165~0182、國際公開第2015/199219號的0138~0151段的記載,且該內容被編入本說明書中。As the photoradical polymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, and hexaarylbisimidazole , Oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, amino acetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, thiophene Metal compounds, organoboron compounds, iron arene complexes, etc. For details, refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, 0138 to 0151 of International Publication No. 2015/199219, and this content is incorporated in this specification.
作為酮化合物,例如可例示日本特開2015-087611號公報的0087段中記載的化合物,且該內容被編入本說明書中。市售品中,還可較佳地使用KAYACURE DETX(Nippon Kayaku Co., Ltd.製)。As the ketone compound, for example, the compound described in paragraph 0087 of JP 2015-087611 A can be exemplified, and the content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.
本發明的一實施態樣中,作為光自由基聚合起始劑,能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言,例如能夠使用日本特開平10-291969號公報中所記載的胺基苯乙酮系起始劑、日本專利第4225898號中所記載的醯基氧化膦系起始劑。In one aspect of the present invention, as the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the phosphonium oxide-based initiator described in Japanese Patent No. 4225898 can be used.
作為羥基苯乙酮系起始劑,能夠使用IRGACURE 184(IRGACURE為註冊商標)、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127(商品名:均為BASF SE製)。As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (brand names: all manufactured by BASF SE) can be used.
作為胺基苯乙酮系起始劑,能夠使用作為市售品之IRGACURE 907、IRGACURE 369及IRGACURE 379(商品名:均為BASF SE製)。As the aminoacetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (brand names: all manufactured by BASF SE), which are commercially available products, can be used.
作為胺基苯乙酮系起始劑,還能夠使用吸收極大波長與365nm或405nm等波長光源匹配之日本特開2009-191179號公報中所記載的化合物。As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 having an absorption maximum wavelength matched with a wavelength light source such as 365 nm or 405 nm can also be used.
作為醯基膦系起始劑,可列舉2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又,能夠使用作為市售品之IRGACURE-819或IRGACURE-TPO(商品名:均為BASF SE製)。Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, IRGACURE-819 or IRGACURE-TPO (brand name: both manufactured by BASF SE), which are commercially available products, can be used.
作為茂金屬化合物,可例示IRGACURE-784(BASF SE製)等。As the metallocene compound, IRGACURE-784 (manufactured by BASF SE) and the like can be exemplified.
作為光自由基聚合起始劑,更佳為可列舉肟化合物。藉由使用肟化合物,能夠更有效地提高曝光寬容度。肟化合物中,曝光寬容度(曝光餘量)較廣,並且還起到光硬化促進劑的作用,因此為特佳。As the photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, the exposure latitude can be improved more effectively. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred.
作為肟化合物的具體例,能夠使用日本特開2001-233842號公報中所記載的化合物、日本特開2000-080068號公報中所記載的化合物、日本特開2006-342166號公報中所記載的化合物。As specific examples of the oxime compound, the compounds described in Japanese Patent Application Publication No. 2001-233842, the compounds described in Japanese Patent Application Publication No. 2000-080068, and the compounds described in Japanese Patent Application Publication No. 2006-342166 can be used. .
作為較佳的肟化合物,例如可列舉下述結構的化合物、3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-(4-甲苯磺醯氧基)亞胺基丁烷-2-酮、及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。本發明的硬化性樹脂組成物中,尤其作為光自由基聚合起始劑使用肟化合物(肟系光聚合起始劑)為較佳。肟系光聚合起始劑在分子內具有>C=N-O-C(=O)-的連接基。As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3 -Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one , 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one and the like. In the curable resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.
[化學式33] [Chemical formula 33]
市售品中,還可較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04(以上為BASF SE製)、ADEKA OPTOMER N-1919(ADEKA CORPORATION製、日本特開2012-014052號公報中所記載的光自由基聚合起始劑2)。又,還能夠使用TR-PBG-304(Changzhou Tronly New Electronic Materials CO., LTD.製)、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930(ADEKA CORPORATION製)。又,能夠使用DFI-091(DAITO CHEMIX Co., Ltd.製)。Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF SE), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japanese Patent Publication 2012-014052 The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.
還能夠使用具有氟原子之肟化合物。作為這種肟化合物的具體例,可列舉日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36~40、日本特開2013-164471號公報的0101段中所記載之化合物(C-3)等。An oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36-40, and the compounds described in paragraph 0345 of JP 2014-500852 A. The compound (C-3) and the like described in paragraph 0101 of the 2013-164471 Bulletin.
作為最佳的肟化合物,可列舉日本特開2007-269779號公報中所示出之具有特定取代基之肟化合物、或日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。As the best oxime compound, oxime compounds having specific substituents shown in Japanese Patent Application Publication No. 2007-269779, or oximes having sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.
從曝光靈敏度的觀點考慮,光自由基聚合起始劑為選自包括三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基㗁二唑化合物、3-芳基取代香豆素化合物之群組中之化合物為較佳。From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyl triketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Benzene-iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.
進一步較佳的光自由基聚合起始劑為三鹵甲基三𠯤化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物,選自包括三鹵甲基三𠯤化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中之至少一種化合物為更進一步較佳,使用茂金屬化合物或肟化合物為更進一步較佳,肟化合物為更進一步較佳。Further preferred photo-radical polymerization initiators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group including trihalomethyltriketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds At least one compound in the group is more preferable, a metallocene compound or an oxime compound is more preferable, and an oxime compound is still more preferable.
又,光自由基聚合起始劑還能夠使用二苯甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮(米其勒酮(Michler’s ketone))等N,N’-四烷基-4,4’-二胺基二苯甲酮,2-苄基-2-二甲基胺基-1-(4-口末啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-口末啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環進行縮環而成之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又,還能夠使用以下述式(I)表示之化合物。In addition, the photoradical polymerization initiator can also use benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. ,N'-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-porolinylphenyl)-butanone- Aromatic ketones such as 1,2-methyl-1-[4-(methylthio)phenyl]-2-endolinyl-acetone-1, alkylanthraquinones, etc. are condensed with aromatic rings. Quinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, a compound represented by the following formula (I) can also be used.
[化學式34] [Chemical formula 34]
式(I)中,RI00 為碳數1~20的烷基、藉由一個以上的氧原子而中斷之碳數2~20的烷基、碳數1~12的烷氧基、苯基、碳數1~20的烷基、碳數1~12的烷氧基、鹵素原子、環戊基、環己基、碳數2~12的烯基、被藉由一個以上的氧原子而中斷之碳數2~18的烷基及碳數1~4的烷基中的至少一個取代之苯基或聯苯基,RI01 為以式(II)表示之基團,或者為與RI00 相同的基團,RI02 ~RI04 分別獨立地為碳數1~12的烷基、碳數1~12的烷氧基或鹵素。In the formula (I), R I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, a phenyl group, C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, carbon interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of an alkyl group having 2 to 18 and an alkyl group having 1 to 4 carbons, R I01 is a group represented by formula (II), or the same group as R I00 Group, R I02 to R I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or halogen.
[化學式35] [Chemical formula 35]
式中,RI05 ~RI07 與上述式(I)的RI02 ~RI04 相同。In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).
又,光自由基聚合起始劑還能夠使用國際公開第2015/125469號的0048~0055段中所記載的化合物。In addition, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.
含有光聚合起始劑時,其含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1~30質量%為較佳,更佳為0.1~20質量%,進一步較佳為0.5~15質量%,更進一步較佳為1.0~10質量%。光聚合起始劑可以僅含有一種,亦可以含有兩種以上。含有兩種以上的光聚合起始劑時,其合計為上述範圍為較佳。When the photopolymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15 % By mass, more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one kind or two or more kinds. When two or more kinds of photopolymerization initiators are contained, it is preferable that the total of them is in the above-mentioned range.
[熱聚合起始劑] 本發明的硬化性樹脂組成物作為聚合起始劑亦可以含有熱聚合起始劑,尤其可以含有熱自由基聚合起始劑。熱自由基聚合起始劑為藉由熱的能量而產生自由基並起始或促進具有聚合性之化合物的聚合反應之化合物。藉由添加熱自由基聚合起始劑,當特定樹脂為聚醯亞胺前驅物時,能夠使前驅物環化,並且還使特定樹脂及聚合性化合物進行聚合反應,因此能夠實現更高度的耐熱化。[Thermal polymerization initiator] The curable resin composition of the present invention may contain a thermal polymerization initiator as a polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical polymerization initiator, when the specific resin is a polyimide precursor, the precursor can be cyclized, and the specific resin and polymerizable compound can be polymerized, so higher heat resistance can be achieved化.
作為熱自由基聚合起始劑,具體而言,可列舉日本特開2008-063554號公報的0074~0118段中所記載之化合物。Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.
含有熱聚合起始劑時,其含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1~30質量%為較佳,更佳為0.1~20質量%,進一步較佳為5~15質量%。熱聚合起始劑可以僅含有一種,亦可以含有兩種以上。含有兩種以上的熱聚合起始劑時,其合計為上述範圍為較佳。When a thermal polymerization initiator is contained, its content is preferably 0.1-30% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 5-15 quality%. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are contained, the total of them is preferably in the above-mentioned range.
<聚合性化合物> [自由基聚合性化合物] 本發明的硬化性樹脂組成物含有聚合性化合物。 作為聚合性化合物,能夠使用自由基聚合性化合物。自由基聚合性化合物為具有自由基聚合性基之化合物。作為自由基聚合性基,可列舉乙烯基、烯丙基、乙烯基苯基、(甲基)丙烯醯基等具有乙烯性不飽和鍵之基團。自由基聚合性基為(甲基)丙烯醯基為較佳,從反應性的觀點考慮,(甲基)丙烯醯氧基為更佳。<Polymerizable compound> [Free radical polymerizable compound] The curable resin composition of the present invention contains a polymerizable compound. As the polymerizable compound, a radical polymerizable compound can be used. The radical polymerizable compound is a compound having a radical polymerizable group. Examples of radical polymerizable groups include groups having ethylenically unsaturated bonds, such as vinyl groups, allyl groups, vinyl phenyl groups, and (meth)acrylic groups. The radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferable.
自由基聚合性化合物所具有之自由基聚合性基的數量可以為一個,亦可以為兩個以上,自由基聚合性化合物具有兩個以上的自由基聚合性基為較佳,具有三個以上為更佳。上限為十五個以下為較佳,十個以下為更佳,八個以下為進一步較佳。The number of radically polymerizable groups possessed by the radically polymerizable compound may be one or two or more. The radically polymerizable compound preferably has two or more radically polymerizable groups, and three or more are Better. The upper limit is preferably fifteen or less, more preferably ten or less, and even more preferably eight or less.
自由基聚合性化合物的分子量為2,000以下為較佳,1,500以下為更佳,900以下為進一步較佳。自由基聚合性化合物的分子量的下限為100以上為較佳。The molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.
從顯影性的觀點考慮,本發明的硬化性樹脂組成物含有至少一種包含兩個以上的自由基聚合性基之2官能以上的自由基聚合性化合物為較佳,含有至少一種3官能以上的自由基聚合性化合物為更佳。又,亦可以為2官能自由基聚合性化合物與3官能以上的自由基聚合性化合物的混合物。例如2官能以上的聚合性單體的官能基數量表示1個分子中的自由基聚合性基的數量為兩個以上。From the viewpoint of developability, the curable resin composition of the present invention preferably contains at least one bifunctional or more radically polymerizable compound containing two or more radically polymerizable groups, and at least one trifunctional or more functionally free radical polymerizable compound. A base polymerizable compound is more preferable. Moreover, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or more radical polymerizable compound. For example, the number of functional groups of a bifunctional or more polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
作為自由基聚合性化合物的具體例,可列舉不飽和羧酸(例如,丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸等)或其酯類、醯胺類,較佳為不飽和羧酸與多元醇化合物的酯及不飽和羧酸與多元胺化合物的醯胺類。又,還可較佳地使用具有羥基或胺基、氫硫基等親和性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物、與單官能、或多官能的羧酸的脫水縮合反應物等。又,具有異氰酸酯基或環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能、或者多官能醇類、胺類、硫醇類的加成反應物、以及具有鹵素基或甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯胺類與單官能、或者多官能醇類、胺類、硫醇類的取代反應物亦為較佳。又,作為另一例,替代上述不飽和羧酸,還能夠使用替換成不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等之化合物群組。作為具體例,能夠參閱日本特開2016-027357號公報的0113~0122段的記載,且該等內容被編入本說明書中。Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amides Types, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amine groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogens Substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as sulfonyl groups or toluene sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can also be used. As a specific example, the description in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated in this specification.
又,自由基聚合性化合物在常壓下具有100℃以上的沸點之化合物亦較佳。作為其例,能夠列舉聚乙二醇二(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三(丙烯醯氧基乙基)異三聚氰酸酯、甘油或三羥甲基乙烷等在多官能醇中加成環氧乙烷或環氧丙烷之後進行(甲基)丙烯酸酯化之化合物、如日本特公昭48-041708號公報、日本特公昭50-006034號公報、日本特開昭51-037193號各公報中所記載之(甲基)丙烯酸胺甲酸乙酯類、日本特開昭48-064183號、日本特公昭49-043191號、日本特公昭52-030490號各公報中所記載之聚酯丙烯酸酯類,作為環氧樹脂與(甲基)丙烯酸的反應產物之環氧丙烯酸酯類等多官能的丙烯酸酯或甲基丙烯酸酯及該等的混合物。又,日本特開2008-292970號公報的0254~0257段中所記載的化合物亦較佳。又,還能夠列舉使(甲基)丙烯酸環氧丙酯等具有環狀醚基及乙烯性不飽和鍵之化合物與多官能羧酸反應而獲得之多官能(甲基)丙烯酸酯等。In addition, a radically polymerizable compound having a boiling point of 100°C or higher under normal pressure is also preferable. As examples, polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentyl erythritol tri(meth)acrylate can be cited. Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexylene glycol ) Acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohol Compounds that are (meth)acrylated after addition of ethylene oxide or propylene oxide, such as Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193. (Meth) urethane acrylates described in the gazette, and polyester acrylates described in each gazette of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490 Types, epoxy acrylates and other polyfunctional acrylates or methacrylates as the reaction product of epoxy resin and (meth)acrylic acid, and mixtures of these. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. Moreover, the polyfunctional (meth)acrylate etc. which are made to react the compound which has a cyclic ether group and ethylenically unsaturated bond, such as glycidyl (meth)acrylate, and a polyfunctional carboxylic acid are mentioned.
又,作為除了上述以外的較佳的自由基聚合性化合物,還能夠使用日本特開2010-160418號公報、日本特開2010-129825號公報、日本專利第4364216號公報等中所記載之具有茀環,且具有兩個以上的含有乙烯性不飽和鍵的基團之化合物或卡多(cardo)樹脂。In addition, as a preferable radical polymerizable compound other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. It is a compound or cardo resin with two or more groups containing ethylenically unsaturated bonds.
進而,作為其他例子,還能夠列舉日本特公昭46-043946號公報、日本特公平01-040337號公報、日本特公平01-040336號公報中所記載的特定的不飽和化合物、或日本特開平02-025493號公報中所記載的乙烯基膦酸系化合物等。又,還能夠使用日本特開昭61-022048號公報中所記載的包含全氟烷基的化合物。進而,還能夠使用“Journal of the Adhesion Society of Japan”vol.20、No.7、300~308頁(1984年)中作為光聚合性單體及寡聚物所介紹者。Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or Japanese Patent Application Publication No. 02 Vinylphosphonic acid-based compounds and the like described in Bulletin -025493. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).
除了上述以外,亦能夠較佳地使用日本特開2015-034964號公報的0048~0051段中所記載的化合物、國際公開第2015/199219號的0087~0131段中所記載的化合物,且該等內容被編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Application Publication No. 2015-034964, the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these The content is compiled into this manual.
又,日本特開平10-062986號公報中作為式(1)及式(2)而與其具體例一同記載的如下化合物亦能夠用作自由基聚合性化合物,該化合物為在多官能醇中加成環氧乙烷或環氧丙烷之後進行(甲基)丙烯酸酯化而成之化合物。In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as radically polymerizable compounds, which are added to polyfunctional alcohols. Ethylene oxide or propylene oxide is then (meth)acrylated compound.
進而,作為其他自由基聚合性化合物,還能夠使用日本特開2015-187211號公報的0104~0131段中所記載的化合物,且該等內容被編入本說明書中。Furthermore, as other radically polymerizable compounds, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used, and these contents are incorporated in this specification.
作為自由基聚合性化合物,二新戊四醇三丙烯酸酯(作為市售品為KAYARAD D-330;Nippon Kayaku Co., Ltd.製)、二新戊四醇四丙烯酸酯(作為市售品為KAYARAD D-320;Nippon Kayaku Co., Ltd.製、A-TMMT:Shin-Nakamura Chemical Co., Ltd.製)、二新戊四醇五(甲基)丙烯酸酯(作為市售品為KAYARAD D-310;Nippon Kayaku Co., Ltd.製)、二新戊四醇六(甲基)丙烯酸酯(作為市售品為KAYARAD DPHA;Nippon Kayaku Co., Ltd.製、A-DPH;Shin-Nakamura Chemical Co., Ltd.製)及該等的(甲基)丙烯醯基經由乙二醇殘基或丙二醇殘基鍵結之結構為較佳。亦能夠使用該等的寡聚物類型。As a radically polymerizable compound, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., dineopentylerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentyl erythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.
作為自由基聚合性化合物的市售品,例如可列舉Sartomer Company, Inc製的作為具有四個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有四個乙烯氧基鏈之2官能丙烯酸甲酯之Sartomer Company, Inc製SR-209、231、239、Nippon Kayaku Co., Ltd.製的作為具有六個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有三個異伸丁氧基鏈之3官能丙烯酸酯之TPA-330、胺甲酸乙酯寡聚物UAS-10、UAB-140(NIPPON PAPER INDUSTRIES CO., LTD.製)、NK酯M-40G、NK酯4G、NK酯M-9300、NK酯A-9300、UA-7200(Shin-Nakamura Chemical Co., Ltd製)、DPHA-40H(Nippon Kayaku Co., Ltd.製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(Kyoeisha chemical Co., Ltd.製)、BLEMMER PME400(NOF CORPORATION製)等。Commercial products of radically polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc as a 4-functional acrylate having four ethyleneoxy chains, and SR-494 as a bifunctional acrylate having four ethyleneoxy chains. SR-209, 231, 239 manufactured by Sartomer Company, Inc. of methyl acrylate, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with six pentyloxy chains, as having three different TPA-330 of trifunctional acrylate of butoxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G , NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.
作為自由基聚合性化合物,如日本特公昭48-041708號公報、日本特開昭51-037193號公報、日本特公平02-032293號公報、日本特公平02-016765號公報中所記載之那樣的胺甲酸乙酯丙烯酸酯類、日本特公昭58-049860號公報、日本特公昭56-017654號公報、日本特公昭62-039417號公報、日本特公昭62-039418號公報中所記載的具有環氧乙烷系骨架之胺甲酸乙酯化合物類亦較佳。進而,作為自由基聚合性化合物,還能夠使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中所記載之在分子內具有胺基結構或硫化物結構之化合物。As a radically polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Urethane acrylates, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have epoxy resins described in Urethane compounds with an ethane-based skeleton are also preferred. Furthermore, as the radically polymerizable compound, those described in JP 63-277653, JP 63-260909, and 01-105238 having an amino group in the molecule can also be used. Structure or sulfide structure compound.
自由基聚合性化合物亦可以為具有羧基、磷酸基等酸基之自由基聚合性化合物。具有酸基之自由基聚合性化合物為脂肪族多羥基化合物與不飽和羧酸的酯為較佳,使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基反應而具有酸基之自由基聚合性化合物為更佳。特佳為使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基反應而具有酸基之自由基聚合性化合物中,脂肪族多羥基化合物為新戊四醇或二新戊四醇之化合物。作為市售品,例如作為TOAGOSEI CO., Ltd.製多元酸改質丙烯酸類寡聚物,可列舉M-510、M-520等。The radically polymerizable compound may also be a radically polymerizable compound having an acid group such as a carboxyl group and a phosphoric acid group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. The non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have the freedom of an acid group A base polymerizable compound is more preferable. Particularly preferably, the non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Among the radically polymerizable compounds, the aliphatic polyhydroxy compound is one of neopentylerythritol or dineopentaerythritol. Compound. As a commercially available product, as a polyacid modified acrylic oligomer manufactured by TOAGOSEI CO., Ltd., M-510, M-520, etc. are mentioned, for example.
具有酸基之自由基聚合性化合物的較佳酸值為0.1~40mgKOH/g,特佳為5~30mgKOH/g。只要自由基聚合性化合物的酸值在上述範圍內,則製造上的操作性優異,而且顯影性優異。又,聚合性良好。上述酸值遵照JIS K 0070:1992的記載測量。The preferred acid value of the radically polymerizable compound having an acid group is 0.1-40 mgKOH/g, and particularly preferably 5-30 mgKOH/g. As long as the acid value of the radically polymerizable compound is within the above range, the workability in production is excellent, and the developability is also excellent. In addition, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.
從抑制伴隨硬化膜的彈性係數控制之翹曲的觀點考慮,本發明的硬化性樹脂組成物作為自由基聚合性化合物,能夠較佳地使用單官能自由基聚合性化合物。作為單官能自由基聚合性化合物,可較佳地使用正丁基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、丁氧基乙基(甲基)丙烯酸酯、卡必醇(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、芐基(甲基)丙烯酸酯、苯氧基乙基(甲基)丙烯酸酯、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸環氧丙酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯等(甲基)丙烯酸衍生物、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基化合物類、烯丙基環氧丙基醚、鄰苯二甲酸二烯丙酯、偏苯三酸三烯丙酯等烯丙基化合物類等。作為單官能自由基聚合性化合物,為了抑制曝光前的揮發,在常壓下具有100℃以上的沸點之化合物亦較佳。From the viewpoint of suppressing warpage accompanying the control of the elastic coefficient of the cured film, the curable resin composition of the present invention can preferably use a monofunctional radical polymerizable compound as a radical polymerizable compound. As the monofunctional radical polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth)acrylic acid Derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid Allyl compounds such as allyl esters, etc. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.
[除了上述自由基聚合性化合物以外的聚合性化合物] 本發明的硬化性樹脂組成物能夠進一步含有除了上述自由基聚合性化合物以外的聚合性化合物。作為除了上述自由基聚合性化合物以外的聚合性化合物,可列舉具有羥甲基、烷氧基甲基或醯氧基甲基之化合物;環氧化合物;氧雜環丁烷化合物;苯并㗁𠯤化合物。[Polymerizable compounds other than the above-mentioned radically polymerizable compounds] The curable resin composition of the present invention can further contain a polymerizable compound other than the above-mentioned radical polymerizable compound. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having methylol, alkoxymethyl, or oxymethyl; epoxy compounds; oxetane compounds; Compound.
-具有羥甲基、烷氧基甲基或醯氧基甲基之化合物- 作為具有羥甲基、烷氧基甲基或醯氧基甲基之化合物,以下述式(AM1)、(AM4)或(AM5)表示之化合物為較佳。-Compounds with hydroxymethyl, alkoxymethyl or oxymethyl- As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferred.
[化學式36] (式中,t表示1~20的整數,R104 表示碳數1~200的t價有機基,R105 表示以-OR106 或-OCO-R107 表示之基團,R106 表示氫原子或碳數1~10的有機基,R107 表示碳數1~10的有機基。) [化學式37] (式中,R404 表示碳數1~200的2價有機基,R405 表示以-OR406 或-OCO-R407 表示之基團,R406 表示氫原子或碳數1~10的有機基,R407 表示碳數1~10的有機基。) [化學式38] (式中,u表示3~8的整數,R504 表示碳數1~200的u價有機基,R505 表示以-OR506 或-OCO-R507 表示之基團,R506 表示氫原子或碳數1~10的有機基,R507 表示碳數1~10的有機基。)[Chemical formula 36] (In the formula, t represents an integer from 1 to 20, R 104 represents a t-valent organic group with a carbon number of 1 to 200, R 105 represents a group represented by -OR 106 or -OCO-R 107 , and R 106 represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, R 107 represents an organic group having 1 to 10 carbon atoms.) [Chemical formula 37] (In the formula, R 404 represents a divalent organic group with 1 to 200 carbons, R 405 represents a group represented by -OR 406 or -OCO-R 407 , and R 406 represents a hydrogen atom or an organic group with 1 to 10 carbons. , R 407 represents an organic group having 1 to 10 carbons.) [Chemical formula 38] (In the formula, u represents an integer from 3 to 8, R 504 represents a U-valent organic group with a carbon number of 1 to 200, R 505 represents a group represented by -OR 506 or -OCO-R 507 , and R 506 represents a hydrogen atom or An organic group having 1 to 10 carbons, R 507 represents an organic group having 1 to 10 carbons.)
作為以式(AM4)表示之化合物的具體例,可列舉46DMOC、46DMOEP(以上為商品名,ASAHI YUKIZAI CORPORATION製)、DML-MBPC、DML-MBOC、DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、dimethylolBisOC-P、DML-PFP、DML-PSBP、DML-MTrisPC(以上為商品名,Honshu Chemical Industry Co., Ltd.製)、NIKALAC MX-290(商品名,Sanwa Chemical Co., Ltd.製)、2,6-dimethoxymethyl-4-t-butylphenol(2,6-二甲氧基甲基-4-第三丁基苯酚)、2,6-dimethoxymethyl-p-cresol(2,6-二甲氧基甲基-對甲酚)、2,6-diacetoxymethyl-p-cresol(2,6-二乙醯氧基甲基-對甲酚)等。Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol) Wait.
又,作為以式(AM5)表示之化合物的具體例,可列舉TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP(以上為商品名,Honshu Chemical Industry Co., Ltd.製)、TM-BIP-A(商品名,ASAHI YUKIZAI CORPORATION製)、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MW-100LM(以上為商品名,Sanwa Chemical Co., Ltd.製)。Also, as specific examples of the compound represented by the formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA , HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade names, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above are trade names, manufactured by Sanwa Chemical Co., Ltd.).
-環氧化合物(具有環氧基之化合物)- 作為環氧化合物,為在一個分子中具有兩個以上的環氧基之化合物為較佳。環氧基在200℃以下進行交聯反應,並且不會引起來自於交聯之脫水反應,因此不易引起膜收縮。因此,含有環氧化合物,說明可有效地抑制硬化性樹脂組成物的低溫硬化及翹曲。-Epoxy compound (compound with epoxy group)- As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes cross-linking reaction below 200°C, and does not cause dehydration reaction from cross-linking, so it is difficult to cause film shrinkage. Therefore, the inclusion of an epoxy compound indicates that the low-temperature curing and warpage of the curable resin composition can be effectively suppressed.
環氧化合物包含聚環氧乙烷基為較佳。藉此,彈性係數進一步下降,又,能夠抑制翹曲。聚環氧乙烷基表示環氧乙烷的重複單元數為2以上者,重複單元數為2~15為較佳。The epoxy compound preferably contains a polyethylene oxide group. Thereby, the coefficient of elasticity is further reduced, and it is possible to suppress warpage. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.
作為環氧化合物的例子,能夠列舉雙酚A型環氧樹脂;雙酚F型環氧樹脂;丙二醇二環氧丙基醚等伸烷基二醇型環氧樹脂;聚丙二醇二環氧丙基醚等聚伸烷基二醇型環氧樹脂;聚甲基(環氧丙基氧基丙基)矽氧烷等含環氧基的聚矽氧等,但並不限定於該等。具體而言,可列舉EPICLON(註冊商標)850-S、EPICLON(註冊商標)HP-4032、EPICLON(註冊商標)HP-7200、EPICLON(註冊商標)HP-820、EPICLON(註冊商標)HP-4700、EPICLON(註冊商標)EXA-4710、EPICLON(註冊商標)HP-4770、EPICLON(註冊商標)EXA-859CRP、EPICLON(註冊商標)EXA-1514、EPICLON(註冊商標)EXA-4880、EPICLON(註冊商標)EXA-4850-150、EPICLON(註冊商標)EXA-4850-1000、EPICLON(註冊商標)EXA-4816、EPICLON(註冊商標)EXA-4822(以上為商品名,DIC Corporation製)、RIKARESIN(註冊商標)BEO-60E(商品名,New Japan Chemical Co., Ltd.製)、EP-4003S、EP-4000S(以上為商品名,ADEKA CORPORATION製)等。其中,從抑制翹曲及耐熱性優異之觀點考慮,包含聚環氧乙烷基之環氧樹脂為較佳。例如,EPICLON(註冊商標)EXA-4880、EPICLON(註冊商標)EXA-4822、RIKARESIN(註冊商標)BEO-60E包含聚環氧乙烷基,因此較佳。Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diglycidyl ether Polyalkylene glycol type epoxy resins such as ethers; epoxy-containing polysiloxanes such as polymethyl(glycidoxypropyl)siloxanes, etc., but are not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700 , EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) ) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are trade names, manufactured by DIC Corporation), RIKARESIN (registered trademark) ) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (trade name above, manufactured by ADEKA CORPORATION), etc. Among them, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.
-氧雜環丁烷化合物(具有氧雜環丁基之化合物)- 作為氧雜環丁烷化合物,能夠列舉在一個分子中具有兩個以上的氧雜環丁烷環之化合物、3-乙基-3-羥甲氧雜環丁烷、1,4-雙{[(3-乙基-3-氧雜環丁基)甲氧基]甲基}苯、3-乙基-3-(2-乙基己基甲基)氧雜環丁烷、1,4-苯二羧酸-雙[(3-乙基-3-氧雜環丁基)甲基]酯等。作為具體的例子,能夠較佳地使用TOAGOSEI CO., LTD.製ARON OXETANE系列(例如,OXT-121、OXT-221、OXT-191、OXT-223),該等可以單獨使用或混合兩種以上使用。-Oxetane compounds (compounds with oxetanyl groups)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, and 1,4-bis{[ (3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzene Dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester and the like. As a specific example, ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, which can be used alone or in combination of two or more use.
-苯并㗁𠯤化合物(具有聚苯并㗁唑基之化合物)- 苯并㗁𠯤化合物由於來自於開環加成反應之交聯反應,硬化時不產生脫氣,且進而減少熱收縮而抑制產生翹曲,因此為較佳。-Benzo 㗁 𠯤 compounds (compounds with polybenzo azole groups)- Since the benzoxa compound is derived from the cross-linking reaction of the ring-opening addition reaction, it does not produce outgassing during hardening, and further reduces heat shrinkage and suppresses warpage, so it is preferable.
作為苯并㗁𠯤化合物的較佳的例子,可列舉B-a型苯并㗁𠯤、B-m型苯并㗁𠯤(以上為商品名,Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并㗁𠯤加成物、酚醛清漆型二氫苯并㗁𠯤化合物。該等可以單獨使用或混合兩種以上使用。As a preferable example of the benzoglyph compound, there can be mentioned Ba-type benzoglyph, Bm-type benzoglyph (the above are trade names, manufactured by Shikoku Chemicals Corporation), and the benzoglyphthylene resin of polyhydroxystyrene. Finished product, novolac-type dihydrobenzo 㗁𠯤 compound. These can be used alone or in combination of two or more.
聚合性化合物的含量相對於本發明的硬化性樹脂組成物的總固體成分超過0質量%且為60質量%以下為較佳。下限為5質量%以上為更佳。上限為50質量%以下為更佳,30質量%以下為進一步較佳。The content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.
聚合性化合物可以單獨使用一種,亦可以混合使用兩種以上。同時使用兩種以上時,其合計量成為上述範圍為較佳。A polymerizable compound may be used individually by 1 type, and may mix and
<溶劑> 本發明的硬化性樹脂組成物含有溶劑。溶劑能夠任意使用公知的溶劑。溶劑較佳為有機溶劑。作為有機溶劑,可列舉酯類、醚類、酮類、芳香族烴類、亞碸類、醯胺類等化合物。<Solvent> The curable resin composition of the present invention contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfenes, and amines.
作為酯類,例如可列舉乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯(例如,烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯(例如,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、乙氧基乙酸乙酯等))、3-烷氧基丙酸烷基酯類(例如,3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等(例如,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-乙氧基丙酸乙酯等))、2-烷氧基丙酸烷基酯類(例如,2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等(例如,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-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯(例如,2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等)、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-氧代丁酸甲酯、2-氧代丁酸乙酯等作為較佳者。Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate , Butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3- Alkoxy propionic acid alkyl esters (for example, 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate Ester, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2-alkoxy-2- Ethyl methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate , Propylpyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, etc. are preferred.
作為醚類,例如可列舉二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等作為較佳者。As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. The better.
作為酮類,例如可列舉甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮等作為較佳者。As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones, for example.
作為芳香族烴類,例如可列舉甲苯、二甲苯、苯甲醚、檸檬烯等作為較佳者。As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferred.
作為亞碸類,例如可列舉二甲基亞碸作為較佳者。As the sulfenites, for example, dimethyl sulfenite is preferable.
作為醯胺類,可列舉N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺等作為較佳者。Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide Etc. as the better ones.
關於溶劑,從塗佈面性狀的改良等的觀點考慮,混合兩種以上之形態亦較佳。Regarding the solvent, from the viewpoint of improvement of coating surface properties, etc., a form in which two or more types are mixed is also preferable.
本發明中,選自3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、環戊酮、γ-丁內酯、二甲基亞碸、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、N-甲基-2-吡咯啶酮、丙二醇甲醚及丙二醇甲醚乙酸酯中之一種溶劑或由兩種以上構成之混合溶劑為較佳。同時使用二甲基亞碸和γ-丁內酯為特佳。In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate , Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol One solvent of acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more types is preferred. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.
從塗佈性的觀點考慮,將溶劑的含量設為本發明的硬化性樹脂組成物的總固體成分濃度成為5~80質量%之量為較佳,設為成為5~75質量%之量為更佳,設為成為10~70質量%之量為進一步較佳,設為成為40~70質量%為更進一步較佳。溶劑含量依塗膜的所期望的厚度和塗佈方法調節即可。From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and the amount is 5 to 75% by mass. More preferably, it is more preferable to set it as 10-70 mass %, and it is still more preferable to set it as 40-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
溶劑可以僅含有一種,亦可以含有兩種以上。含有兩種以上溶劑時,其合計為上述範圍為較佳。The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably in the above-mentioned range.
<熱酸產生劑> 本發明的硬化性樹脂組成物含有熱酸產生劑為較佳。 熱酸產生劑具有藉由加熱產生酸,且促進選自具有羥甲基、烷氧基甲基或醯氧基甲基之化合物、環氧化合物、氧雜環丁烷化合物及苯并㗁化合物中之至少一種化合物或特定樹脂中所包含之羥甲基的交聯反應之效果。 又,本發明的硬化性樹脂組成物含有熱酸產生劑時,特定樹脂作為聚合性基包含羥甲基為較佳。<Hot acid generator> The curable resin composition of the present invention preferably contains a thermal acid generator. The thermal acid generator is capable of generating acid by heating, and promotes selected from compounds having methylol, alkoxymethyl, or acyloxymethyl, epoxy compounds, oxetane compounds, and benzox compounds The effect of the crosslinking reaction of at least one compound or the methylol contained in the specific resin. Furthermore, when the curable resin composition of the present invention contains a thermal acid generator, it is preferable that the specific resin contains a methylol group as a polymerizable group.
熱酸產生劑的熱分解開始溫度為50℃~270℃為較佳,50℃~250℃為更佳。又,若作為熱酸產生劑選擇一種將硬化性樹脂組成物塗佈於基板之後進行之乾燥(預烘烤:約70~140℃)中不產生酸,而藉由之後的曝光、顯影而圖案化之後進行之最終加熱(硬化:約100~400℃)中產生酸者,則能夠抑制顯影中的靈敏度下降,因此為較佳。 關於熱分解開始溫度,將熱酸產生劑在耐壓膠囊中以5℃/分鐘加熱至500℃時,作為溫度最低的發熱峰的峰值溫度而求出。 作為測量熱分解開始溫度時使用之設備,可列舉Q2000(TA Instruments. 製)等。The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, more preferably 50°C to 250°C. In addition, if a thermal acid generator is selected as a thermal acid generator, the curing resin composition is applied to the substrate and then dried (pre-baking: about 70 to 140°C), which does not generate acid, but is patterned by subsequent exposure and development. In the final heating (curing: about 100 to 400°C) that is performed after conversion, acid is generated, which can suppress the decrease in sensitivity during development, which is preferable. Regarding the thermal decomposition start temperature, when the thermal acid generator is heated in a pressure-resistant capsule to 500°C at 5°C/min, it is determined as the peak temperature of the heat generation peak with the lowest temperature. As a device used to measure the start temperature of thermal decomposition, Q2000 (manufactured by TA Instruments.) can be cited.
從熱酸產生劑產生之酸為強酸為較佳,例如對甲苯磺酸、苯磺酸等芳磺酸、甲磺酸、乙磺酸、丁磺酸等烷磺酸、或者三氟甲磺酸等鹵烷磺酸等為較佳。作為這種熱酸產生劑的例子,可列舉日本特開2013-072935號公報的0055段中所記載者。The acid generated from the thermal acid generator is preferably a strong acid, such as aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or trifluoromethanesulfonic acid Haloalkanesulfonic acids and the like are preferred. As an example of such a thermal acid generator, the one described in paragraph 0055 of JP 2013-072935 A can be cited.
其中,從在硬化膜中殘留得少且不易降低硬化膜物理性質之觀點考慮,產生碳數1~4的烷磺酸或碳數1~4的鹵烷磺酸者為更佳,作為熱酸產生劑,甲磺酸(4-羥基苯基)二甲基鋶鹽、甲磺酸(4-((甲氧基羰基)氧基)苯基)二甲基鋶鹽、甲磺酸苄基(4-羥基苯基)甲基鋶鹽、甲磺酸苄基(4-((甲氧基羰基)氧基)苯基)甲基鋶鹽、甲磺酸(4-羥基苯基)甲基((2-甲基苯基)甲基)鋶鹽、三氟甲磺酸(4-羥基苯基)二甲基鋶鹽、三氟甲磺酸(4-((甲氧基羰基)氧基)苯基)二甲基鋶鹽、三氟甲磺酸苄基(4-羥基苯基)甲基鋶鹽、三氟甲磺酸苄基(4-((甲氧基羰基)氧基)苯基)甲基鋶鹽、三氟甲磺酸(4-羥基苯基)甲基((2-甲基苯基)甲基)鋶鹽、3-(5-(((丙磺醯基)氧基)亞胺基)噻吩-2(5H)-亞基)-2-(鄰甲苯基)丙腈、2,2-雙(3-(甲磺醯基胺基)-4-羥基苯基)六氟丙烷。Among them, from the viewpoint of leaving little residue in the cured film and not easily degrading the physical properties of the cured film, it is more preferable to produce alkanesulfonic acid with 1 to 4 carbon atoms or haloalkanesulfonic acid with 1 to 4 carbon atoms, as the thermal acid Producer, methanesulfonic acid (4-hydroxyphenyl) dimethyl sulfonate, methanesulfonic acid (4-((methoxycarbonyl)oxy) phenyl) dimethyl sulfonate, benzyl methanesulfonate ( 4-Hydroxyphenyl)methylsulfonate, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylsulfonate, methanesulfonate (4-hydroxyphenyl)methyl( (2-Methylphenyl)methyl)silium salt, trifluoromethanesulfonic acid (4-hydroxyphenyl)dimethylsilium salt, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy) Phenyl) dimethyl sulfonate, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methyl sulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl)oxy)phenyl ) Methyl sulfonate, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonate, 3-(5-(((propanesulfonyl)oxy ) Imino) thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexa Fluoropropane.
又,作為熱酸產生劑,日本特開2013-167742號公報的0059段中所記載的化合物亦較佳。In addition, as the thermal acid generator, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable.
熱酸產生劑的含量相對於特定樹脂100質量份為0.01質量份以上為較佳,0.1質量份以上為更佳。藉由含有0.01質量份以上,交聯反應得到促進,因此能夠進一步提高硬化膜的機械特性及耐藥品性。又,從硬化膜的電絕緣性的觀點考慮,20質量份以下為較佳,15質量份以下為更佳,10質量份以下為進一步較佳。The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the specific resin, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, and therefore the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of the cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is more preferable.
<鎓鹽> 本發明的硬化性樹脂組成物含有鎓鹽為較佳。 尤其,特定樹脂為聚醯亞胺前驅物時,硬化性樹脂組成物含有鎓鹽為較佳。 鎓鹽的種類等並無特別限定,可較佳地列舉銨鹽、亞胺鹽、鋶鹽、錪鹽或鏻鹽。 其中,從熱穩定性高的觀點考慮,銨鹽或亞胺鹽為較佳,從與聚合物的相溶性的觀點考慮,鋶鹽、錪鹽或鏻鹽為較佳。<Onium salt> The curable resin composition of the present invention preferably contains an onium salt. In particular, when the specific resin is a polyimide precursor, the curable resin composition preferably contains an onium salt. The type of onium salt and the like are not particularly limited, and preferably ammonium salt, imine salt, sulphur salt, iodonium salt or phosphonium salt is mentioned. Among them, from the viewpoint of high thermal stability, an ammonium salt or an imine salt is preferable, and from the viewpoint of compatibility with a polymer, a sulfonium salt, an phosphonium salt, or a phosphonium salt is preferable.
又,鎓鹽為具有鎓結構之陽離子與陰離子的鹽,上述陽離子與陰離子可以經由共價鍵鍵結,亦可以不經由共價鍵鍵結。 亦即,鎓鹽可以為在同一個分子結構內具有陽離子部和陰離子部之分子內鹽,亦可以為作為分別不同的分子之陽離子分子與陰離子分子進行離子鍵結之分子間鹽,分子間鹽為較佳。又,在本發明的硬化性樹脂組成物中,上述陽離子部或陽離子分子與上述陰離子部或陰離子分子可以藉由離子鍵鍵結,亦可以解離。 作為鎓鹽中的陽離子,銨陽離子、吡啶鎓陽離子、鋶陽離子、錪陽離子或鏻陽離子為較佳,選自包括四烷基銨陽離子、鋶陽離子及錪陽離子之群組中之至少一種陽離子為更佳。In addition, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded via a covalent bond, or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cation part and an anion part in the same molecular structure, or an intermolecular salt in which cation molecules and anion molecules are ionically bonded as separate molecules. Intermolecular salts For better. In addition, in the curable resin composition of the present invention, the cation portion or cation molecule and the anion portion or anion molecule may be bonded by an ionic bond or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, sulfonium cations and phosphonium cations is more good.
本發明中使用的鎓鹽亦可以為熱鹼產生劑。 熱鹼產生劑表示藉由加熱產生鹼之化合物,例如可列舉加熱至40℃以上便產生鹼之酸性化合物等。The onium salt used in the present invention may also be a thermal base generator. The thermal base generator means a compound that generates a base by heating, and for example, an acidic compound that generates a base when heated to 40° C. or more can be cited.
[銨鹽] 本發明中,銨鹽表示銨陽離子與陰離子的鹽。[Ammonium salt] In the present invention, ammonium salt means a salt of an ammonium cation and an anion.
-銨陽離子- 作為銨陽離子,第四銨陽離子為較佳。 又,作為銨陽離子,以下述式(101)表示之陽離子為較佳。 [化學式39] 式(101)中,R1 ~R4 分別獨立地表示氫原子或烴基,R1 ~R4 中的至少兩個可以分別鍵結而形成環。-Ammonium cation- As the ammonium cation, a fourth ammonium cation is preferred. In addition, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 39] In formula (101), R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
式(101)中,R1 ~R4 分別獨立地為烴基為較佳,烷基或芳基為更佳,碳數1~10的烷基或碳數6~12的芳基為進一步較佳。R1 ~R4 亦可以具有取代基,作為取代基的例子,可列舉羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。 R1 ~R4 中的至少兩個分別鍵結而形成環時,上述環亦可以包含雜原子。作為上述雜原子,可列舉氮原子。In formula (101), R 1 to R 4 are each independently a hydrocarbon group preferably, an alkyl group or an aryl group is more preferable, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable . R 1 to R 4 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. When at least two of R 1 to R 4 are bonded to each other to form a ring, the ring may include a hetero atom. As said hetero atom, a nitrogen atom can be mentioned.
銨陽離子以下述式(Y1-1)及(Y1-2)中的任一個表示為較佳。 [化學式40] The ammonium cation is preferably represented by either of the following formulas (Y1-1) and (Y1-2). [Chemical formula 40]
式(Y1-1)及(Y1-2)中,R101 表示n價有機基,R1 的含義與式(101)中的R1 相同,Ar101 及Ar102 分別獨立地表示芳基,n表示1以上的整數。 式(Y1-1)中,R101 為從脂肪族烴、芳香族烴或由該等鍵結而成之結構去除n個氫原子之基團為較佳,從碳數2~30的飽和脂肪族烴、苯或萘去除n個氫原子之基團為更佳。 式(Y1-1)中,n為1~4為較佳,1或2為更佳,1為進一步較佳。 式(Y1-2)中,Ar101 及Ar102 分別獨立地為苯基或萘基為較佳,苯基為更佳。In Formula (Y1-1) and (Y1-2), R 101 represents a n-valent organic group, with the same meaning as R in formula (101) R 1 is 1, Ar 101 and Ar 102 each independently represent an aryl group, n Represents an integer of 1 or more. In the formula (Y1-1), R 101 is preferably a group that removes n hydrogen atoms from aliphatic hydrocarbons, aromatic hydrocarbons, or structures formed by these bonds, preferably from saturated fats with 2-30 carbons Group hydrocarbon, benzene or naphthalene is more preferably a group with n hydrogen atoms removed. In formula (Y1-1), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In the formula (Y1-2), Ar 101 and Ar 102 are each independently preferably a phenyl group or a naphthyl group, and a phenyl group is more preferable.
-陰離子- 作為銨鹽中的陰離子,選自羧酸根陰離子、苯酚陰離子、磷酸根陰離子及硫酸根陰離子中的一種為較佳,從能夠兼顧鹽的穩定性及熱分解性的理由考慮,羧酸根陰離子為更佳。亦即,銨鹽為銨陽離子與羧酸根陰離子的鹽為更佳。 羧酸根陰離子為具有兩個以上的羧基之2價以上的羧酸的陰離子為較佳,2價羧酸的陰離子為更佳。依該態樣,能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。尤其,藉由使用2價羧酸的陰離子,能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。-Anion- As the anion in the ammonium salt, one selected from the group consisting of carboxylate anion, phenol anion, phosphate anion, and sulfate anion is preferred. For the reason that the stability and thermal decomposition of the salt can be balanced, the carboxylate anion is more preferred. good. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, the stability, curability, and developability of the curable resin composition can be further improved. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the curable resin composition can be further improved.
羧酸根陰離子以下述式(X1)表示為較佳。 [化學式41] 式(X1)中,EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [Chemical formula 41] In formula (X1), EWG represents an electron withdrawing group.
本實施形態中拉電子基團是指哈密特取代基常數σm表示正的值者。其中,σm在都野雄甫總說、Journal of Synthetic Organic Chemistry, Japan第23卷第8號(1965)p.631-642中有詳細說明。另外,本實施形態中的拉電子基團並不限定於上述文獻中所記載之取代基。 作為σm表示正的值之取代基的例子,可列舉CF3 基(σm=0.43)、CF3 C(=O)基(σm=0.63)、HC≡C基(σm=0.21)、CH2 =CH基(σm=0.06)、Ac基(σm=0.38)、MeOC(=O)基(σm=0.37)、MeC(=O)CH=CH基(σm=0.21)、PhC(=O)基(σm=0.34)、H2 NC(=O)CH2 基(σm=0.06)等。另外,Me表示甲基,Ac表示乙醯基,Ph表示苯基。(以下,相同)。In this embodiment, the electron withdrawing group refers to a Hammett substituent constant σm showing a positive value. Among them, σm is described in detail in Yufu Tono, Journal of Synthetic Organic Chemistry, Japan Volume 23 No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents whose σm represents a positive value include CF 3 group (σm=0.43), CF 3 C(=O) group (σm=0.63), HC≡C group (σm=0.21), CH 2 = CH base (σm=0.06), Ac base (σm=0.38), MeOC (=O) base (σm=0.37), MeC (=O) CH=CH base (σm=0.21), PhC (=O) base ( σm=0.34), H 2 NC (=O) CH 2 base (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group. (Following, the same).
EWG為以下述式(EWG-1)~(EWG-6)表示之基團為較佳。 [化學式42] 式(EWG-1)~(EWG-6)中,Rx1 ~Rx3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基,Ar表示芳香族基。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical formula 42] In the formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aromatic group.
本發明中,羧酸根陰離子以下述式(XA)表示為較佳。 [化學式43] 式(XA)中,L10 表示單鍵或選自包括伸烷基、伸烯基、芳香族基、-NRX -及該等的組合之群組中之2價連接基,RX 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical formula 43] In formula (XA), L 10 represents a single bond or a divalent linking group selected from the group consisting of alkylene, alkenylene, aromatic, -NR X -and combinations thereof, R X represents hydrogen Atom, alkyl, alkenyl or aryl.
作為羧酸根陰離子的具體例,可列舉順丁烯二酸根陰離子、鄰苯二甲酸根陰離子、N-苯基亞胺基二乙酸根陰離子及草酸根陰離子。Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion.
從特定樹脂容易在低溫下進行環化及容易提高硬化性樹脂組成物的保存穩定性的觀點考慮,本發明中的鎓鹽作為陽離子包含銨陽離子,上述鎓鹽作為陰離子包含共軛酸的pKa(pKaH)為2.5以下之陰離子為較佳,包含1.8以下的陰離子為更佳。 上述pKa的下限並無特別限定,從所產生之鹼不易中和且改善特定樹脂等的環化效率之觀點考慮,-3以上為較佳,-2以上為更佳。 作為上述pKa,能夠參閱Determination of Organic Structures by Physical Methods(著者:Brown,H.C.,McDaniel,D.H.,Hafliger,O.,Nachod,F.C.;編著:Braude,E.A.,Nachod, F.C.;Academic Press,New York,1955)或Data for Biochemical Research(著者:Dawson,R.M.C.et al;Oxford,Clarendon Press,1959)中所記載的值。關於未記載於該等文獻的化合物,採用利用ACD/pKa(ACD/Labs製)的軟體並藉由結構式計算之值。From the viewpoints that the specific resin is easily cyclized at low temperature and the storage stability of the curable resin composition is easily improved, the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt contains the pKa of a conjugate acid as an anion ( An anion having a pKaH) of 2.5 or less is preferred, and an anion having a pKaH) of 1.8 or less is more preferred. The lower limit of the above-mentioned pKa is not particularly limited. From the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific resin or the like is improved, -3 or more is preferable, and -2 or more is more preferable. As the above pKa, you can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Edited: Braude, EA, Nachod, FC; Academic Press, New York, 1955 ) Or Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated by the structural formula using software using ACD/pKa (manufactured by ACD/Labs) is used.
作為銨鹽的具體例,能夠列舉以下化合物,但本發明並不限定於此。 [化學式44] As specific examples of the ammonium salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 44]
[亞胺鹽] 本發明中,亞胺鹽表示亞胺陽離子與陰離子的鹽。作為陰離子,可例示與上述銨鹽中的陰離子相同者,且較佳的態樣亦相同。[Imine salt] In the present invention, the imine salt means a salt of an imine cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.
-亞胺陽離子- 作為亞胺陽離子,吡啶鎓陽離子為較佳。 又,作為亞胺陽離子,以下述式(102)表示之陽離子亦較佳。 [化學式45] -Imine cation- As the imine cation, pyridinium cation is preferred. Moreover, as the imine cation, a cation represented by the following formula (102) is also preferable. [Chemical formula 45]
式(102)中,R5 及R6 分別獨立地表示氫原子或烴基,R7 表示烴基,R5 ~R7 中的至少兩個可以分別鍵結而形成環。 式(102)中,R5 及R6 的含義與上述式(101)中的R1 ~R4 相同,且較佳的態樣亦相同。 式(102)中,R7 與R5 及R6 中的至少一個鍵結而形成環為較佳。上述環亦可以包含雜原子。作為上述雜原子,可列舉氮原子。又,作為上述環,吡啶環為較佳。In formula (102), R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group, R 7 represents a hydrocarbon group, and at least two of R 5 to R 7 may be bonded to each other to form a ring. In formula (102), R 5 and R 6 have the same meanings as R 1 to R 4 in the above formula (101), and preferred aspects are also the same. In the formula (102), it is preferable that R 7 is bonded to at least one of R 5 and R 6 to form a ring. The aforementioned ring may also contain heteroatoms. As said hetero atom, a nitrogen atom can be mentioned. In addition, as the above-mentioned ring, a pyridine ring is preferred.
亞胺陽離子為以下述式(Y1-3)~(Y1-5)中的任一個表示者為較佳。 [化學式46] 式(Y1-3)~(Y1-5)中,R101 表示n價有機基,R5 的含義與式(102)中的R5 相同,R7 的含義與式(102)中的R7 相同,n表示1以上的整數,m表示0以上的整數。 式(Y1-3)中,R101 為從脂肪族烴、芳香族烴或由該等鍵結而成之結構去除n個氫原子之基團為較佳,從碳數2~30的飽和脂肪族烴、苯或萘去除n個氫原子之基團為更佳。 式(Y1-3)中,n為1~4為較佳,1或2為更佳,1為進一步較佳。 式(Y1-5)中,m為0~4為較佳,1或2為更佳,1為進一步較佳。The imine cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5). [Chemical formula 46] In Formula (Y1-3) ~ (Y1-5), R 101 represents a n-valent organic group, with the same meaning as R in formula (102) 5 R 5, and R in the meaning of formula (102) 7 R 7 Similarly, n represents an integer of 1 or more, and m represents an integer of 0 or more. In formula (Y1-3), R 101 is preferably a group that removes n hydrogen atoms from aliphatic hydrocarbons, aromatic hydrocarbons, or structures formed by these bonds, and is preferably a saturated fat with 2-30 carbons. Group hydrocarbon, benzene or naphthalene is more preferably a group with n hydrogen atoms removed. In the formula (Y1-3), n is preferably 1 to 4, 1 or 2 is more preferable, and 1 is even more preferable. In formula (Y1-5), m is preferably from 0 to 4, 1 or 2 is more preferably, and 1 is even more preferably.
作為亞胺鹽的具體例,能夠列舉以下化合物,但本發明並不限定於此。 [化學式47] As specific examples of the imine salt, the following compounds can be cited, but the present invention is not limited to these. [Chemical formula 47]
[鋶鹽] 本發明中,鋶鹽表示鋶陽離子與陰離子的鹽。作為陰離子,可例示與上述銨鹽中的陰離子相同者,且較佳的態樣亦相同。[Salt] In the present invention, a sulfonium salt means a salt of sulfonium cation and anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.
-鋶陽離子- 作為鋶陽離子,第三鋶陽離子為較佳,三芳基鋶陽離子為更佳。 又,作為鋶陽離子,以下述式(103)表示之陽離子為較佳。 [化學式48] -Alium cation- As the alumnium cation, the third alumnium cation is preferred, and the triaryl alumnium cation is more preferred. Moreover, as a cation, a cation represented by the following formula (103) is preferable. [Chemical formula 48]
式(103)中,R8 ~R10 分別獨立地表示烴基。 R8 ~R10 分別獨立地為烷基或芳基為較佳,碳數1~10的烷基或碳數6~12的芳基為更佳,碳數6~12的芳基為進一步較佳,苯基為進一步較佳。 R8 ~R10 亦可以具有取代基,作為取代基的例子,可列舉羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。該等中,作為取代基,具有烷基或烷氧基為較佳,具有支鏈烷基或烷氧基為更佳,具有碳數3~10的支鏈烷基或碳數1~10的烷氧基為進一步較佳。 R8 ~R10 可以為相同的基團,亦可以為不同之基團,從合成適性上的觀點考慮,相同的基團為較佳。In formula (103), R 8 to R 10 each independently represent a hydrocarbon group. R 8 to R 10 are each independently an alkyl group or an aryl group, preferably, an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R 8 to R 10 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among these, as the substituent, it is preferable to have an alkyl group or an alkoxy group, and it is more preferable to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbons or one having 1 to 10 carbons Alkoxy is further preferred. R 8 to R 10 may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.
[錪鹽] 本發明中,錪鹽表示錪陽離子與陰離子的鹽。作為陰離子,可例示與上述銨鹽中的陰離子相同者,且較佳的態樣亦相同。[Salt] In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.
-錪陽離子- 作為錪陽離子,二芳基錪陽離子為較佳。 又,作為錪陽離子,以下述式(104)表示之陽離子為較佳。 [化學式49] -Iiodonium cation- As the iodonium cation, a diaryl iodonium cation is preferred. In addition, as the iodonium cation, a cation represented by the following formula (104) is preferred. [Chemical formula 49]
式(104)中,R11 及R12 分別獨立地表示烴基。 R11 及R12 分別獨立地為烷基或芳基為較佳,碳數1~10的烷基或碳數6~12的芳基為更佳,碳數6~12的芳基為進一步較佳,苯基為進一步較佳。 R11 及R12 亦可以具有取代基,作為取代基的例子,可列舉羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。其中,作為取代基,具有烷基或烷氧基為較佳,具有支鏈烷基或烷氧基為更佳,具有碳數3~10的支鏈烷基或碳數1~10的烷氧基為進一步較佳。 R11 及R12 可以為相同的基團,亦可以為不同之基團,從合成適性上的觀點考慮,相同的基團為較佳。In formula (104), R 11 and R 12 each independently represent a hydrocarbon group. It is preferable that R 11 and R 12 are independently an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R 11 and R 12 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred The base is further preferred. R 11 and R 12 may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.
[鏻鹽] 本發明中,鏻鹽表示鏻陽離子與陰離子的鹽。作為陰離子,可例示與上述銨鹽中的陰離子相同者,且較佳的態樣亦相同。[Phosphonium salt] In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt can be exemplified, and the preferred aspect is also the same.
-鏻陽離子- 作為鏻陽離子,第四鏻陽離子為較佳,可列舉四烷基鏻陽離子、三芳基單烷基鏻陽離子等。 又,作為鏻陽離子,以下述式(105)表示之陽離子為較佳。 [化學式50] -Phosphonium cation- As the phosphonium cation, a fourth phosphonium cation is preferred, and tetraalkyl phosphonium cations, triaryl monoalkyl phosphonium cations and the like are mentioned. In addition, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 50]
式(105)中,R13 ~R16 分別獨立地表示氫原子或烴基。 R13 ~R16 分別獨立地為烷基或芳基為較佳,碳數1~10的烷基或碳數6~12的芳基為更佳,碳數6~12的芳基為進一步較佳,苯基為進一步較佳。 R13 ~R16 亦可以具有取代基,作為取代基的例子,可列舉羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。其中,作為取代基,具有烷基或烷氧基為較佳,具有支鏈烷基或烷氧基為更佳,具有碳數3~10的支鏈烷基或碳數1~10的烷氧基為進一步較佳。 R13 ~R16 可以為相同的基團,亦可以為不同之基團,從合成適性上的觀點考慮,相同的基團為較佳。In formula (105), R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group. It is preferable that R 13 to R 16 are independently an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbons or an aryl group having 6 to 12 carbons is more preferable, and an aryl group having 6 to 12 carbons is more preferable. Preferably, phenyl is further preferred. R 13 to R 16 may have substituents. Examples of substituents include hydroxyl, aryl, alkoxy, aryloxy, arylcarbonyl, alkylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, Oxo and so on. Among them, as the substituent, an alkyl group or an alkoxy group is preferred, and a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbons or an alkoxy group having 1 to 10 carbons is more preferred The base is further preferred. R 13 to R 16 may be the same group or different groups. From the viewpoint of synthetic suitability, the same group is preferred.
本發明的硬化性樹脂組成物含有鎓鹽時,鎓鹽的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1~50質量%為較佳。下限為0.5質量%以上為更佳,0.85質量%以上為進一步較佳,1質量%以上為更進一步較佳。上限為30質量%以下為更佳,20質量%以下為進一步較佳,10質量%以下為更進一步較佳,可以為5質量%以下,亦可以為4質量%以下。 鎓鹽能夠使用一種或兩種以上。使用兩種以上時,合計量為上述範圍為較佳。When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, more preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, and may be 5% by mass or less, or may be 4% by mass or less. One type or two or more types of onium salts can be used. When two or more are used, the total amount is preferably in the above-mentioned range.
<熱鹼產生劑> 本發明的硬化性樹脂組成物亦可以包含熱鹼產生劑。 尤其,特定樹脂為聚醯亞胺前驅物時,硬化性樹脂組成物含有熱鹼產生劑為較佳。 熱鹼產生劑可以為符合上述鎓鹽之化合物,亦可以為除了上述鎓鹽以外的其他熱鹼產生劑。 作為其他熱鹼產生劑,可列舉非離子系熱鹼產生劑。 作為非離子系熱鹼產生劑,可列舉以式(B1)或式(B2)表示之化合物。 [化學式51] <Thermal base generator> The curable resin composition of the present invention may contain a thermal base generator. In particular, when the specific resin is a polyimide precursor, the curable resin composition preferably contains a thermal alkali generator. The thermal base generator may be a compound conforming to the above-mentioned onium salt, or may be another thermal base generator other than the above-mentioned onium salt. Examples of other hot alkali generators include nonionic hot alkali generators. Examples of the nonionic thermal base generator include compounds represented by formula (B1) or formula (B2). [Chemical formula 51]
式(B1)及式(B2)中,Rb1 、Rb2 及Rb3 分別獨立為不具有第三胺結構之有機基、鹵素原子或氫原子。其中,Rb1 及Rb2 不會同時成為氫原子。又,Rb1 、Rb2 及Rb3 均不具有羧基。另外,本說明書中,第三胺結構是指3價氮原子的三個鍵結鍵均與烴系的碳原子進行共價鍵結之結構。因此,所鍵結之碳原子為形成羰基之碳原子時,亦即在與氮原子一同形成醯胺基時,不限於此。In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group without a third amine structure, a halogen atom, or a hydrogen atom. Among them, Rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Moreover, none of Rb 1 , Rb 2 and Rb 3 has a carboxyl group. In addition, in this specification, the third amine structure refers to a structure in which all three bonding bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amido group together with a nitrogen atom, it is not limited to this.
式(B1)、(B2)中,Rb1 、Rb2 及Rb3 中的至少一個包含環狀結構為較佳,至少兩個包含環狀結構為更佳。作為環狀結構,可以為單環及縮合環中的任一個,單環或兩個單環縮合而成之縮合環為較佳。單環為5員環或6員環為較佳,6員環為更佳。單環為環己烷環及苯環為較佳,環己烷環為更佳。In formulas (B1) and (B2), it is preferable that at least one of Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two contain a cyclic structure. The cyclic structure may be any one of a monocyclic ring and a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferable. A single ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferred. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferable.
更具體而言,Rb1 及Rb2 為氫原子、烷基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳)、烯基(碳數2~24為較佳,2~18為更佳,3~12為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~10為進一步較佳)或芳烷基(碳數7~25為較佳,7~19為更佳,7~12為進一步較佳)為較佳。該等基團亦可以在發揮本發明的效果之範圍內具有取代基。Rb1 與Rb2 可以相互鍵結而形成環。作為所形成之環,4~7員的含氮雜環為較佳。尤其,Rb1 及Rb2 為可以具有取代基之直鏈、支鏈或環狀的烷基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳)為較佳,可以具有取代基之環烷基(碳數3~24為較佳,3~18為更佳,3~12為進一步較佳)為更佳,可以具有取代基之環己基為進一步較佳。More specifically, Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferably, and 3-12 is more preferably), alkenyl (carbon number 2-24 Is preferred, 2-18 is more preferred, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred) or aralkyl The group (the carbon number is preferably 7-25, 7-19 is more preferable, and 7-12 is still more preferable) is preferable. These groups may also have substituents within the range in which the effects of the present invention are exhibited. Rb 1 and Rb 2 may be bonded to each other to form a ring. As the ring formed, a 4- to 7-membered nitrogen-containing heterocyclic ring is preferred. In particular, Rb 1 and Rb 2 are linear, branched or cyclic alkyl groups which may have substituents (1-24 carbon atoms are preferred, 2-18 are more preferred, and 3-12 are further preferred). Preferably, the cycloalkyl group that may have a substituent (the carbon number is preferably 3-24, more preferably 3-18, and even more preferably 3-12) is more preferable, and the cyclohexyl group that may have a substituent is more preferable. good.
作為Rb3 ,可列舉烷基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~10為進一步較佳)、烯基(碳數2~24為較佳,2~12為更佳,2~6為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~12為進一步較佳)、芳烯基(碳數8~24為較佳,8~20為更佳,8~16為進一步較佳)、烷氧基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳)、芳氧基(碳數6~22為較佳,6~18為更佳,6~12為進一步較佳)、或芳烷氧基(碳數7~23為較佳,7~19為更佳,7~12為進一步較佳)。其中,環烷基(碳數3~24為較佳,3~18為更佳,3~12為進一步較佳)、芳烯基、芳烷氧基為較佳。在發揮本發明的效果之範圍內Rb3 亦可以進一步具有取代基。Examples of Rb 3 include alkyl groups (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is even more preferable), and aryl groups (the carbon number is preferably 6-22, and 6-18 is More preferably, 6-10 is further preferred), alkenyl (carbon number 2-24 is preferred, 2-12 is more preferred, 2-6 is further preferred), aralkyl (carbon number 7-23 is Preferably, 7-19 is more preferred, 7-12 is further preferred), aralkenyl (carbon number 8-24 is preferred, 8-20 is more preferred, 8-16 is further preferred), alkoxy Group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), aryloxy group (the carbon number is 6-22 is preferable, 6-18 is more preferable, 6-12 is more preferable) Is further preferred) or aralkyloxy (the carbon number is preferably 7 to 23, 7 to 19 is more preferred, and 7 to 12 is even more preferred). Among them, cycloalkyl (3 to 24 carbon atoms is preferred, 3 to 18 is more preferred, and 3 to 12 is more preferred), aralkenyl, and aralkoxy are preferred. Rb 3 may further have a substituent as long as the effect of the present invention is exerted.
以式(B1)表示之化合物為以下述式(B1-1)或下述式(B1-2)表示之化合物為較佳。 [化學式52] The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 52]
式中,Rb11 及Rb12 和Rb31 及Rb32 的含義分別與式(B1)中的Rb1 及Rb2 相同。 Rb13 為烷基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳)、烯基(碳數2~24為較佳,2~18為更佳,3~12為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~12為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~12為進一步較佳),可以在發揮本發明的效果之範圍內具有取代基。其中,Rb13 為芳烷基為較佳。In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 have the same meanings as Rb 1 and Rb 2 in the formula (B1), respectively. Rb 13 is an alkyl group (the carbon number is preferably 1-24, 2-18 is more preferable, and 3-12 is more preferable), alkenyl group (the carbon number is 2-24 is preferable, and 2-18 is more preferable, 3-12 is more preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl group (carbon number 7-23 is preferred, 7 to 19 are more preferable, and 7 to 12 are more preferable), and may have a substituent within the range where the effects of the present invention are exhibited. Among them, Rb 13 is preferably an aralkyl group.
Rb33 及Rb34 分別獨立地為氫原子、烷基(碳數1~12為較佳,1~8為更佳,1~3為進一步較佳)、烯基(碳數2~12為較佳,2~8為更佳,2~3為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~10為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~11為進一步較佳),氫原子為較佳。Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (the carbon number is preferably 1 to 12, and 1 to 8 is more preferable, and 1 to 3 is more preferable), and an alkenyl group (the carbon number is 2 to 12 is more preferable). Preferably, 2-8 is more preferable, 2-3 is more preferable), aryl (carbon number 6-22 is preferable, 6-18 is more preferable, 6-10 is more preferable), aralkyl ( The carbon number is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11), and preferably a hydrogen atom.
Rb35 為烷基(碳數1~24為較佳,1~12為更佳,3~8為進一步較佳)、烯基(碳數2~12為較佳,2~12為更佳,3~8為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~12為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~12為進一步較佳),芳基為較佳。Rb 35 is an alkyl group (the carbon number is preferably 1-24, 1-12 is more preferable, and 3-8 is even more preferable), alkenyl group (the carbon number is 2-12 is preferable, and 2-12 is more preferable, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 is more preferred, 7-12 is further preferred), aryl is preferred.
又,以式(B1-1)表示之化合物為以式(B1-1a)表示之化合物亦較佳。 [化學式53] Furthermore, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 53]
Rb11
及Rb12
的含義與式(B1-1)中的Rb11
及Rb12
相同。
Rb15
及Rb16
為氫原子、烷基(碳數1~12為較佳,1~6為更佳,1~3為進一步較佳)、烯基(碳數2~12為較佳,2~6為更佳,2~3為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~10為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~11為進一步較佳),氫原子或甲基為較佳。
Rb17
為烷基(碳數1~24為較佳,1~12為更佳,3~8為進一步較佳)、烯基(碳數2~12為較佳,2~12為更佳,3~8為進一步較佳)、芳基(碳數6~22為較佳,6~18為更佳,6~12為進一步較佳)、芳烷基(碳數7~23為較佳,7~19為更佳,7~12為進一步較佳),其中芳基為較佳。 The meanings of Rb 11 and Rb 12 are the same as Rb 11 and Rb 12 in formula (B1-1). Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (1 to 12 carbon atoms are preferred, 1 to 6 are more preferred, and 1 to 3 are more preferred), alkenyl groups (
非離子系熱鹼產生劑的分子量為800以下為較佳,600以下為更佳,500以下為進一步較佳。作為下限,100以上為較佳,200以上為更佳,300以上為進一步較佳。The molecular weight of the nonionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, 100 or more is preferable, 200 or more is more preferable, and 300 or more is more preferable.
上述鎓鹽中,關於作為熱鹼產生劑的化合物的具體例或其他熱鹼產生劑的具體例,能夠列舉以下化合物。 [化學式54] [化學式55] Among the above-mentioned onium salts, the following compounds can be cited as specific examples of compounds as thermal base generators or other specific examples of thermal base generators. [Chemical formula 54] [Chemical formula 55]
[化學式56] [Chemical formula 56]
熱鹼產生劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1~50質量%為較佳。下限為0.5質量%以上為更佳,1質量%以上為進一步較佳。上限為30質量%以下為更佳,20質量%以下為進一步較佳。熱鹼產生劑能夠使用一種或兩種以上。使用兩種以上時,合計量為上述範圍為較佳。The content of the thermal base generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. One kind or two or more kinds of thermal base generators can be used. When two or more are used, the total amount is preferably in the above-mentioned range.
<遷移抑制劑> 本發明的硬化性樹脂組成物進一步含有遷移抑制劑為較佳。藉由含有遷移抑制劑,能夠有效地抑制來自於金屬層(金屬配線)的金屬離子轉移到硬化性樹脂組成物層內。<Migration inhibitor> The curable resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, it is possible to effectively suppress the transfer of metal ions from the metal layer (metal wiring) into the curable resin composition layer.
作為遷移抑制劑,並無特別限制,可列舉具有雜環(吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、2H-吡喃環及6H-吡喃環、三𠯤環)之化合物、硫脲類及具有氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其,能夠較佳地使用1,2,4-三唑、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring). Ring, pyridine ring, pyran ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-pyran ring, 6H-pyran ring, tricyclic ring) compound, thiourea Classes and compounds with sulfhydryl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
或者,還能夠使用捕捉鹵素離子等陰離子之離子捕捉劑。Alternatively, an ion scavenger that traps anions such as halogen ions can also be used.
作為其他遷移抑制劑,能夠使用日本特開2013-015701號公報的0094段中所記載的防鏽劑、日本特開2009-283711號公報的0073~0076段中所記載的化合物、日本特開2011-059656號公報的0052段中所記載的化合物、日本特開2012-194520號公報的0114段、0116段及0118段中所記載的化合物、國際公開第2015/199219號的0166段中所記載的化合物等。As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011 can be used. -059656 The compound described in paragraph 0052 of JP 2012-194520 A, the compound described in paragraph 0114, paragraph 0116, and paragraph 0118 of JP 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219 Compound etc.
作為遷移抑制劑的具體例,能夠列舉下述化合物。As specific examples of migration inhibitors, the following compounds can be cited.
[化學式57] [Chemical formula 57]
硬化性樹脂組成物具有遷移抑制劑時,遷移抑制劑的含量相對於硬化性樹脂組成物的總固體成分為0.01~5.0質量%為較佳,0.05~2.0質量%為更佳,0.1~1.0質量%為進一步較佳。When the curable resin composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the curable resin composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass % Is more preferable.
遷移抑制劑可以為僅一種,亦可以為兩種以上。遷移抑制劑為兩種以上時,其合計為上述範圍為較佳。There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, it is preferable that the total of them is in the above-mentioned range.
<聚合抑制劑> 本發明的硬化性樹脂組成物含有聚合抑制劑為較佳。<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.
作為聚合抑制劑,例如可較佳地使用對苯二酚、對甲氧基苯酚、二-第三丁基-對甲酚、鄰苯三酚、對-第三丁基鄰苯二酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙(3-甲基-6-第三丁基苯酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基苯酚)、N-亞硝基-N-苯基羥基胺鋁鹽、啡噻𠯤、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-4-甲基苯酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-(N-乙基-N-磺基丙基胺)苯酚、N-亞硝基-N-(1-萘基)羥胺銨鹽、雙(4-羥基-3,5-第三丁基)苯基甲烷等。又,還能夠使用日本特開2015-127817號公報的0060段中所記載的聚合抑制劑及國際公開第2015/125469號的0031~0046段中所記載的化合物。As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, p-tertiary butylcatechol, 1 ,4-Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl -6-tertiary butyl phenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothionine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine Tetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquine Phenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N- Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.
又,能夠使用下述化合物(Me為甲基)。In addition, the following compounds (Me is a methyl group) can be used.
[化學式58] [Chemical formula 58]
本發明的硬化性樹脂組成物具有聚合抑制劑時,聚合抑制劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.01~5質量%為較佳,0.02~3質量%為更佳,0.05~2.5質量%為進一步較佳。When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the curable resin composition of the present invention is preferably 0.01 to 5% by mass, and more preferably 0.02 to 3% by mass. Preferably, 0.05 to 2.5% by mass is more preferable.
聚合抑制劑可以為僅一種,亦可以為兩種以上。聚合抑制劑為兩種以上時,其合計為上述範圍為較佳。There may be only one type of polymerization inhibitor, or two or more types. When there are two or more polymerization inhibitors, it is preferable that the sum total is the above-mentioned range.
<金屬接著性改良劑> 本發明的硬化性樹脂組成物含有用於提高與使用於電極或配線等之金屬材料的接著性之金屬接著性改良劑為較佳。作為金屬接著性改良劑,可列舉矽烷偶合劑等。<Metal adhesion improver> The curable resin composition of the present invention preferably contains a metal adhesive improving agent for improving the adhesiveness with metal materials used for electrodes, wiring, and the like. As the metal adhesion improver, a silane coupling agent and the like can be mentioned.
作為矽烷偶合劑的例,可列舉國際公開第2015/199219號的0167段中所記載的化合物、日本特開2014-191002號公報的0062~0073段中所記載的化合物、國際公開第2011/080992號的0063~0071段中所記載的化合物、日本特開2014-191252號公報的0060~0061段中所記載的化合物、日本特開2014-041264號公報的0045~0052段中所記載的化合物、國際公開第2014/097594號的0055段中所記載的化合物。又,如日本特開2011-128358號公報的0050~0058段中所記載,使用不同的兩種以上的矽烷偶合劑亦較佳。又,矽烷偶合劑使用下述化合物亦較佳。以下式中,Et表示乙基。Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264, The compound described in paragraph 0055 of International Publication No. 2014/097594. In addition, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group.
[化學式59] [Chemical formula 59]
又,作為金屬接著性改良劑,還能夠使用日本特開2014-186186號公報的0046~0049段中所記載的化合物、日本特開2013-072935號公報的0032~0043段中所記載的硫化物系化合物。In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and sulfides described in paragraphs 0032 to 043 of JP 2013-072935 can also be used. Department of compounds.
金屬接著性改良劑的含量相對於特定樹脂100質量份較佳為0.1~30質量份,更佳為0.5~15質量份的範圍,進一步較佳為0.5~5質量份的範圍。藉由設為上述下限值以上,硬化步驟後的硬化膜與金屬層的接著性變得良好,藉由設為上述上限值以下,硬化步驟後的硬化膜的耐熱性、機械特性變得良好。金屬接著性改良劑可以僅為一種,亦可以為兩種以上。使用兩種以上時,其合計為上述範圍為較佳。The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the specific resin, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass. By setting it to be higher than the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes better, and by setting it to be less than the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, it is preferable that the sum total is the above-mentioned range.
<其他添加劑> 本發明的硬化性樹脂組成物能夠依需要摻和各種添加物,例如N-苯基二乙醇胺等敏化劑、鏈轉移劑、界面活性劑、高級脂肪酸衍生物、無機粒子、硬化劑、硬化觸媒、填充劑、抗氧化劑、紫外線吸收劑、凝聚抑制劑等。摻和該等添加劑時,將其合計摻和量設為硬化性樹脂組成物的固體成分的3質量%以下為較佳。<Other additives> The curable resin composition of the present invention can be blended with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening touch Medium, filler, antioxidant, ultraviolet absorber, aggregation inhibitor, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
[敏化劑] 本發明的硬化性樹脂組成物亦可以具有敏化劑。敏化劑吸收特定的活性放射線而成為電子激勵狀態。成為電子激勵狀態之敏化劑與熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑等接觸,而產生電子轉移、能量轉移、發熱等作用。藉此,熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑引起化學變化而分解,並產生自由基、酸或鹼。 作為敏化劑,可列舉N-苯基二乙醇胺等敏化劑。 又,作為敏化劑,亦可以使用增感色素。 關於增感色素,具體能夠參閱日本特開2016-027357號公報的0161~0163段的記載,且該內容被編入本說明書中。[Sensitizer] The curable resin composition of the present invention may have a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal hardening accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, etc., to generate electron transfer, energy transfer, heat generation, and the like. Thereby, the thermal hardening accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator cause chemical changes to decompose, and generate free radicals, acids, or alkalis. Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, as a sensitizer, a sensitizing dye can also be used. Regarding the sensitizing dye, refer to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, and the content is incorporated in this specification.
本發明的硬化性樹脂組成物含有敏化劑時,敏化劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.01~20質量%為較佳,0.1~15質量%為更佳,0.5~10質量%為進一步較佳。敏化劑可以單獨使用一種,亦可以同時使用兩種以上。When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the curable resin composition of the present invention is preferably 0.01-20% by mass, and more preferably 0.1-15% by mass. Preferably, 0.5 to 10% by mass is more preferable. One kind of sensitizer may be used alone, or two or more kinds may be used at the same time.
[鏈轉移劑] 本發明的硬化性樹脂組成物亦可以具有鏈轉移劑。鏈轉移劑例如於高分子詞典第三版(高分子學會(The Society of Polymer Science, Japan)編,2005年)683-684頁中被定義。作為鏈轉移劑,例如使用在分子內具有SH、PH、SiH及GeH之化合物群組。該等對低活性自由基供給氫而產生自由基,或者在經氧化之後可藉由去質子來產生自由基。尤其,能夠較佳地使用硫醇化合物。[Chain transfer agent] The curable resin composition of the present invention may have a chain transfer agent. The chain transfer agent is defined, for example, in pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. These low-activity free radicals are supplied with hydrogen to generate free radicals, or they can be deprotonated to generate free radicals after being oxidized. In particular, thiol compounds can be preferably used.
又,鏈轉移劑還能夠使用國際公開第2015/199219號的0152~0153段中所記載的化合物。In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.
本發明的硬化性樹脂組成物具有鏈轉移劑時,鏈轉移劑的含量相對於本發明的硬化性樹脂組成物的總固體成分100質量份為0.01~20質量份為較佳,1~10質量份為更佳,1~5質量份為進一步較佳。鏈轉移劑可以為僅一種,亦可以為兩種以上。鏈轉移劑為兩種以上時,其合計為上述範圍為較佳。When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention, preferably 1-10 parts by mass Parts are more preferable, and 1 to 5 parts by mass are still more preferable. There may be only one type of chain transfer agent, or two or more types. When there are two or more chain transfer agents, the total of them is preferably in the above-mentioned range.
[界面活性劑] 從進一步提高塗佈性的觀點考慮,本發明的硬化性樹脂組成物中亦可以添加各種界面活性劑。作為界面活性劑,能夠使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、聚矽氧系界面活性劑等各種界面活性劑。又,下述界面活性劑亦較佳。下述式中,表示主鏈的重複單元之括號表示各重複單元的含量(莫耳%),表示側鏈的重複單元之括號表示各重複單元的重複數。 [化學式60] 又,界面活性劑還能夠使用國際公開第2015/199219號的0159~0165段中所記載的化合物。[Surfactant] From the viewpoint of further improving coatability, various surfactants may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating units of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the repeating number of each repeating unit. [Chemical formula 60] In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
本發明的硬化性樹脂組成物具有界面活性劑時,界面活性劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.001~2.0質量%為較佳,更佳為0.005~1.0質量%。界面活性劑可以為僅一種,亦可以為兩種以上。界面活性劑為兩種以上時,其合計為上述範圍為較佳。When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the curable resin composition of the present invention, more preferably 0.005 to 1.0 mass% %. There may be only one type of surfactant, or two or more types. When there are two or more surfactants, it is preferable that the sum total is the above-mentioned range.
[高級脂肪酸衍生物] 為了防止因氧導致的聚合阻礙,本發明的硬化性樹脂組成物中亦可以添加如二十二酸或二十二酸醯胺的高級脂肪酸衍生物,而使其在塗佈後的乾燥過程中偏在於硬化性樹脂組成物的表面。[Higher fatty acid derivatives] In order to prevent polymerization inhibition due to oxygen, the curable resin composition of the present invention can also be added with higher fatty acid derivatives such as behenic acid or behenic acid amide, so that it can be used in the drying process after coating. Partially on the surface of the curable resin composition.
又,高級脂肪酸衍生物還能夠使用國際公開第2015/199219號的0155段中所記載的化合物。In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.
本發明的硬化性樹脂組成物具有高級脂肪酸衍生物時,高級脂肪酸衍生物的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1~10質量%為較佳。高級脂肪酸衍生物可以為僅一種,亦可以為兩種以上。高級脂肪酸衍生物為兩種以上時,其合計為上述範圍為較佳。When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, the total of them is preferably in the above-mentioned range.
<關於其他所含物質的限制> 從塗佈面性狀的觀點考慮,本發明的硬化性樹脂組成物的水分含量小於5質量%為較佳,小於1質量%為更佳,小於0.6質量%為進一步較佳。<Restrictions on other contained substances> From the viewpoint of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass.
從絕緣性的觀點考慮,本發明的硬化性樹脂組成物的金屬含量小於5質量ppm(parts per million(百萬分率))為較佳,小於1質量ppm為更佳,小於0.5質量ppm為進一步較佳。作為金屬,可列舉鈉、鉀、鎂、鈣、鐵、鉻、鎳等。包含複數種金屬時,該等金屬的合計為上述範圍為較佳。From the viewpoint of insulation, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably in the above-mentioned range.
又,作為減少意外包含在本發明的硬化性樹脂組成物中之金屬雜質之方法,能夠列舉如下方法:作為構成本發明的硬化性樹脂組成物之原料而選擇金屬含量較少的原料;對構成本發明的硬化性樹脂組成物之原料進行過濾器過濾;將聚四氟乙烯等內襯於裝置內以在盡可能抑制污染之條件下進行蒸餾。In addition, as a method of reducing the metal impurities accidentally contained in the curable resin composition of the present invention, the following method can be cited: as a raw material constituting the curable resin composition of the present invention, a raw material with a small metal content is selected; The raw material of the curable resin composition of the present invention is filtered by a filter; the device is lined with polytetrafluoroethylene, etc., so that the distillation can be carried out under the condition of suppressing pollution as much as possible.
若考慮作為半導體材料的用途,且從配線腐蝕性的觀點考慮,本發明的硬化性樹脂組成物中,鹵素原子的含量小於500質量ppm為較佳,小於300質量ppm為更佳,小於200質量ppm為進一步較佳。其中,以鹵素離子的狀態存在者小於5質量ppm為較佳,小於1質量ppm為更佳,小於0.5質量ppm為進一步較佳。作為鹵素原子,可列舉氯原子及溴原子。氯原子及溴原子或氯離子及溴離子的合計分別為上述範圍為較佳。Considering the use as a semiconductor material and from the perspective of wiring corrosion, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. ppm is more preferable. Among them, less than 5 mass ppm is preferable in the state of halogen ions, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned ranges.
作為本發明的硬化性樹脂組成物的收容容器,能夠使用以往公知的收容容器。又,作為收容容器,以抑制雜質混入原材料或硬化性樹脂組成物中為目的,使用由6種6層樹脂構成容器內壁之多層瓶、將6種樹脂形成為7層結構之瓶亦較佳。作為這種容器,例如可列舉日本特開2015-123351號公報中所記載的容器。As the storage container of the curable resin composition of the present invention, a conventionally known storage container can be used. In addition, as a container, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure for the purpose of preventing impurities from mixing into the raw material or the curable resin composition. . As such a container, for example, the container described in JP 2015-123351 A can be cited.
<硬化性樹脂組成物的製備> 本發明的硬化性樹脂組成物能夠藉由混合上述各成分來製備。混合方法並無特別限定,能夠藉由以往公知的方法來進行。<Preparation of curable resin composition> The curable resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method.
又,以去除硬化性樹脂組成物中的灰塵或微粒等異物為目的,進行使用過濾器之過濾為較佳。過濾器孔徑為1μm以下為較佳,0.5μm以下為更佳,0.1μm以下為進一步較佳。過濾器的材質為聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器可以使用藉由有機溶劑預先清洗者。過濾器的過濾步驟中,亦可以串聯或並聯複數種過濾器而使用。使用複數種過濾器時,可以組合使用孔徑或材質不同之過濾器。又,可以將各種材料過濾複數次。過濾複數次時,可以為循環過濾。又,亦可以在加壓之後進行過濾。加壓之後進行過濾時,進行加壓之壓力為0.05MPa以上且0.3MPa以下為較佳。 除了使用過濾器之過濾以外,還可以進行使用吸附材料之雜質去除處理。亦可以組合過濾器過濾與使用吸附材料之雜質去除處理。作為吸附材料,能夠使用公知的吸附材料。例如,可列舉矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。In addition, for the purpose of removing foreign matter such as dust or particles in the curable resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filtering step of the filter, multiple filters may be used in series or in parallel. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.
<硬化性樹脂組成物的用途> 本發明的硬化性樹脂組成物用於形成再配線層用層間絕緣膜為較佳。 又,還能夠用於半導體器件的絕緣膜的形成或應力緩衝膜的形成等。<Use of curable resin composition> The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for the formation of an insulating film of a semiconductor device, the formation of a stress buffer film, and the like.
(硬化膜、積層體、半導體器件及該等的製造方法) 接著,對硬化膜、積層體、半導體器件及該等的製造方法進行說明。(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method thereof will be described.
本發明的硬化膜係將本發明的硬化性樹脂組成物硬化而成。本發明的硬化膜的膜厚例如能夠設為0.5μm以上,且能夠設為1μm以上。又,作為上限值,能夠設為100μm以下,且還能夠設為30μm以下。The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more, for example. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.
可以將本發明的硬化膜積層2層以上,進而積層3~7層來作為積層體。本發明的積層體為具有2層以上的硬化膜且在硬化膜之間具有金屬層之積層體為較佳。又,本發明的積層體包含2層以上的硬化膜,在任意上述硬化膜彼此之間包含金屬層之態樣為較佳。例如,可較佳地列舉至少包含依序積層有第一硬化膜、金屬層、第二硬化膜這3個層之層結構之積層體。上述第一硬化膜及上述第二硬化膜均為本發明的硬化膜,例如可較佳地列舉上述第一硬化膜及上述第二硬化膜均為將本發明的硬化性樹脂組成物硬化而成之膜之態樣。用於形成上述第一硬化膜之本發明的硬化性樹脂組成物與用於形成上述第二硬化膜之本發明的硬化性樹脂組成物可以為組成相同的組成物,亦可以為組成不同的組成物,從製造適性上的觀點考慮,組成相同的組成物為較佳。這種金屬層可較佳地用作再配線層等的金屬配線。Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. In addition, the laminate of the present invention includes two or more cured films, and it is preferable to include a metal layer between any of the above-mentioned cured films. For example, a laminated body including at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are sequentially laminated can be preferably cited. The first cured film and the second cured film are both cured films of the present invention. For example, preferably, the first cured film and the second cured film are formed by curing the curable resin composition of the present invention. The state of the film. The curable resin composition of the present invention for forming the above-mentioned first cured film and the curable resin composition of the present invention for forming the above-mentioned second cured film may have the same composition or different compositions. From the viewpoint of manufacturing suitability, a composition having the same composition is preferable. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.
作為能夠適用本發明的硬化膜的領域,可列舉半導體器件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外,還可列舉密封膜、基板材料(柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜)或藉由對如上述實際安裝用途的絕緣膜進行蝕刻而形成圖案之情況等。關於該等用途,例如能夠參閱Science & Technology Co.,Ltd.“聚醯亞胺的高功能化和應用技術”2008年4月、柿本雅明/監修、CMC技術圖書館“聚醯亞胺材料的基礎和開發”2011年11月發行、日本聚醯亞胺・芳香族系高分子研究會/編“最新聚醯亞胺 基礎和應用”NTS,2010年8月等。Examples of the fields to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, and an interlayer insulating film), or a case where a pattern is formed by etching an insulating film for actual mounting purposes as described above, etc. can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Yamin/Supervisor, CMC Technical Library "Polyimide Materials Fundamentals and Development" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.
又,本發明中的硬化膜還能夠使用於膠印版面或網版版面等版面的製造、蝕刻成形組件的用途、電子尤其微電子中的保護漆及介電層的製造等中。In addition, the cured film in the present invention can also be used in the production of offset printing plates or screen plates, the use of etching and forming components, and the production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.
本發明的硬化膜的製造方法(以下,亦簡稱為“本發明的製造方法”。)包括將本發明的硬化性樹脂組成物適用於基材而形成膜之膜形成步驟為較佳。 進而,本發明的硬化膜的製造方法包括上述膜形成步驟,並且進一步包括將上述膜曝光之曝光步驟及將上述膜顯影之(對上述膜進行顯影處理)顯影步驟為更佳。 進而,本發明的硬化膜的製造方法包括上述膜形成步驟(及依需要包括上述顯影步驟),並且進一步包括在50~450℃下加熱上述膜之加熱步驟為更佳。 具體而言,包括以下(a)~(d)的步驟亦較佳。 (a)將硬化性樹脂組成物適用於基材而形成膜(硬化性樹脂組成物層)之膜形成步驟 (b)膜形成步驟之後,將膜曝光之曝光步驟 (c)將曝光之上述膜進行顯影處理之顯影步驟 (d)將顯影之上述膜在50~450℃下加熱之加熱步驟 藉由在上述加熱步驟中進行加熱,能夠進一步使藉由曝光硬化之樹脂層硬化。在該加熱步驟中,例如上述熱鹼產生劑分解,可獲得充分的硬化性。The production method of the cured film of the present invention (hereinafter, also simply referred to as "the production method of the present invention") preferably includes a film formation step of applying the curable resin composition of the present invention to a substrate to form a film. Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming step, and further includes an exposure step of exposing the above-mentioned film and a development step of developing the above-mentioned film (performing a development process on the above-mentioned film). Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming step (and the above-mentioned development step as necessary), and further includes a heating step of heating the above-mentioned film at 50 to 450°C. Specifically, it is also preferable to include the following steps (a) to (d). (A) Film formation step of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (B) Exposure step of exposing the film after the film formation step (C) The developing step of developing the above-mentioned exposed film (D) Heating step of heating the developed film at 50~450℃ By heating in the above heating step, the resin layer hardened by exposure can be further hardened. In this heating step, for example, the above-mentioned hot alkali generator is decomposed, and sufficient hardenability can be obtained.
本發明的較佳的實施形態之積層體的製造方法包括本發明的硬化膜的製造方法。本實施形態的積層體的製造方法按照上述之硬化膜的製造方法,形成硬化膜之後,進而再次進行(a)的步驟或(a)~(c)的步驟或(a)~(d)的步驟。尤其,依序將上述各步驟進行複數次,例如2~5次(亦即,合計3~6次)為較佳。藉由如此積層硬化膜,能夠形成積層體。本發明中,尤其在設置有硬化膜之部分之上面或硬化膜之間或該兩個位置設置金屬層為較佳。另外,在積層體的製造中,無需重複(a)~(d)的所有步驟,能夠如上述藉由進行複數次至少(a)、較佳為(a)~(c)或(a)~(d)的步驟而獲得硬化膜的積層體。 <膜形成步驟(層形成步驟)> 本發明的較佳的實施形態之製造方法包括將硬化性樹脂組成物適用於基材而形成膜(層狀)之膜形成步驟(層形成步驟)。The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminate of this embodiment follows the above-mentioned method of manufacturing a cured film, and after forming a cured film, the step (a) or the steps (a) to (c) or the steps (a) to (d) are performed again. step. In particular, it is preferable to perform the above-mentioned steps multiple times in sequence, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminate can be formed. In the present invention, it is particularly preferable to provide a metal layer on the upper surface of the part where the cured film is provided, between the cured films, or at the two positions. In addition, in the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and it is possible to perform at least (a), preferably (a) to (c) or (a) to multiple times as described above. In the step (d), a laminated body of a cured film is obtained. <Film formation step (layer formation step)> The manufacturing method of the preferred embodiment of the present invention includes a film formation step (layer formation step) of applying a curable resin composition to a substrate to form a film (layered).
基材的種類能夠依用途而適當設定,但並無特別限制,可列舉矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基材、石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材、紙、SOG(Spin On Glass)、TFT(薄膜晶體管)陣列基材、電漿顯示面板(PDP)的電極板等。本發明中,尤其半導體製作基材為較佳,矽基材為更佳。 又,作為基材,例如使用板狀的基材(基板)。The type of substrate can be appropriately set according to the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and steam. Coating, magnetic film, reflective film, Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, etc. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates are more preferred. In addition, as the base material, for example, a plate-shaped base material (substrate) is used.
又,在樹脂層的表面或金屬層的表面形成硬化性樹脂組成物層時,樹脂層或金屬層成為基材。In addition, when the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.
作為將硬化性樹脂組成物適用於基材之方法,塗佈為較佳。As a method of applying the curable resin composition to the substrate, coating is preferred.
具體而言,作為所適用之方法,可例示浸塗法、氣刀塗佈法、簾式塗佈法、線棒塗佈法、凹版塗佈法、擠壓塗佈法、噴塗法、旋塗法、狹縫塗佈法及噴墨法等。從硬化性樹脂組成物層的厚度均勻性的觀點考慮,更佳為旋塗法、狹縫塗佈法、噴塗法、噴墨法。依方法調整適當的固體成分濃度或塗佈條件,藉此能夠獲得所期望的厚度的樹脂層。又,還能夠依基材的形狀適當選擇塗佈方法,若為晶圓等圓形基材,則旋塗法或噴塗法、噴墨法等為較佳,若為矩形基材,則狹縫塗佈法或噴塗法、噴墨法等為較佳。為旋塗法時,例如能夠以500~2,000rpm(revolutions per minute:每分鐘轉數)的轉速適用10秒~1分鐘左右。 又,還能夠適用將藉由上述賦予方法預先在偽支撐體上賦予而形成之塗膜轉印在基材上之方法。 關於轉印方法,本發明中亦能夠較佳地採用日本特開2006-023696號公報的0023段、0036~0051段或日本特開2006-047592號公報的0096~0108段中所記載的製作方法。Specifically, as the applicable method, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, and the spin coating method can be exemplified. Method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, the spin coating method, the slit coating method, the spray method, and the inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. For round substrates such as wafers, spin coating, spray coating, and inkjet methods are preferred. For rectangular substrates, slits Coating method, spraying method, inkjet method, etc. are preferable. In the case of a spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. In addition, it is also possible to apply a method of transferring a coating film formed by applying the above-mentioned applying method on a pseudo support in advance to a substrate. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used in the present invention. .
<乾燥步驟> 本發明的製造方法亦可以包括在形成上述膜(硬化性樹脂組成物層)之後,膜形成步驟(層形成步驟)之後,為了去除溶劑而進行乾燥之步驟。較佳的乾燥溫度為50~150℃,70~130℃為更佳,90~110℃為進一步較佳。作為乾燥時間,可例示30秒~20分鐘,1分鐘~10分鐘為較佳,3分鐘~7分鐘為更佳。<Drying step> The production method of the present invention may also include a step of drying in order to remove the solvent after the film formation step (layer formation step) after the film (curable resin composition layer) is formed. The preferred drying temperature is 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
<曝光步驟> 本發明的製造方法亦可以包括將上述膜(硬化性樹脂組成物層)曝光之曝光步驟。曝光量只要能夠將硬化性樹脂組成物硬化,則無特別限定,例如以波長365nm下的曝光能量換算計照射100~10,000mJ/cm2 為較佳,照射200~8,000mJ/cm2 為更佳。<Exposure Step> The manufacturing method of the present invention may also include an exposure step of exposing the above-mentioned film (curable resin composition layer). As long as the amount of exposure can be cured curable resin composition is not particularly limited, for example, under an exposure energy in terms of wavelength of 365nm is irradiated 100 ~ 10,000mJ / cm 2 is preferred, irradiation of 200 ~ 8,000mJ / cm 2 is more preferably .
曝光波長能夠在190~1,000nm的範圍內適當設定,240~550nm為較佳。The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
關於曝光波長,若以與光源的關係描述,則可列舉(1)半導體雷射(波長830nm、532nm、488nm、405nm etc.)、(2)金屬鹵化物燈、(3)高壓水銀燈、g射線(波長436nm)、h射線(波長405nm)、i射線(波長365nm)、寬(g、h、i射線的3波長)、(4)準分子雷射、KrF準分子雷射(波長248nm)、ArF準分子雷射(波長193nm)、F2準分子雷射(波長157nm)、(5)極紫外線;EUV(波長13.6nm)、(6)電子束等。關於本發明中的硬化性樹脂組成物,尤其基於高壓水銀燈之曝光為較佳,其中,基於i射線之曝光為較佳。藉此,可得到尤其高的曝光靈敏度。Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the curable resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained.
<顯影步驟> 本發明的製造方法亦可以包括對曝光之膜(硬化性樹脂組成物層)進行顯影處理之顯影步驟。藉由進行顯影,未曝光的部分(非曝光部)被去除。關於顯影方法,只要能夠形成所期望的圖案,則並無特別限制,例如能夠採用覆液式、噴霧、浸漬、超音波等顯影方法。<Development step> The manufacturing method of the present invention may also include a development step of developing the exposed film (curable resin composition layer). By performing development, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, a development method such as a liquid coating method, spraying, dipping, and ultrasonic can be adopted.
顯影使用顯影液來進行。關於顯影液,只要可去除未曝光的部分(非曝光部),則使用上能夠不加以特別限制。 本發明中,將作為顯影液使用鹼顯影液之情況稱為鹼性顯影,將作為顯影液使用含有50質量%以上有機溶劑之顯影液之情況稱為溶劑顯影。The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, there is no particular limitation on its use. In the present invention, the case of using an alkaline developer as the developer is referred to as alkaline development, and the case of using a developer containing 50% by mass or more of an organic solvent as the developer is referred to as solvent development.
鹼性顯影中,顯影液中有機溶劑的含量相對於顯影液的總質量為10質量%以下為較佳,5質量%以下為更佳,1質量%以下為進一步較佳,不含有機溶劑為特佳。 鹼性顯影中的顯影液為pH為9~14之水溶液為更佳。 作為鹼性顯影中的顯影液中所含之鹼性化合物,例如可列舉氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、偏矽酸鉀、氨或胺等。作為胺,例如可列舉乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙胺、烷醇胺、二甲基乙醇胺、三乙醇胺、四級銨氫氧化物、氫氧化四甲基銨(TMAH)或氫氧化四乙基銨、氫氧化四丁基銨等。其中,不含金屬的鹼性化合物為較佳,銨化合物為更佳。 鹼性化合物可以為僅一種,亦可以為兩種以上。鹼性化合物為兩種以上時,其合計為上述範圍為較佳。In alkaline development, the content of the organic solvent in the developer relative to the total mass of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 1% by mass or less, and no organic solvent is included. Especially good. It is more preferable that the developer in alkaline development is an aqueous solution with a pH of 9-14. As the alkaline compound contained in the developer in alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, partial Sodium silicate, potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, hydrogen Tetramethylammonium oxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Among them, metal-free basic compounds are preferred, and ammonium compounds are more preferred. There may be only one kind of basic compound, or two or more kinds. When there are two or more basic compounds, the total of them is preferably in the above-mentioned range.
溶劑顯影中,顯影液含有90%以上有機溶劑為更佳。本發明中,顯影液含有ClogP值為-1~5的有機溶劑為較佳,含有ClogP值為0~3的有機溶劑為更佳。ClogP值能夠藉由ChemBioDraw(化學生物圖)輸入結構式而作為計算值來求出。In solvent development, it is more preferable that the developer contains more than 90% organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated as a calculated value by inputting the structural formula from ChemBioDraw (Chemical Biological Diagram).
關於有機溶劑,作為酯類,例如可較佳地列舉乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯(例:烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯(例如,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、乙氧基乙酸乙酯等))、3-烷氧基丙酸烷基酯類(例:3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等(例如,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-乙氧基丙酸乙酯等))、2-烷氧基丙酸烷基酯類(例:2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等(例如,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-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯(例如,2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等)、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-氧代丁酸甲酯、2-氧代丁酸乙酯等,以及作為醚類,例如可較佳地列舉二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等,以及作為酮類,例如可較佳地列舉甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等,以及作為芳香族烴類,例如可較佳地列舉甲苯、二甲苯、大茴香醚、檸檬烯等,作為亞碸類,可較佳地列舉二甲基亞碸。Regarding organic solvents, as esters, for example, ethyl acetate, n-butyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid can be preferably cited. Ethyl, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate Esters, etc.)), 3-alkoxypropionic acid alkyl esters (e.g. 3-alkoxy methyl propionate, 3-alkoxy ethyl propionate, etc. (e.g. 3-methoxy propionate methyl Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionic acid alkyl esters (example: 2 -Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-Methoxy Propionate, 2-Ethoxy Propionate, 2-Ethoxy Propionate)), 2-Alkoxy-2-Methyl Propionate and 2 -Ethyl alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl ester, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example Preferably, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as Ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons For example, toluene, xylene, anisole, limonene, etc. can be preferably cited, and as the sulphurite, dimethyl sulphite can be preferably cited.
本發明中,尤其環戊酮、γ-丁內酯為較佳,環戊酮為更佳。In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred.
顯影液的50質量%以上為有機溶劑為較佳,70質量%以上為有機溶劑為更佳,90質量%以上為有機溶劑為進一步較佳。又,亦可以為顯影液的100質量%為有機溶劑。It is preferable that 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.
作為顯影時間,10秒~5分鐘為較佳。顯影時的顯影液的溫度並無特別限定,通常能夠在20~40℃下進行。As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developer during development is not particularly limited, and it can usually be performed at 20 to 40°C.
亦可以在使用顯影液之處理之後,進一步進行沖洗。 為溶劑顯影時,使用與顯影液不同之有機溶劑進行沖洗為較佳。 為鹼性顯影時,使用純水進行沖洗為較佳。 沖洗時間為5秒~1分鐘為較佳。It can also be further rinsed after the treatment with the developer. In the case of solvent development, it is better to use an organic solvent different from the developer for rinsing. In the case of alkaline development, it is better to rinse with pure water. The rinsing time is preferably 5 seconds to 1 minute.
<加熱步驟> 本發明的製造方法包括將顯影之上述膜在50~450℃下加熱之步驟(加熱步驟)為較佳。 在膜形成步驟(層形成步驟)、乾燥步驟及顯影步驟之後包括加熱步驟為較佳。 本發明的硬化性樹脂組成物含有除了特定樹脂以外的聚合性化合物,但能夠在該步驟中使特定樹脂以外的未反應的聚合性化合物進行硬化反應及使特定樹脂中的未反應的聚合性基進行硬化反應等。 又,特定樹脂為聚醯亞胺前驅物並且硬化性樹脂組成物含有熱鹼產生劑時,在加熱步驟中,例如熱鹼產生劑進行分解,藉此產生鹼且使聚醯亞胺前驅物進行環化反應。 作為加熱步驟中的層的加熱溫度(最高加熱溫度),50℃以上為較佳,80℃以上為更佳,140℃以上為進一步較佳,150℃以上為尤其較佳,160℃以上為更進一步較佳,170℃以上為最佳。作為上限,450℃以下為較佳,350℃以下為更佳,250℃以下為進一步較佳,220℃以下為特佳。<Heating step> The manufacturing method of the present invention preferably includes a step of heating the developed film at 50 to 450°C (heating step). It is preferable to include a heating step after the film formation step (layer formation step), the drying step, and the development step. The curable resin composition of the present invention contains a polymerizable compound other than the specific resin, but in this step, the unreacted polymerizable compound other than the specific resin can be cured and the unreacted polymerizable group in the specific resin can be cured. Carry out hardening reaction and so on. In addition, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal alkali generator, in the heating step, for example, the thermal alkali generator is decomposed, thereby generating alkali and causing the polyimide precursor to proceed. Cyclization reaction. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is more preferred, 150°C or higher is particularly preferred, and 160°C or higher is more preferred. More preferably, 170°C or higher is most preferred. As the upper limit, 450°C or lower is preferred, 350°C or lower is more preferred, 250°C or lower is more preferred, and 220°C or lower is particularly preferred.
關於加熱,從加熱開始時的溫度至最高加熱溫度以1~12℃/分鐘的升溫速度進行為較佳,2~10℃/分鐘為更佳,3~10℃/分鐘為進一步較佳。藉由將升溫速度設為1℃/分鐘以上,能夠確保生產性,並且還防止胺的過度揮發,藉由將升溫速度設為12℃/分鐘以下,能夠緩和硬化膜的殘存應力。Regarding heating, it is preferable to perform the heating rate from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1-12°C/min, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the temperature increase rate to 1°C/min or more, productivity can be ensured and excessive volatilization of amine can be prevented. By setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be alleviated.
加熱開始時的溫度為20℃~150℃為較佳,20℃~130℃為更佳,25℃~120℃為進一步較佳。加熱開始時的溫度是指,開始加熱至最高加熱溫度之步驟時的溫度。例如,將硬化性樹脂組成物適用於基材上之後進行乾燥時,為該乾燥後的膜(層)的溫度,例如從比硬化性樹脂組成物中所含之溶劑的沸點低30~200℃的溫度開始逐漸升溫為較佳。The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the curable resin composition is applied to a substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition It’s better to start to warm up gradually.
加熱時間(最高加熱溫度下的加熱時間)為10~360分鐘為較佳,20~300分鐘為更佳,30~240分鐘為進一步較佳。The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes.
尤其形成多層積層體時,從硬化膜的層間的密接性的觀點考慮,在180℃~320℃的加熱溫度下進行加熱為較佳,在180℃~260℃下進行加熱為更佳。其理由雖不確定,但認為其原因在於藉由設為該溫度,層間的特定樹脂中的聚合性基彼此進行交聯反應。In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, it is preferable to heat at a heating temperature of 180°C to 320°C, and more preferably to heat at 180°C to 260°C. Although the reason is uncertain, it is thought that the reason is that by setting the temperature at this temperature, the polymerizable groups in the specific resin between the layers undergo a crosslinking reaction with each other.
加熱可以分階段進行。作為例子,可以進行以3℃/分鐘從25℃升溫至180℃,且在180℃下保持60分鐘,以2℃/分鐘從180℃升溫至200℃,且在200℃下保持120分鐘之前處理步驟。作為前處理步驟的加熱溫度為100~200℃為較佳,110~190℃為更佳,120~185℃為進一步較佳。在該前處理步驟中,如美國專利9159547號說明書中所記載,一邊照射紫外線一邊進行處理亦較佳。藉由該等前處理步驟,能夠提高膜的特性。前處理步驟在10秒~2小時左右的短時間內進行即可,15秒~30分鐘為更佳。前處理可以為兩階段以上的步驟,例如可以在100~150℃的範圍內進行前處理步驟1,之後在150~200℃的範圍內進行前處理步驟2。Heating can be carried out in stages. As an example, it is possible to perform the treatment before raising the temperature from 25°C to 180°C at 3°C/min, and keeping it at 180°C for 60 minutes, heating it from 180°C to 200°C at 2°C/min, and keeping it at 200°C for 120 minutes. step. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and even more preferably 120 to 185°C. In this pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferable to perform treatment while irradiating with ultraviolet rays. Through these pretreatment steps, the characteristics of the film can be improved. The pretreatment step may be carried out in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be a two-stage or more step. For example, the
進而,可以在加熱之後進行冷卻,作為此時的冷卻速度,1~5℃/分鐘為較佳。Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/min.
加熱步驟藉由充入氮、氦、氬等非活性氣體等而在低氧濃度的環境下進行,這在防止特定樹脂分解的方面為較佳。氧濃度為50ppm(體積比)以下為較佳,20ppm(體積比)以下為更佳。The heating step is performed in a low oxygen concentration environment by charging inert gas such as nitrogen, helium, argon, etc., which is preferable in terms of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
<金屬層形成步驟> 本發明的製造方法包括在顯影處理後的膜(硬化性樹脂組成物層)的表面形成金屬層之金屬層形成步驟為較佳。<Metal layer formation steps> The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.
作為金屬層,並無特別限定,能夠使用現有的金屬種類,可例示銅、鋁、鎳、釩、鈦、鉻、鈷、金及鎢,銅及鋁為更佳,銅為進一步較佳。The metal layer is not particularly limited, and existing metal types can be used. Examples of copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, copper and aluminum are more preferable, and copper is still more preferable.
金屬層的形成方法並無特別限定,能夠適用現有的方法。例如,能夠使用日本特開2007-157879號公報、日本特表2001-521288號公報、日本特開2004-214501號公報、日本特開2004-101850號公報中所記載之方法。例如,可考慮光微影、剝離、電解電鍍、無電解電鍍、蝕刻、印刷及組合該等之方法等。更具體而言,可列舉組合濺射、光微影及蝕刻之圖案化方法、組合光微影與電解電鍍之圖案化方法。The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be cited.
作為金屬層的厚度,最厚的部分為0.1~50μm為較佳,1~10μm為更佳。As for the thickness of the metal layer, the thickest part is preferably 0.1-50 μm, more preferably 1-10 μm.
<積層步驟> 本發明的製造方法進一步包括積層步驟為較佳。<Layering Steps> Preferably, the manufacturing method of the present invention further includes a layering step.
積層步驟為包括在硬化膜(樹脂層)或金屬層的表面,再次依序進行(a)膜形成步驟(層形成步驟)、(b)曝光步驟、(c)顯影步驟、(d)加熱步驟之一系列步驟。其中,可以為僅重複(a)膜形成步驟之態樣。又,亦可以設為(d)加熱步驟在積層的最後或中間統括進行之態樣。亦即,亦可以設為如下態樣:重複進行既定次數的(a)~(c)的步驟,之後進行(d)的加熱,藉此將所積層之硬化性樹脂組成物層統括硬化。又,亦可以在(c)顯影步驟之後包括(e)金屬層形成步驟,此時可以每次都進行(d)的加熱,亦可以在積層既定次數之後統括進行(d)的加熱。積層步驟中可以進一步適當包括上述乾燥步驟和加熱步驟等是毋庸置疑的。The lamination step includes on the surface of the cured film (resin layer) or metal layer, and again in sequence (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step A series of steps. Among them, it may be an aspect in which only (a) the film forming step is repeated. In addition, the heating step (d) may be performed collectively at the end or in the middle of the build-up. That is, it is also possible to adopt a configuration in which the steps (a) to (c) are repeated a predetermined number of times, and then the heating of (d) is performed, thereby collectively curing the laminated curable resin composition layers. In addition, the (e) metal layer forming step may be included after the (c) development step. In this case, the heating of (d) may be performed every time, or the heating of (d) may be collectively performed after a predetermined number of laminations. It goes without saying that the above-mentioned drying step and heating step can be further included in the layering step as appropriate.
在積層步驟之後進一步進行積層步驟時,可以在上述加熱步驟之後、上述曝光步驟之後或上述金屬層形成步驟之後,進一步進行表面活化處理步驟。作為表面活化處理,可例示電漿處理。When the layering step is further performed after the layering step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified.
上述積層步驟進行2~5次為較佳,進行3~5次為更佳。The above-mentioned layering step is preferably performed 2 to 5 times, and more preferably 3 to 5 times.
例如,如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層的樹脂層為3層以上且7層以下的結構為較佳,3層以上且5層以下為進一步較佳。For example, a resin layer such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably a structure having 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
本發明中,尤其以在設置金屬層之後進一步覆蓋上述金屬層之方式形成上述硬化性樹脂組成物的硬化膜(樹脂層)之態樣為較佳。具體而言,可列舉依序重複(a)膜形成步驟、(b)曝光步驟、(c)顯影步驟、(e)金屬層形成步驟、(d)加熱步驟之態樣、或依序重複(a)膜形成步驟、(b)曝光步驟、(c)顯影步驟、(e)金屬層形成步驟,最後或中間統括設置(d)加熱步驟之態樣。藉由交替進行積層硬化性樹脂組成物層(樹脂層)之積層步驟和金屬層形成步驟,能夠交替積層硬化性樹脂組成物層(樹脂層)和金屬層。In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition in such a manner that the metal layer is further covered after the metal layer is provided. Specifically, it can be enumerated to repeat (a) a film formation step, (b) an exposure step, (c) a development step, (e) a metal layer formation step, (d) a heating step, or repeat sequentially ( a) Film formation step, (b) exposure step, (c) development step, (e) metal layer formation step, and (d) heating step in the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.
本發明中亦揭示包含本發明的硬化膜或積層體之半導體器件。作為將本發明的硬化性樹脂組成物使用在再配線層用層間絕緣膜的形成中之半導體器件的具體例,能夠參閱日本特開2016-027357號公報的0213~0218段的記載及圖1的記載,且該等內容被編入本說明書中。The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the curable resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 and FIG. 1 Records, and these contents are incorporated into this manual.
(聚醯亞胺或聚醯亞胺前驅物) 本發明的聚醯亞胺或聚醯亞胺前驅物包含以下述式(1-1)表示之結構為較佳。 [化學式61] 式(1-1)中,R1 分別獨立地表示氫原子或烷基,Z1 表示包含聚合性基之基團,n表示2以上的整數,m表示2以上的整數,*表示與其他結構的鍵結部位。(Polyimine or polyimine precursor) The polyimine or polyimine precursor of the present invention preferably includes a structure represented by the following formula (1-1). [Chemical formula 61] In formula (1-1), R 1 each independently represents a hydrogen atom or an alkyl group, Z 1 represents a group containing a polymerizable group, n represents an integer of 2 or more, m represents an integer of 2 or more, and * represents other structures The bonding site.
上述式(1-1)的含義與特定樹脂中的式(1-1)相同,且較佳的態樣亦相同。 本發明的聚醯亞胺或聚醯亞胺前驅物除了將上述式(1-1)作為必要條件以外,含義與上述特定樹脂中的聚醯亞胺或聚醯亞胺前驅物相同,且較佳的態樣亦相同。The meaning of the above formula (1-1) is the same as the formula (1-1) in the specific resin, and preferred aspects are also the same. The polyimine or polyimine precursor of the present invention has the same meaning as the polyimine or polyimine precursor in the above specific resin except that the above formula (1-1) is used as a necessary condition, and is more The good looks are the same.
<用途> 本發明的聚醯亞胺或聚醯亞胺前驅物用作硬化性樹脂組成物中所包含之樹脂為較佳。 又,例如層間絕緣膜用組成物等使用習知之聚醯亞胺或聚醯亞胺前驅物之組成物中,並無特別限制,能夠使用本發明的聚醯亞胺或聚醯亞胺前驅物來替換習知之聚醯亞胺或聚醯亞胺前驅物的一部分或全部。 認為含有本發明的聚醯亞胺或聚醯亞胺前驅物之組成物的塗佈性優異,因此本發明的聚醯亞胺或聚醯亞胺前驅物例如在用於形成絕緣膜的組成物等藉由塗佈形成塗佈膜之用途中使用之組成物中較佳地使用。 [實施例]<Use> The polyimide or polyimine precursor of the present invention is preferably used as the resin contained in the curable resin composition. In addition, there are no particular restrictions on compositions using conventional polyimide or polyimide precursors such as compositions for interlayer insulating films, and the polyimide or polyimide precursor of the present invention can be used To replace part or all of the conventional polyimide or polyimide precursor. It is considered that the composition containing the polyimide or polyimine precursor of the present invention has excellent coating properties. Therefore, the polyimide or polyimine precursor of the present invention is used, for example, in a composition for forming an insulating film. It is preferably used in a composition used in applications where a coating film is formed by coating. [Example]
以下,列舉實施例對本發明進行進一步詳細的說明。示於以下實施例之材料、使用量、比例、處理內容、處理步驟等只要不脫離本發明的宗旨,則能夠適當地進行變更。從而,本發明的範圍不限定於以下所示之具體例。以下,除非另有指明,則“份”、“%”為質量基準。Hereinafter, the present invention will be further described in detail by way of examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Hereinafter, unless otherwise specified, "parts" and "%" are quality standards.
(特定樹脂的合成) <合成例1:聚醯亞胺(PI-1)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將3,5-二胺苯甲酸15.21g(100毫莫耳)溶解於N-甲基吡咯啶酮(NMP)130.0g中。接著,添加氧二鄰苯二甲酸二酐31.02g(100毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了4小時。將上述反應液冷卻至25℃之後,添加BLEMMER PE-200(NOF CORPORATION製)28.4g(100毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺12.6g(100毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。藉由過濾去除聚醯亞胺前驅物樹脂,在1.5升甲醇中再次攪拌30分鐘並再次進行了過濾。接著,在減壓之狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-1。PI-1的重量平均分子量(Mw)為29,500,數量平均分子量(Mn)為13,500。 推測PI-1的結構為以下述式(PI-1)表示之結構。 又,方括號的附註表示各重複單元的含有比(莫耳比),m=91、q=9。 [化學式62] (Synthesis of specific resin) <Synthesis example 1: Synthesis of polyimide (PI-1)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the 3 15.21 g (100 millimoles) of 5-diaminobenzoic acid was dissolved in 130.0 g of N-methylpyrrolidone (NMP). Next, 31.02 g (100 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 28.4 g (100 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-1. The weight average molecular weight (Mw) of PI-1 is 29,500, and the number average molecular weight (Mn) is 13,500. It is estimated that the structure of PI-1 is a structure represented by the following formula (PI-1). Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=91 and q=9. [Chemical formula 62]
<合成例2:聚醯亞胺(PI-2)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將3,5-二胺苯甲酸15.21g(100毫莫耳)溶解於N-甲基吡咯啶酮(NMP)130.0g中。接著,添加氧二鄰苯二甲酸二酐31.02g(100毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了4小時。將上述反應液冷卻至25℃之後,添加BLEMMER AP-400(NOF CORPORATION製)33.6g(80毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g及N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺12.6g(90毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。藉由過濾去除聚醯亞胺前驅物樹脂,在1.5升甲醇中再次攪拌30分鐘並再次進行了過濾。接著,在減壓之狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-2。PI-2的重量平均分子量(Mw)為25,100,數量平均分子量(Mn)為12,100。 推測PI-2的結構為以下述式(PI-2)表示之結構。 又,方括號的附註表示各重複單元的含有比(莫耳比),m=85、q=15。 [化學式63] 上述(PI-2)中,C3 H6 的記載中,隨機包含1-甲基伸乙基(下述(P1))和2-甲基伸乙基(下述(P2))。下述式(P1)及式(P2)中,*1 與式(PI-2)中的羰基側的結構鍵結,*2 與式(PI-7)中的丙烯醯氧基側的結構鍵結。 [化學式64] <Synthesis example 2: Synthesis of polyimide (PI-2)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 31.02 g (100 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 33.6 g (80 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (90 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-2. The weight average molecular weight (Mw) of PI-2 is 25,100, and the number average molecular weight (Mn) is 12,100. It is estimated that the structure of PI-2 is a structure represented by the following formula (PI-2). Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=85 and q=15. [Chemical formula 63] In the above (PI-2), in the description of C 3 H 6 , 1-methylethylene ((P1) below) and 2-methylethylene ((P2) below) are randomly included. In the following formulas (P1) and (P2), * 1 is bonded to the structure on the carbonyl side of the formula (PI-2), and * 2 is bonded to the structure on the propyleneoxy group side of the formula (PI-7) Knot. [Chemical formula 64]
<合成例3:聚醯亞胺(PI-3)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將雙(4-胺基-3-羧基苯基)甲烷14.3g(50毫莫耳)溶解於N-甲基吡咯啶酮(NMP)100.0g中。接著,添加氧二鄰苯二甲酸二酐9.31g(30毫莫耳)、4,4’-(六氟亞異丙基)二鄰苯二甲酸二酐8.88g(20毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了5小時。將上述反應液冷卻至25℃之後,添加BLEMMER PE-200(NOF CORPORATION製)14.2g(50毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺6.3g(50毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。藉由過濾去除聚醯亞胺前驅物樹脂,在1.5升甲醇中再次攪拌30分鐘並再次進行了過濾。接著,在減壓之狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-3。PI-3的重量平均分子量(Mw)為31,000,數量平均分子量(Mn)為13,900。 推測PI-3的結構為以下述式(PI-3)表示之結構。式(PI-3)中,*表示R與氧原子鍵結之鍵結部位。 [化學式65] <Synthesis Example 3: Synthesis of Polyimide (PI-3)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the bis(4-amino- 14.3 g (50 millimoles) of 3-carboxyphenyl)methane was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Next, 9.31 g (30 millimoles) of oxydiphthalic dianhydride and 8.88 g (20 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while being charged with nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 5 hours. After cooling the above reaction liquid to 25°C, 14.2 g (50 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 6.3 g (50 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or lower for 5 hours, and the temperature was raised to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-3. The weight average molecular weight (Mw) of PI-3 is 31,000, and the number average molecular weight (Mn) is 13,900. It is estimated that the structure of PI-3 is a structure represented by the following formula (PI-3). In the formula (PI-3), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 65]
<合成例4:聚醯亞胺(PI-4)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將3,5-二胺苯甲酸15.21g(100毫莫耳)溶解於N-甲基吡咯啶酮(NMP)130.0g中。接著,添加氧二鄰苯二甲酸二酐15.51g(50毫莫耳)及4,4’-(六氟亞異丙基)二鄰苯二甲酸二酐22.1g(50毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了4小時。將上述反應液冷卻至25℃之後,添加甲基丙烯酸2-羥基乙酯7.80g(60毫莫耳)、六乙二醇單甲醚13.6g(40毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺12.6g(100毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。過濾去除聚醯亞胺前驅物樹脂,將過濾物混合於1.5升甲醇中,再次攪拌30分鐘並再次進行了過濾。接著,在減壓之狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-4。PI-4的重量平均分子量(Mw)為28,300,數量平均分子量(Mn)為13,000。 推測PI-4的結構為以下述式(PI-4)表示之結構。式(PI-4)中,*表示R1 與氧原子鍵結之鍵結部位。 又,方括號的附註表示各重複單元的含有比(莫耳比),m=50、q=50。 [化學式66] <Synthesis Example 4: Synthesis of Polyimide (PI-4)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 15.51 g (50 millimoles) of oxydiphthalic dianhydride and 22.1 g (50 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 7.80 g (60 millimoles) of 2-hydroxyethyl methacrylate, 13.6 g (40 millimoles) of hexaethylene glycol monomethyl ether, N,N'-di 0.61 g (5 millimoles) of methylaminopyridine, 0.06 g of p-methoxyphenol, and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-4. The weight average molecular weight (Mw) of PI-4 is 28,300, and the number average molecular weight (Mn) is 13,000. It is estimated that the structure of PI-4 is a structure represented by the following formula (PI-4). In the formula (PI-4), * represents the bonding site where R 1 is bonded to the oxygen atom. Note that the square brackets indicate the content ratio (mole ratio) of each repeating unit, m=50 and q=50. [Chemical formula 66]
<合成例5:聚醯亞胺(PI-5)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將3,5-二胺苯甲酸15.21g(100毫莫耳)溶解於N-甲基吡咯啶酮(NMP)130.0g中。接著,添加氧二鄰苯二甲酸二酐15.5g(50毫莫耳)、4,4’-(六氟亞異丙基)二鄰苯二甲酸二酐13.3g(30毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了4小時。將上述反應液冷卻至25℃之後,添加BLEMMER AP-400(NOF CORPORATION製)21.3g(50毫莫耳)、1-羥基-2,3-環氧丙烷2.22g(30毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺12.6g(100毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。過濾去除聚醯亞胺前驅物樹脂,將過濾物混合於1.5升甲醇中,再次攪拌30分鐘並再次進行了過濾。接著,在減壓之狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-5。PI-5的重量平均分子量(Mw)為33,300,數量平均分子量(Mn)為15,000。 推測PI-5的結構為以下述式(PI-5)表示之結構。式(PI-5)中,*表示R1 與氧原子鍵結之鍵結部位。 [化學式67] 上述(PI-5)中,C3 H6 的記載中,隨機包含1-甲基伸乙基(上述(P1))和2-甲基伸乙基(上述(P2))。式(P1)及式(P2)中,*1 與式(PI-5)中的R1 中的丙烯酸酯基側的結構鍵結,*2 與式(PI-5)中的R1 中的*側的結構鍵結。<Synthesis example 5: Synthesis of polyimide (PI-5)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 3,5-diaminobenzene was removed while removing water. 15.21g (100 millimoles) of formic acid was dissolved in 130.0g of N-methylpyrrolidone (NMP). Next, 15.5 g (50 millimoles) of oxydiphthalic dianhydride and 13.3 g (30 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, the temperature was increased to 180° C. while charging nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 4 hours. After cooling the above reaction liquid to 25°C, 21.3 g (50 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 2.22 g (30 millimoles) of 1-hydroxy-2,3-propylene oxide, and N , N'-dimethylaminopyridine 0.61g (5 millimoles), p-methoxyphenol 0.06g, and N-methylpyrrolidone 130.0g were dissolved and cooled to 0°C. Next, 12.6 g (100 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-5. The weight average molecular weight (Mw) of PI-5 is 33,300, and the number average molecular weight (Mn) is 15,000. It is estimated that the structure of PI-5 is a structure represented by the following formula (PI-5). In the formula (PI-5), * represents the bonding site where R 1 is bonded to the oxygen atom. [Chemical formula 67] In the above (PI-5), the description of C 3 H 6 randomly includes 1-methylethylene (the above (P1)) and 2-methylethylene (the above (P2)). In formula (P1) and formula (P2), * 1 is bonded to the structure on the side of the acrylate group in R 1 in formula (PI-5) , and * 2 is bonded to the structure in R 1 in formula (PI-5) *Structural bonding on the side.
<合成例6:聚醯亞胺(PI-6)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將雙(2-(3-胺基丙氧基)乙基)醚6.91g(30毫莫耳)、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷25.6g(70毫莫耳)溶解於N-甲基吡咯啶酮(NMP)100.0g中。接著,添加氧二鄰苯二甲酸二酐310.2g(100毫莫耳)、4,4’-(六氟亞異丙基)二鄰苯二甲酸二酐13.3g(30毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,充入200ml/min的流量的氮,並使溫度升溫至180℃而攪拌5小時,並將反應液冷卻至25℃。添加三乙胺12.1g(120毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮80.0g進行溶解,並冷卻為0℃。接著,滴加1小時甲基丙烯醯氯10.4g(100毫莫耳),並在25℃以下攪拌了4小時。接著,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2,000rpm的速度攪拌了30分鐘。過濾去除聚醯亞胺前驅物樹脂,將過濾物混合於1.5升甲醇中,再次攪拌30分鐘並再次進行了過濾。接著,在減壓狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-6。PI-6的重量平均分子量(Mw)為29,900,數量平均分子量(Mn)為14,300。 推測PI-6的結構為以下述式(PI-6)表示之結構。式(PI-6)中,*表示R與氧原子鍵結之鍵結部位。 [化學式68] <Synthesis Example 6: Synthesis of Polyimide (PI-6)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, the bis(2-(3- Aminopropoxy) ethyl) ether 6.91g (30 millimoles), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 25.6g (70 millimoles) dissolved in N -Methylpyrrolidone (NMP) 100.0g. Next, 310.2 g (100 millimoles) of oxydiphthalic dianhydride and 13.3 g (30 millimoles) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride were added, and It was stirred for 2 hours at a temperature of 40°C. Next, after adding 50 mL of toluene, nitrogen was charged at a flow rate of 200 ml/min, and the temperature was raised to 180°C and stirred for 5 hours, and the reaction liquid was cooled to 25°C. 12.1 g (120 millimoles) of triethylamine, 0.06 g of p-methoxyphenol, and 80.0 g of N-methylpyrrolidone were added to dissolve, and the mixture was cooled to 0°C. Then, 10.4 g (100 millimoles) of methacrylic acid chloride was added dropwise for 1 hour, and the mixture was stirred at 25°C or lower for 4 hours. Next, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at a speed of 2,000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under reduced pressure, the obtained polyimide was dried at 40°C for 1 day to obtain PI-6. The weight average molecular weight (Mw) of PI-6 is 29,900, and the number average molecular weight (Mn) is 14,300. It is estimated that the structure of PI-6 is a structure represented by the following formula (PI-6). In the formula (PI-6), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 68]
<合成例7:聚醯亞胺(PI-7)的合成> 除了代替在PI-6的合成中使用之2,2-雙(3-胺基-4-羥基苯基)六氟丙烷而使用了相同莫耳量的4,6-二羥基-1,3-苯二胺以外,以與PI-6相同的方法合成了PI-7。PI-7的重量平均分子量(Mw)為27,400,數量平均分子量(Mn)為13,300。 推測PI-7的結構為以下述式(PI-7)表示之結構。式(PI-7)中,*表示R與氧原子鍵結之鍵結部位。 [化學式69] <Synthesis Example 7: Synthesis of Polyimide (PI-7)> Except for replacing 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane used in the synthesis of PI-6 PI-7 was synthesized by the same method as PI-6 except for the same molar amount of 4,6-dihydroxy-1,3-phenylenediamine. The weight average molecular weight (Mw) of PI-7 is 27,400, and the number average molecular weight (Mn) is 13,300. It is estimated that the structure of PI-7 is a structure represented by the following formula (PI-7). In the formula (PI-7), * represents the bonding site where R is bonded to the oxygen atom. [Chemical formula 69]
<合成例8:聚醯亞胺(PI-8)的合成> 除了代替在PI-4的合成中使用之甲基丙烯酸2-羥基乙酯、六乙二醇單甲醚而使用了甘油二甲基丙烯酸酯(NOF CORPORATION製)30(毫莫耳)及BLEMMER PE-200(NOF CORPORATION製)(70毫莫耳)以外,以與PI-4相同的方法合成了PI-8。PI-8的重量平均分子量(Mw)為25,900,數量平均分子量(Mn)為12,900。 推測PI-8的結構為以下述式(PI-8)表示之結構。式(PI-8)中,*表示R1 與氧原子鍵結之鍵結部位。 [化學式70] <合成例9:聚醯亞胺(PI-9)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將3,5-二胺苯甲酸4.56g(30毫莫耳)及9,9-雙(4-胺基-3-甲基苯基)茀7.53g(20毫莫耳)溶解於N-甲基吡咯啶酮(NMP)80.0g中。接著,添加氧二鄰苯二甲酸二酐15.51g(50毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加30mL甲苯之後,一邊充入200ml/min的流量的氮,一邊使溫度升溫至180℃,並攪拌了5小時。將上述反應液冷卻至25℃之後,添加BLEMMER PE-200(NOF CORPORATION製)14.2g(50毫莫耳)、N,N’-二甲基胺基吡啶0.61g(5毫莫耳)、對甲氧基苯酚0.06g、N-甲基吡咯啶酮130.0g進行溶解,並冷卻為0℃。接著,添加二異丙基碳二亞胺6.3g(50毫莫耳),並在10℃以下攪拌5小時,並使其升溫至室溫。接著,將其冷卻為25℃,使其在1.5升水/甲醇=75/25(體積比)中沉澱,並以2,000rpm的速度攪拌了30分鐘。過濾去除所析出之聚醯亞胺樹脂,用1升水進行沖洗之後,將過濾物混合於1.5升甲醇中,再次攪拌30分鐘並再次進行了過濾。在減壓狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了PI-9。PI-9的重量平均分子量(Mw)為31,600,數量平均分子量(Mn)為11,500。 推測PI-9的結構為以下述式(PI-9)表示之結構。式(PI-9)中,*表示R1 與氧原子鍵結之鍵結部位。 又,方括號的附註表示各重複單元的含有比(莫耳比),m=3、q=2。 [化學式71] <Synthesis Example 8: Synthesis of Polyimide (PI-8)> Except for replacing 2-hydroxyethyl methacrylate and hexaethylene glycol monomethyl ether used in the synthesis of PI-4, dimethylglycerol was used PI-8 was synthesized in the same manner as PI-4 except for the base acrylate (manufactured by NOF CORPORATION) 30 (millimolar) and BLEMMER PE-200 (manufactured by NOF CORPORATION) (70 millimolar). The weight average molecular weight (Mw) of PI-8 is 25,900, and the number average molecular weight (Mn) is 12,900. It is estimated that the structure of PI-8 is a structure represented by the following formula (PI-8). In the formula (PI-8), * represents the bonding site where R 1 is bonded to the oxygen atom. [Chemical formula 70] <Synthesis Example 9: Synthesis of Polyimide (PI-9)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 3,5-diaminobenzene was removed while removing water. Formic acid 4.56g (30 millimoles) and 9,9-bis(4-amino-3-methylphenyl) 7.53g (20 millimoles) dissolved in N-methylpyrrolidone (NMP) 80.0 g中. Next, 15.51 g (50 millimoles) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, after adding 30 mL of toluene, the temperature was increased to 180° C. while being charged with nitrogen at a flow rate of 200 ml/min, and the mixture was stirred for 5 hours. After cooling the above reaction liquid to 25°C, 14.2 g (50 millimoles) of BLEMMER PE-200 (manufactured by NOF CORPORATION), 0.61 g (5 millimoles) of N,N'-dimethylaminopyridine, and 0.06 g of methoxyphenol and 130.0 g of N-methylpyrrolidone were dissolved and cooled to 0°C. Next, 6.3 g (50 millimoles) of diisopropylcarbodiimide was added, and the mixture was stirred at 10° C. or less for 5 hours, and the temperature was raised to room temperature. Next, it was cooled to 25°C, precipitated in 1.5 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was removed by filtration, and after rinsing with 1 liter of water, the filtrate was mixed in 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Under reduced pressure, the obtained polyimine was dried at 40°C for 1 day to obtain PI-9. The weight average molecular weight (Mw) of PI-9 is 31,600, and the number average molecular weight (Mn) is 11,500. It is estimated that the structure of PI-9 is a structure represented by the following formula (PI-9). In the formula (PI-9), * represents the bonding site where R 1 is bonded to the oxygen atom. Note that the square brackets indicate the content ratio (molar ratio) of each repeating unit, m=3 and q=2. [Chemical formula 71]
<合成例10:聚醯亞胺前驅物(PA-1)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊使氧代二鄰苯二甲酸二酐20.0g(64.5毫莫耳)懸浮於二甘二甲醚140mL中。連續添加甲基丙烯酸2-羥基乙酯10.1g(77毫莫耳)、BLEMMER AP-400(NOF CORPORATION製)12.6g(39毫莫耳)、氫醌0.05g及吡啶10.7g(135毫莫耳),並在60℃的溫度下攪拌了18小時。接著,將混合物冷卻至-20℃之後,滴加了90分鐘亞硫醯氯16.1g(135.5毫莫耳)。獲得了吡啶鹽酸鹽的白色沉澱物。接著,將混合物加溫至室溫,攪拌2小時後,添加吡啶9.7g(123毫莫耳)及N-甲基吡咯啶酮(NMP)25mL,藉此獲得了透明溶液。接著,在所獲得之透明溶液中添加將4,4’-二胺基二苯醚11.7g(58.7毫莫耳)溶解於NMP 100mL中而成者時,滴加1小時完成。添加上述二胺之期間,黏度增加。接著,添加甲烷5.6g(17.5毫莫耳)和3,5-二-第三丁基-4-羥甲苯0.05g,並將混合物攪拌了2小時。接著,使聚醯亞胺前驅物樹脂在4升水中沉澱,並以500rpm的速度將水-聚醯亞胺前驅物樹脂混合物攪拌了15分鐘。過濾去除聚醯亞胺前驅物樹脂,並在4升水中再次攪拌30分鐘並再次進行了過濾。接著,在減壓狀態下,將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PA-1的分子量,Mw=25,100、Mn=13,200。 推測PA-1的結構為以下述式(PA-1)表示之結構。式(PA-1)中,*表示R與氧原子鍵結之鍵結部位。 [化學式72] 上述(PA-1)中,C3 H6 的記載中,隨機包含1-甲基伸乙基(上述(P1))和2-甲基伸乙基(上述(P2))。式(P1)及式(P2)中,*1 與式(PA-1)中的R中的丙烯醯氧基側的結構鍵結,*2 與式(PA-1)中的R中的*側的結構鍵結。<Synthesis Example 10: Synthesis of Polyimide Precursor (PA-1)> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, the oxodiphthalene was removed while removing water. 20.0 g (64.5 millimoles) of dicarboxylic dianhydride was suspended in 140 mL of diglyme. Continuously add 10.1g (77 millimoles) of 2-hydroxyethyl methacrylate, 12.6g (39 millimoles) of BLEMMER AP-400 (manufactured by NOF CORPORATION), 0.05g of hydroquinone and 10.7g (135 millimoles) of pyridine ) And stirred for 18 hours at 60°C. Next, after cooling the mixture to -20°C, 16.1 g (135.5 millimoles) of sulfite chloride was added dropwise for 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature, and after stirring for 2 hours, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, when 11.7 g (58.7 millimoles) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent solution, the dripping was completed for 1 hour. During the addition of the above diamine, the viscosity increases. Next, 5.6 g (17.5 millimoles) of methane and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, under a reduced pressure state, the obtained polyimide precursor resin was dried at 45°C for 1 day. Regarding the molecular weight of the polyimide precursor PA-1, Mw=25,100 and Mn=13,200. It is estimated that the structure of PA-1 is a structure represented by the following formula (PA-1). In the formula (PA-1), * represents the bonding site where R and the oxygen atom are bonded. [Chemical formula 72] In the above (PA-1), the description of C 3 H 6 randomly includes 1-methylethylene (the above (P1)) and 2-methylethylene (the above (P2)). In formula (P1) and formula (P2), * 1 is bonded to the structure on the propyleneoxy group side of R in formula (PA-1), and * 2 is bonded to * in R in formula (PA-1) Structural bonding on the side.
<合成例11:比較例用聚醯亞胺(A-1)的合成> 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中,一邊去除水分,一邊將4,4’-二胺基二苯醚31.0g(100毫莫耳)溶解於N-甲基吡咯啶酮(NMP)180.0g中。接著,添加4,4’-(六氟亞異丙基)二鄰苯二甲酸二 酐44.4g(100毫莫耳),並在40℃的溫度下攪拌了2小時。接著,添加50mL甲苯之後,充入200ml/min的流量的氮,並使溫度升溫至180℃而攪拌6小時,並冷卻至室溫。接著,添加N-甲基吡咯啶酮130.0g,進行稀釋之後,使聚醯亞胺在2升水中沉澱,並將水-聚醯亞胺混合物以2000rpm的速度攪拌了30分鐘。過濾去除聚醯亞胺前驅物樹脂,將過濾物與1.5升甲醇進行混合,再次攪拌30分鐘並再次進行了過濾。接著,在減壓狀態下,將所獲得之聚醯亞胺在40℃下乾燥1天,而獲得了A-1。A-1的重量平均分子量(Mw)為30,100,數量平均分子量(Mn)為14,500。 推測A-1的結構為以下述式(A-1)表示之結構。 比較例用聚醯亞胺前驅物(A-1)不包含聚伸烷氧基及聚合性基,不屬於特定樹脂。 [化學式73] <Synthesis Example 11: Synthesis of Polyimide (A-1) for Comparative Example> In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, the 4, 4' -31.0g (100 millimoles) of diaminodiphenyl ether is dissolved in 180.0g of N-methylpyrrolidone (NMP). Next, 4,4 '- (hexafluoro isopropylidene) diphthalic acid dianhydride, 44.4g (100 mmol), and stirred for 2 hours at a temperature of 40 ℃. Next, after adding 50 mL of toluene, nitrogen was charged at a flow rate of 200 ml/min, and the temperature was raised to 180° C., stirred for 6 hours, and cooled to room temperature. Next, 130.0 g of N-methylpyrrolidone was added, and after diluting, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2000 rpm for 30 minutes. The polyimide precursor resin was removed by filtration, and the filtrate was mixed with 1.5 liters of methanol, stirred again for 30 minutes, and filtered again. Next, under a reduced pressure state, the obtained polyimide was dried at 40°C for 1 day to obtain A-1. The weight average molecular weight (Mw) of A-1 is 30,100, and the number average molecular weight (Mn) is 14,500. It is estimated that the structure of A-1 is a structure represented by the following formula (A-1). The polyimide precursor (A-1) for the comparative example does not contain a polyalkyleneoxy group and a polymerizable group, and is not a specific resin. [Chemical formula 73]
<合成例12:比較例用聚醯亞胺(A-2)的合成> 將4,4’-氧代二鄰苯二甲酸二酐(ODPA)155.1g加入到可分離式燒瓶中,並加入了甲基丙烯酸2-羥基乙酯(HEMA)134.0g及γ-丁內酯400ml。一邊在室溫下攪拌,一邊加入吡啶79.1g,藉此獲得了反應混合物。基於反應之發熱結束之後,靜置冷卻至室溫,進一步靜置16小時。<Synthesis Example 12: Synthesis of Polyimide (A-2) for Comparative Example> Put 155.1g of 4,4'-oxodiphthalic dianhydride (ODPA) into the separable flask, and add 134.0g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400ml. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the heat generation due to the reaction is over, it is allowed to stand to cool to room temperature, and then to stand for 16 hours.
接著,在冰冷條件下,一邊攪拌將二環己碳二亞胺(DCC)206.3g溶解於γ-丁內酯180ml中之溶液,一邊在反應混合物中加入40分鐘。接著,一邊攪拌使4,4’-二胺基二苯醚93.0g懸浮於γ-丁內酯350ml中之懸浮液,一邊加入60分鐘。進一步在室溫下攪拌2小時之後,加入30ml乙醇,並攪拌了1小時。之後,加入了400ml的γ-丁內酯。藉由過濾去除反應混合物中產生之沉澱物,而獲得了反應液。Next, under ice-cooling conditions, while stirring a solution of 206.3 g of dicyclohexanecarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone, it was added to the reaction mixture for 40 minutes. Next, while stirring a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone, the suspension was added for 60 minutes. After further stirring for 2 hours at room temperature, 30 ml of ethanol was added and stirring was carried out for 1 hour. After that, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.
將所獲得之反應液加入到3升乙醇中,而產生了由粗聚合物構成之沉澱物。過濾回收所產生之粗聚合物,並溶解於1.5升四氫呋喃中,而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加於28升水中使聚合物沉澱,過濾回收所獲得之沉澱物之後進行真空乾燥,藉此獲得了粉末狀的比較例用聚醯亞胺前驅物(A-2)。對比較例用聚醯亞胺前驅物(A-2)的重量平均分子量(Mw)進行了測量,結果為20,000。The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate composed of crude polymer was produced. The produced crude polymer was recovered by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was recovered by filtration and then vacuum-dried to obtain a powdery polyimide precursor (A- for Comparative Example). 2). The weight average molecular weight (Mw) of the polyimide precursor (A-2) for the comparative example was measured, and the result was 20,000.
<合成例13:比較例用聚醯亞胺前驅物(A-3)的合成> 合成例12中,除了代替4,4’-氧代二鄰苯二甲酸二酐155.1g而使用了3,3’,4,4’-聯苯四羧酸二酐147.1g以外,以與合成例18中記載的方法相同的方法進行了反應,藉此獲得了比較例用聚醯亞胺前驅物(A-3)。對比較例用聚醯亞胺前驅物(A-3)的重量平均分子量(Mw)進行了測量,結果為22,000。<Synthesis Example 13: Synthesis of Polyimide Precursor (A-3) for Comparative Example> In Synthesis Example 12, in place of 155.1 g of 4,4'-oxodiphthalic dianhydride, 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used in order to synthesize The reaction was carried out in the same manner as the method described in Example 18, thereby obtaining the polyimide precursor (A-3) for the comparative example. The weight average molecular weight (Mw) of the polyimide precursor (A-3) for the comparative example was measured, and the result was 22,000.
比較例用聚醯亞胺前驅物(A-2)及(A-3)不包含聚伸烷氧基,不屬於特定樹脂。The polyimide precursors (A-2) and (A-3) used in the comparative example do not contain polyalkoxy groups and are not specific resins.
<實施例及比較例> 各實施例中,分別混合下述表1中所記載的成分,而獲得了各硬化性樹脂組成物。又,各比較例中,分別混合下述表1中所記載的成分,而獲得了各比較用組成物。使所獲得之硬化性樹脂組成物及比較用組成物通過細孔寬度為0.8μm的聚四氟乙烯製過濾器來進行了加壓過濾。 表1中,“質量份”欄中的數值表示各成分的含量(質量份)。 表1中,例如“種類”欄中的“PI-1/PI-2”、“質量份”欄中的“16/16”等記載表示分別使用了16質量份的PI-1,使用了16質量份的PI-2。 又,表1中,“-”的記載表示不含有對應成分。<Examples and Comparative Examples> In each example, the components described in the following Table 1 were mixed to obtain each curable resin composition. Moreover, in each comparative example, the components described in the following Table 1 were mixed, respectively, and each comparative composition was obtained. The obtained curable resin composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In Table 1, the numerical value in the "parts by mass" column represents the content (parts by mass) of each component. In Table 1, for example, "PI-1/PI-2" in the "Type" column, and "16/16" in the "Parts by mass" column indicate that 16 parts by mass of PI-1 were used, and 16 Parts of PI-2 by mass. In addition, in Table 1, the description of "-" indicates that the corresponding component is not contained.
[表1]
表1中所記載之各成分,具體如下述。The details of each component described in Table 1 are as follows.
[特定樹脂或比較用樹脂] ・PI-1~PI-8:上述中所合成之PI-1~PI-8 ・PA-1:上述中所合成之PA-1 ・A-1~A-3:上述中所合成之A-1~A-3[Specific resin or resin for comparison] ・PI-1~PI-8: PI-1~PI-8 synthesized above ・PA-1: PA-1 synthesized in the above ・A-1~A-3: A-1~A-3 synthesized above
[溶劑] ・DMSO:二甲基亞碸 ・GBL:γ-丁內酯 ・乳酸乙酯 ・NMP:N-甲基吡咯啶酮 表1中,DMSO/GBL的記載表示將DMSO與GBL以DMSO:GBL=20:80(質量比)的比例進行了混合。 表1中,NMP/乳酸乙酯的記載表示將NMP與乳酸乙酯以NMP:乳酸乙酯=80:20(質量比)的比例進行了混合。[Solvent] ・DMSO: dimethyl sulfide ・GBL: γ-Butyrolactone ・Ethyl Lactate ・NMP: N-methylpyrrolidone In Table 1, the description of DMSO/GBL indicates that DMSO and GBL were mixed at a ratio of DMSO:GBL=20:80 (mass ratio). In Table 1, the description of NMP/ethyl lactate means that NMP and ethyl lactate were mixed at a ratio of NMP: ethyl lactate=80:20 (mass ratio).
[聚合起始劑] ・OXE-01:IRGACURE OXE 01(BASF SE製) ・OXE-02:IRGACURE OXE 02(BASF SE製)[Polymerization initiator] ・OXE-01: IRGACURE OXE 01 (made by BASF SE) ・OXE-02: IRGACURE OXE 02 (made by BASF SE)
[聚合性化合物] ・SR-209:SR-209(Sartomer Company, Inc製) ・SR-231:SR-231(Sartomer Company, Inc製) ・SR-239:SR-239(Sartomer Company, Inc製) ・SR-268:SR-268(Sartomer Company, Inc製) ・A-DPH:二新戊四醇六丙烯酸酯(SHIN-NAKAMURA CHEMICAL CO, LTD.製)[Polymerizable compound] ・SR-209: SR-209 (manufactured by Sartomer Company, Inc) ・SR-231: SR-231 (manufactured by Sartomer Company, Inc) ・SR-239: SR-239 (manufactured by Sartomer Company, Inc) ・SR-268: SR-268 (manufactured by Sartomer Company, Inc) ・A-DPH: Dineopentaerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.)
[聚合抑制劑] ・F-1:1,4-苯醌 ・F-2:4-甲氧基苯酚 ・F-3:1,4-二羥苯 ・F-4:2-亞硝基-1-萘酚(Tokyo Chemical Industry Co., Ltd.製)[Polymerization inhibitor] ・F-1: 1,4-Benzoquinone ・F-2: 4-Methoxyphenol ・F-3: 1,4-Dihydroxybenzene ・F-4: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)
[金屬接著性改良劑] ・G-1~G-4:下述結構的化合物。以下結構式中,Et表示乙基。 [化學式74] [Metal Adhesion Improver] ・G-1 to G-4: Compounds with the following structures. In the following structural formulae, Et represents an ethyl group. [Chemical formula 74]
(遷移抑制劑) ・H-1:1H-四唑 ・H-2:1,2,4-三唑 ・H-3:5-苯基四唑(Migration inhibitor) ・H-1: 1H-tetrazole ・H-2: 1,2,4-triazole ・H-3: 5-Phenyltetrazole
[熱鹼產生劑] ・I-1:下述結構的化合物 [化學式75] [Thermal base generator] ・I-1: Compound of the following structure [Chemical formula 75]
[添加劑] ・J-1:N-苯基二乙醇胺(Tokyo Chemical Industry Co., Ltd.製)[additive] ・J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
<評價> 各實施例及比較例中,分別使用所製備之硬化性樹脂組成物或比較用組成物來進行了塗佈性及膜強度(斷裂伸長率)的評價。 各評價中的評價方法,具體記載於以下。<Evaluation> In each of the Examples and Comparative Examples, the prepared curable resin composition or the comparative composition was used to evaluate the coatability and film strength (elongation at break). The evaluation method in each evaluation is specifically described below.
[塗佈性]
製作出在直徑4英吋的矽基板的一面共形成10個縱100μm、寬20μm、深度5μm的段差之矽製段差基板。
圖1為所形成之段差基板的概略圖。
圖1中,在矽基板1的表面形成有5列2行共10個段差2。
圖1中,段差2為相對於矽基板1的未形成段差的部分的表面具有5μm深度之段差。又,10個各段差中,段差的深度基本相同。
圖1中,A表示段差2的縱向長度,為100μm。
圖1中,B表示段差2的橫向長度,為20μm。
圖1中,橫向上排列之5個段差的間隔均為1mm。
圖1中,縱向上排列之兩個段差的間隔均為2mm。[Coatability]
A total of 10 silicon stepped substrates with 100 μm in length, 20 μm in width, and 5 μm in depth were formed on one side of a silicon substrate with a diameter of 4 inches.
Fig. 1 is a schematic view of the formed stepped substrate.
In FIG. 1, a total of 10
藉由旋塗法,將各實施例及比較例中製備之各硬化性樹脂組成物或比較用組成物分別適用於圖1所示之段差基板,藉此形成了硬化性樹脂組成物層。 將適用所獲得之硬化性樹脂組成物層之矽晶圓在加熱板上以100℃乾燥5分鐘,而在矽晶圓上獲得了約15μm的均勻厚度的硬化性樹脂組成物層。 藉由AFM(原子力顯微鏡),觀察乾燥後的硬化性樹脂組成物層的表面,計算出藉由下述式FL測量之膜的高低差。 式FL:膜的高低差=(硬化性樹脂組成物層的最大高度)-(硬化性樹脂組成物層的最小高度) 又,藉由光學顯微鏡缺陷檢查裝置KLA2360(Applied Materials, Inc.製)及Review SEM Vision G3(Applied Materials, Inc.製)觀察乾燥後的硬化性樹脂組成物層的表面,計算出每1cm2 的缺陷數量。 以上述膜厚差及上述缺陷數量作為指標,按照下述評價基準進行了塗佈性的評價。評價結果記載於表1的“塗佈性”欄中。膜的高低差越小且缺陷數量越少,說明組成物的塗佈性越優異。 -評價基準- A:膜的高低差小於0.3μm,且缺陷數量少於5個/cm2 。 B:膜的高低差小於0.3μm,且缺陷數量為5個/cm2 以上且少於10個/cm2 。 C:膜的高低差為0.3μm以上且小於0.5μm,且缺陷數量少於10個/cm2 。 D:膜的高低差為0.5μm以上及缺陷數量為10個/cm2 以上這兩者中滿足至少一個條件。Each curable resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied to the stepped substrate shown in FIG. 1 by a spin coating method, thereby forming a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer with a uniform thickness of about 15 μm was obtained on the silicon wafer. The surface of the cured resin composition layer after drying was observed by AFM (Atomic Force Microscope), and the height difference of the film measured by the following formula FL was calculated. Formula FL: film height difference = (maximum height of the curable resin composition layer)-(minimum height of the curable resin composition layer) In addition, the optical microscope defect inspection device KLA2360 (manufactured by Applied Materials, Inc.) and Review SEM Vision G3 (manufactured by Applied Materials, Inc.) observed the surface of the cured resin composition layer after drying, and calculated the number of defects per 1 cm 2. Using the difference in film thickness and the number of defects as indicators, the applicability was evaluated in accordance with the following evaluation criteria. The evaluation results are described in the "Applicability" column of Table 1. The smaller the height difference of the film and the smaller the number of defects, the better the coating properties of the composition. -Evaluation Criteria- A: The height difference of the film is less than 0.3 μm, and the number of defects is less than 5/cm 2 . B: The height difference of the film is less than 0.3 μm, and the number of defects is 5/cm 2 or more and less than 10/cm 2 . C: The height difference of the film is 0.3 μm or more and less than 0.5 μm, and the number of defects is less than 10/cm 2 . D: At least one condition is satisfied out of the difference in film height of 0.5 μm or more and the number of defects of 10/cm 2 or more.
[膜強度(斷裂伸長率)] 藉由旋塗法,將各實施例及比較例中製備之各硬化性樹脂組成物或比較用組成物分別適用於矽晶圓上,藉此形成了硬化性樹脂組成物層。 將適用所獲得之硬化性樹脂組成物層之矽晶圓在加熱板上以100℃乾燥5分鐘,而在矽晶圓上獲得了約15μm的均勻厚度的硬化性樹脂組成物層。 使所獲得之硬化性樹脂組成物層(樹脂層)在氮氣環境下以10℃/分鐘的升溫速度升溫,在達到表1的“硬化條件”欄中記載的溫度之後,在該溫度下加熱了3小時。 將硬化後的樹脂層(硬化膜)浸漬於4.9質量%氫氟酸水溶液中,並從矽晶圓剝離了硬化膜。使用衝孔機將剝離之硬化膜沖壓,製作出寬度3mm、試樣長度30mm的試驗片。對於所獲得之試驗片,使用拉伸試驗機(Tensilon),在十字頭速度300mm/分鐘、25℃、65%RH(相對濕度)的環境下,遵照JIS-K6251對膜的長邊方向上的膜斷裂時的伸長率(斷裂伸長率)進行了測量。評價中,各實施例或比較例中各實施5次,並將5次測量中的斷裂伸長率的測量值的算術平均值作為了指標值。 關於上述指標值,按照下述評價基準進行評價,並將評價結果記載於表1。 -評價基準- A:上述指標值為60%以上。 B:上述指標值為55%以上且小於60%。 C:上述指標值為50%以上且小於55%。 D:上述指標值小於50%。[Film strength (elongation at break)] By the spin coating method, each curable resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied to the silicon wafer, thereby forming a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, and a curable resin composition layer with a uniform thickness of about 15 μm was obtained on the silicon wafer. The obtained curable resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature described in the "curing conditions" column of Table 1, it was heated at that temperature 3 hours. The cured resin layer (cured film) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured film was peeled from the silicon wafer. Punch the peeled cured film with a punching machine to produce a test piece with a width of 3 mm and a sample length of 30 mm. For the obtained test piece, using a tensile testing machine (Tensilon), under the environment of crosshead speed 300mm/min, 25°C, 65%RH (relative humidity), in accordance with JIS-K6251 on the long side of the film The elongation at break of the film (elongation at break) was measured. In the evaluation, each Example or Comparative Example was implemented 5 times, and the arithmetic average of the measured values of the elongation at break in the 5 measurements was used as the index value. Regarding the above-mentioned index values, the evaluation was performed in accordance with the following evaluation criteria, and the evaluation results are described in Table 1. -Evaluation criteria- A: The above index value is more than 60%. B: The above index value is 55% or more and less than 60%. C: The above index value is 50% or more and less than 55%. D: The above index value is less than 50%.
從以上結果可知,本發明之含有特定樹脂之硬化性樹脂組成物的塗佈性優異。 比較例1~2之比較用組成物不含有特定樹脂。可知該比較例1~2之比較用組成物的塗佈性差。From the above results, it can be seen that the curable resin composition containing the specific resin of the present invention is excellent in coatability. The comparative compositions of Comparative Examples 1 and 2 do not contain a specific resin. It can be seen that the comparative compositions of Comparative Examples 1 and 2 have poor coating properties.
<實施例101> 將實施例1中所記載之硬化性樹脂組成物旋轉塗佈於表面形成有銅薄層之樹脂基材中的銅薄層的表面,使膜厚達到20μm。將塗佈於樹脂基材之硬化性樹脂組成物在100℃下乾燥2分鐘之後,使用步進機(Nikon Corporation製、NSR1505 i6)進行了曝光。隔著正方形圖案(長寬各100μm的正方形圖案,重複數10)的遮罩,在波長365nm下,以400mJ/cm2 的曝光量進行曝光,而製作出殘留有正方形之圖案。曝光之後,用環戊酮顯影30秒,用PGMEA沖洗20秒而獲得了圖案。 接著,使其在氮氣環境下以10℃/分鐘的升溫速度升溫,達到表1的“硬化條件”欄中所記載的溫度之後,在該溫度下加熱3小時,而形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。又,使用該等再配線層用層間絕緣膜製造出半導體器件,結果確認為正常動作。<Example 101> The curable resin composition described in Example 1 was spin-coated on the surface of the copper thin layer in the resin substrate with the copper thin layer formed on the surface so that the film thickness was 20 μm. The curable resin composition coated on the resin substrate was dried at 100°C for 2 minutes, and then exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask of a square pattern (a square pattern of 100 μm in length and width, repeating counts of ten), exposure was performed at a wavelength of 365 nm at an exposure amount of 400 mJ/cm 2 to create a pattern with squares remaining. After exposure, it was developed with cyclopentanone for 30 seconds and washed with PGMEA for 20 seconds to obtain a pattern. Next, the temperature was raised at a temperature increase rate of 10°C/min in a nitrogen atmosphere to reach the temperature listed in the "hardening conditions" column of Table 1, and then heated at this temperature for 3 hours to form the interlayer for the rewiring layer. Insulating film. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, and as a result, it was confirmed that they were operating normally.
1:矽基板 2:段差 A:段差的縱向長度 B:段差的橫向長度1: Silicon substrate 2: step difference A: The longitudinal length of the level difference B: The horizontal length of the step difference
圖1係實施例中使用之段差基板的概略圖。Fig. 1 is a schematic diagram of a stepped substrate used in the embodiment.
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