TW202212992A - Cured product production method, laminate production method, and semiconductor device production method - Google Patents
Cured product production method, laminate production method, and semiconductor device production method Download PDFInfo
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
Description
本發明係有關一種硬化物的製造方法、積層體的製造方法及半導體元件的製造方法。The present invention relates to a method for producing a cured product, a method for producing a laminate, and a method for producing a semiconductor element.
聚醯亞胺或聚苯并噁唑、聚醯胺醯亞胺等樹脂由於耐熱性及絕緣性等優異,因此適用於各種用途。作為上述用途並無特別限定,但是若舉出實際安裝用半導體元件為例,則可以舉出將包含該等樹脂之圖案用作絕緣膜或密封材料的材料或保護膜的情況等。又,包含該等樹脂之圖案亦可以用作撓性基板的基底膜或覆蓋膜等。Resins such as polyimide, polybenzoxazole, and polyimide imide are suitable for various applications because they are excellent in heat resistance, insulating properties, and the like. The above-mentioned application is not particularly limited, but if a semiconductor element for actual mounting is used as an example, a pattern containing these resins may be used as a material for an insulating film or a sealing material, or a protective film. Moreover, the pattern containing these resins can also be used as a base film, a coverlay film, etc. of a flexible substrate.
例如,在上述用途中,聚醯亞胺、聚苯并噁唑或聚醯胺醯亞胺等樹脂以包含聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物等硬化性樹脂之感光性組成物的形態使用。 將該種感光性組成物例如藉由塗佈等而適用於基材上,之後,依據需要進行曝光、顯影、改質等,從而能夠將聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物等的硬化物形成於基材上。 感光性組成物能夠藉由公知的塗佈方法等而適用,能夠藉由顯影而形成微細的圖案、複雜的形狀的圖案等。因此,可以說硬化物的設計的自由度高等製造上的適應性優異。除了聚醯亞胺或聚苯并噁唑、聚醯胺醯亞胺等樹脂所具有之高性能以外從該種製造上的適應性優異之觀點考慮,越來越期待針對使用了包含硬化性樹脂之感光性組成物之硬化物的製造方法在產業上的應用開發。 For example, in the above applications, resins such as polyimide, polybenzoxazole or polyimide It is used in the form of a photosensitive composition of curable resin such as resin. Such a photosensitive composition is applied to a substrate by, for example, coating, and thereafter, exposure, development, modification, etc. are carried out as necessary, whereby a polyimide precursor and a polybenzoxazole precursor can be prepared. , a cured product such as a polyamide imide precursor is formed on the substrate. The photosensitive composition can be applied by a known coating method or the like, and can form a fine pattern, a pattern of a complicated shape, or the like by development. Therefore, it can be said that the degree of freedom in the design of the cured product is high, and the suitability for manufacture is excellent. In addition to the high performance of resins such as polyimide, polybenzoxazole, polyimide imide, etc., from the viewpoint of excellent suitability for such production, it is increasingly expected that the use of resins containing curable resins Industrial application and development of the manufacturing method of the cured product of the photosensitive composition.
例如,在專利文獻1中,記載有如下方法,其係包括為了形成聚醯亞胺纖維而在第1溫度~第2溫度範圍的溫度下將聚醯胺酸纖維加熱5秒鐘~5分鐘範圍的時間之步驟,其中,上述第1溫度為上述聚醯胺酸的醯亞胺化溫度,並且上述第2溫度為上述聚醯亞胺的分解溫度。 在專利文獻2中,記載有一種樹脂組成物,其係包括包含特定的結構單元之聚醯亞胺前驅物和溶劑,其中,上述溶劑為醯胺系溶劑與沸點為160℃以上的非醯胺系溶劑的混合物,並且以上述樹脂組成物的質量為基準包含多於0ppm且1200ppm以下的量的特定的化合物。 For example, Patent Document 1 describes a method including heating a polyimide fiber at a temperature in the range of the first temperature to the second temperature for 5 seconds to 5 minutes in order to form the polyimide fiber. wherein the first temperature is the imidization temperature of the polyimide, and the second temperature is the decomposition temperature of the polyimide. Patent Document 2 describes a resin composition comprising a polyimide precursor containing a specific structural unit and a solvent, wherein the solvent is an amide-based solvent and a non-amide having a boiling point of 160°C or higher It is a mixture of solvents and contains the specific compound in an amount of more than 0 ppm and 1200 ppm or less based on the mass of the resin composition.
[專利文獻1]日本特表2013-539824號公報 [專利文獻2]日本特開2019-203120號公報 [Patent Document 1] Japanese Patent Publication No. 2013-539824 [Patent Document 2] Japanese Patent Laid-Open No. 2019-203120
在使用了包含聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物等硬化性樹脂之感光性組成物之先前的硬化物的製造方法中,要求提高所獲得之硬化物的斷裂伸長率及提高由硬化物形成之圖案的耐藥品性。In a conventional method for producing a cured product using a photosensitive composition containing a curable resin such as a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor, it is required to improve the obtained The elongation at break of the cured product and the chemical resistance of the pattern formed by the cured product are improved.
本發明的目的為,提供一種可以獲得斷裂伸長率及耐藥品性優異之硬化物之硬化物的製造方法、包括上述硬化物的製造方法之積層體的製造方法及包括上述硬化物的製造方法或上述積層體的製造方法之半導體元件的製造方法。An object of the present invention is to provide a method for producing a cured product that can obtain a cured product excellent in elongation at break and chemical resistance, a method for producing a laminate including the method for producing the above-mentioned cured product, and a method for producing the above-mentioned cured product or The manufacturing method of the semiconductor element which concerns on the manufacturing method of the said laminated body.
將本發明的代表性實施態樣的例子示於以下。 <1>一種硬化物的製造方法,其係包括: 膜形成步驟,將感光性組成物適用於基材上而形成感光性膜; 曝光步驟,選擇性地曝光上述感光性膜; 顯影步驟,使用顯影液對上述曝光後的感光性膜進行顯影而形成圖案;及 電磁波照射步驟,向藉由上述顯影步驟而獲得之圖案照射780nm以上且5μm以下的波長的電磁波。 <2>如<1>所述之硬化物的製造方法,其中,上述感光性組成物包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物、環氧樹脂及酚樹脂之群組中的至少1種樹脂。 <3>如<1>或<2>所述之硬化物的製造方法,其中,上述感光性組成物包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物及聚醯胺醯亞胺前驅物之群組中的至少1種樹脂。 <4>如<1>至<3>之任一項所述之硬化物的製造方法,其中,上述感光性組成物包含聚合性化合物。 <5>如<1>至<4>之任一項所述之硬化物的製造方法,其中,上述感光性組成物包含有機金屬錯合物作為聚合起始劑。 <6>如<1>至<5>之任一項所述之硬化物的製造方法,其中,所獲得之硬化物的玻璃轉移溫度超過200℃。 <7>如<1>至<6>之任一項所述之硬化物的製造方法,其中,上述電磁波照射步驟中之圖案的溫度為300℃以下。 <8>如<1>至<7>之任一項所述之硬化物的製造方法,其中,在上述電磁波照射步驟中,向圖案照射上述電磁波之時間的合計為60分鐘以下。 <9>如<1>至<8>之任一項所述之硬化物的製造方法,其中,上述電磁波照射步驟在惰性氣體環境下進行。 <10>如<1>至<9>之任一項所述之硬化物的製造方法,其中,上述電磁波照射步驟在氧濃度為1000ppm以下的環境下進行。 <11>如<1>至<10>之任一項所述之硬化物的製造方法,其中,上述感光性膜的膜厚為1μm以上。 <12>如<1>至<11>之任一項所述之硬化物的製造方法,其中,上述基材為在形成感光性膜之表面上具備金屬配線之基材。 <13>如<1>至<12>之任一項所述之硬化物的製造方法,其中,上述感光性組成物包含光聚合起始劑或光酸產生劑。 <14>一種積層體的製造方法,其係包括重複複數次<1>至<13>之任一項所述之硬化物的製造方法之步驟。 <15>如<14>所述之積層體的製造方法,其係進一步包括在上述複數次進行之硬化物的製造方法期間,在由硬化物形成之層上形成金屬層之金屬層形成步驟。 <16>一種半導體元件的製造方法,其係包括<1>至<13>之任一項所述之硬化物的製造方法或者<14>或<15>所述之積層體的製造方法。 [發明效果] Examples of typical embodiments of the present invention are shown below. <1> A method for producing a cured product, comprising: The film forming step is to apply the photosensitive composition to the substrate to form a photosensitive film; an exposure step of selectively exposing the photosensitive film; In the developing step, a developing solution is used to develop the exposed photosensitive film to form a pattern; and The electromagnetic wave irradiation process irradiates the pattern obtained by the said developing process with the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less. <2> The method for producing a cured product according to <1>, wherein the photosensitive composition contains a material selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor. , at least one resin in the group of epoxy resin and phenol resin. <3> The method for producing a cured product according to <1> or <2>, wherein the photosensitive composition contains a material selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide amide At least one resin in the group of imine precursors. <4> The method for producing a cured product according to any one of <1> to <3>, wherein the photosensitive composition contains a polymerizable compound. <5> The method for producing a cured product according to any one of <1> to <4>, wherein the photosensitive composition contains an organometallic complex as a polymerization initiator. <6> The method for producing a cured product according to any one of <1> to <5>, wherein the glass transition temperature of the obtained cured product exceeds 200°C. <7> The method for producing a cured product according to any one of <1> to <6>, wherein the temperature of the pattern in the electromagnetic wave irradiation step is 300° C. or lower. <8> The method for producing a cured product according to any one of <1> to <7>, wherein, in the electromagnetic wave irradiation step, the total time for irradiating the pattern with the electromagnetic wave is 60 minutes or less. <9> The method for producing a cured product according to any one of <1> to <8>, wherein the electromagnetic wave irradiation step is performed in an inert gas atmosphere. <10> The method for producing a cured product according to any one of <1> to <9>, wherein the electromagnetic wave irradiation step is performed in an environment with an oxygen concentration of 1000 ppm or less. <11> The method for producing a cured product according to any one of <1> to <10>, wherein the photosensitive film has a thickness of 1 μm or more. <12> The method for producing a cured product according to any one of <1> to <11>, wherein the base material is a base material provided with metal wiring on the surface on which the photosensitive film is formed. <13> The method for producing a cured product according to any one of <1> to <12>, wherein the photosensitive composition contains a photopolymerization initiator or a photoacid generator. <14> A method for producing a layered body comprising repeating the step of repeating the method for producing a cured product according to any one of <1> to <13>. <15> The method for producing a layered product according to <14>, further comprising a metal layer forming step of forming a metal layer on the layer formed of the hardened product during the method for producing a hardened product performed a plurality of times. <16> A method for producing a semiconductor element, comprising the method for producing a cured product according to any one of <1> to <13>, or the method for producing a laminate according to <14> or <15>. [Inventive effect]
依據本發明,提供一種可以獲得斷裂伸長率及耐藥品性優異之硬化物之硬化物的製造方法、包括上述硬化物的製造方法之積層體的製造方法及包括上述硬化物的製造方法或上述積層體的製造方法之半導體元件的製造方法。According to the present invention, there are provided a method for producing a cured product that can obtain a cured product excellent in elongation at break and chemical resistance, a method for producing a layered product including the method for producing the above-described cured product, and a method for producing the above-described cured product or the above-mentioned laminate A method of manufacturing a semiconductor device.
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。 在本說明書中,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。 在本說明書中,“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。 關於本說明書中之基團(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)。 在本說明書中,除非另有說明,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,可以舉出水銀燈的明線光譜、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。 在本說明書中,“(甲基)丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一者,“(甲基)丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一者,“(甲基)丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一者。 在本說明書中,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。 在本說明書中,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,在本說明書中,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。 在本說明書中,除非另有說明,則重量平均分子量(Mw)及數量平均分子量(Mn)為使用凝膠滲透層析(GPC)法進行測定之值,並且被定義為聚苯乙烯換算值。在本說明書中,關於重量平均分子量(Mw)及數量平均分子量(Mn),例如能夠藉由使用HLC-8220GPC(TOSOH CORPORATION製),並將保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000及TSKgel Super HZ2000(以上為TOSOH CORPORATION製)串聯連接而用作管住來求出。除非另有說明,則該等分子量為使用THF(四氫呋喃)作為洗提液進行測定者。其中,在溶解性低的情況等THF不適合作為洗提液的情況下,亦能夠使用NMP(N-甲基-2-吡咯啶酮)。又,除非另有說明,則GPC測定中之檢測為使用UV線(紫外線)的波長254nm檢測器者。 在本說明書中,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,亦可以在成為基準之層與上述其他層之間進一步夾有第3層或第3要素,並且成為基準之層與上述其他層無需接觸。又,除非另有說明,則將對於基材逐漸堆疊層之方向稱為“上”,或者,在具有樹脂組成物層之情況下,將從基材朝向樹脂組成物層之方向稱為“上”,將其相反方向稱為“下”。再者,該種上下方向的設定係為了便於說明本說明書,在實際態樣中,本說明書中之“上”方向亦可以與鉛直朝上不同。 在本說明書中,除非另有說明,則作為組成物中所包含之各成分,組成物亦可以包含與該成分對應之2種以上的化合物。又,除非另有記載,則組成物中之各成分的含量表示與其成分相當之所有化合物的合計含量。 在本說明書中,除非另有說明,則溫度為23℃,氣壓為101,325Pa(1氣壓),相對濕度為50%RH。 在本說明書中,較佳態樣的組合為更佳態樣。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. With regard to the labels of groups (atomic groups) in this specification, the labels of unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "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 the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) are connected in series and used for control, and obtained. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the reference layer among the plurality of layers concerned. That is, a third layer or a third element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise stated, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.
(硬化物的製造方法) 本發明的硬化物的製造方法包括:膜形成步驟,將感光性組成物適用於基材上而形成感光性膜;曝光步驟,選擇性地曝光上述感光性膜;顯影步驟,使用顯影液對上述曝光後的感光性膜進行顯影而形成圖案;及電磁波照射步驟,向藉由上述顯影步驟而獲得之圖案照射780nm以上且5μm以下的波長的電磁波。 依據本發明的硬化物的製造方法,可以獲得斷裂伸長率及耐藥品性優異之硬化物。 可以獲得上述效果之機制雖尚不明確,但是推測為如下。 (Manufacturing method of hardened product) The manufacturing method of the cured product of the present invention includes: a film forming step of applying a photosensitive composition to a substrate to form a photosensitive film; an exposure step of selectively exposing the photosensitive film; The exposed photosensitive film is developed to form a pattern; and an electromagnetic wave irradiation step irradiates an electromagnetic wave having a wavelength of 780 nm or more and 5 μm or less on the pattern obtained by the above-mentioned developing process. According to the method for producing a cured product of the present invention, a cured product excellent in elongation at break and chemical resistance can be obtained. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.
本發明的硬化物的製造方法包括電磁波照射步驟,該電磁波照射步驟向藉由上述顯影步驟而獲得之圖案照射780nm以上且5μm以下的波長的電磁波。 藉由該電磁波照射步驟對感光性膜進行加熱。 關於基於上述電磁波照射步驟之加熱,認為與使用了先前使用之箱式烘箱、加熱板等之加熱相比,非常快速進行,並且在感光性膜接近均勻的狀態下(例如,在由膜中的位置而引起之加熱的不均勻少的狀態下)進行加熱。 因此,推測為例如快速進行感光性膜中所包含之硬化性樹脂的硬化(例如,聚醯亞胺前驅物的環化、環氧樹脂的聚合等)、聚合性化合物的交聯等,並且硬化度、交聯密度等變高,因此可以獲得耐藥品性優異之硬化物。 又,推測為在感光性膜包含硬化性樹脂之情況下,如上所述硬化性樹脂的環化度變高,因此可以獲得斷裂伸長率亦優異之硬化物。 尤其,在感光性膜包含硬化性樹脂及聚合性化合物之情況下,若藉由先前的箱式烘箱等進行加熱,則加熱速度慢,因此有時先進行聚合性化合物的交聯之後,稍後進行硬化性樹脂的硬化。在這種情況下,認為由於交聯後的聚合性化合物的存在而硬化性樹脂的結構變化的自由度降低,有時硬化性樹脂的硬化度降低。在本發明的硬化物的製造方法中,推測為由於藉由電磁波照射步驟進行加熱而加熱速度非常快,在聚合性化合物的交聯的進行度低時能夠進行硬化性樹脂的硬化,因此硬化性樹脂的硬化度變高,斷裂伸長率優異。 The manufacturing method of the hardened|cured material of this invention includes the electromagnetic wave irradiation process which irradiates the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less to the pattern obtained by the said developing process. The photosensitive film is heated by this electromagnetic wave irradiation step. With regard to the heating based on the above-mentioned electromagnetic wave irradiation step, it is considered that compared with the heating using a box oven, a hot plate, etc. which have been used previously, it proceeds very quickly, and in a state where the photosensitive film is nearly uniform (for example, in a state where the photosensitive film is made of Heating is performed in a state with little heating unevenness due to the position. Therefore, it is presumed that, for example, curing of the curable resin contained in the photosensitive film (for example, cyclization of a polyimide precursor, polymerization of an epoxy resin, etc.), crosslinking of a polymerizable compound, and the like proceed rapidly, and curing degree, crosslinking density, etc. are increased, so that a cured product excellent in chemical resistance can be obtained. Moreover, when the photosensitive film contains a curable resin, it is presumed that the degree of cyclization of the curable resin becomes high as described above, so that a cured product excellent in elongation at break can be obtained. In particular, when the photosensitive film contains a curable resin and a polymerizable compound, the heating rate is slow when heated by a conventional oven oven or the like. Hardening of the curable resin is performed. In this case, it is considered that the degree of freedom of structural change of the curable resin decreases due to the presence of the crosslinked polymerizable compound, and the degree of hardening of the curable resin may decrease. In the method for producing the cured product of the present invention, it is presumed that the heating rate is very fast due to the heating by the electromagnetic wave irradiation step, and the curing of the curable resin can proceed when the degree of progress of the crosslinking of the polymerizable compound is low. The degree of hardening of the resin becomes high, and the elongation at break is excellent.
其中,在專利文獻1~專利文獻2中,未記載有包括上述膜形成步驟、曝光步驟、顯影步驟及電磁波照射步驟之硬化物的製造方法。 以下,對本發明的硬化物的製造方法進行詳細說明。 Among them, Patent Documents 1 to 2 do not describe a method for producing a cured product including the above-mentioned film forming step, exposure step, development step, and electromagnetic wave irradiation step. Hereinafter, the manufacturing method of the hardened|cured material of this invention is demonstrated in detail.
<膜形成步驟> 本發明的硬化物的製造方法包括將感光性組成物適用於基材上而形成感光性膜之膜形成步驟。 對膜形成步驟中所使用之感光性組成物的詳細內容將進行後述。 <Film formation step> The manufacturing method of the hardened|cured material of this invention includes the film formation process of applying a photosensitive composition to a base material, and forming a photosensitive film. Details of the photosensitive composition used in the film forming step will be described later.
〔基材〕 基材的種類能夠依據用途適當設定,但是並無特別限制,可以舉出矽、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(例如,可以為由金屬形成之基材及例如藉由電鍍或蒸鍍等而形成金屬層之基材中的任一個)、紙、SOG(Spin On Glass:旋塗式玻璃)、TFT(薄膜晶體管)陣列基材、模具基材、電漿顯示面板(PDP)的電極板等。在本發明中,尤其半導體製作基材為較佳,矽基材、Cu基材及模具基材為更佳。 又,在該等基材的表面上可以設置有由六甲基二矽氮烷(HMDS)等製成之密接層和氧化層等層。 又,基材的形狀並無特別限定,可以為圓形,亦可以為矩形。 作為基材的尺寸,若為圓形,則例如直徑為100~450mm,較佳為200~450mm。若為矩形,則例如短邊的長度為100~1000mm,較佳為200~700mm。 又,作為基材,例如可以使用板狀、較佳為面板狀的基材(基板)。 [Substrate] The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.
又,在樹脂層(例如,由硬化物形成之層)的表面或金屬層的表面上適用感光性組成物而形成感光性膜之情況下,樹脂層或金屬層成為基材。 又,基材為在形成感光性膜之表面上具備金屬配線之基材亦較佳。 在上述態樣中,作為基材的材質,上述半導體製作基材為較佳。 又,上述態樣中之金屬配線可以例示基於銅、鋁、鎳、釩、鈦、鉻、鈷、金、鎢、錫、銀及包含該等金屬之合金之配線,基於銅、鋁及包含該等金屬之合金之配線為更佳,基於包含銅或銅之合金之配線為進一步較佳。 Moreover, when forming a photosensitive film by applying a photosensitive composition to the surface of a resin layer (for example, the layer formed of hardened|cured material) or the surface of a metal layer, a resin layer or a metal layer becomes a base material. Moreover, it is also preferable that the base material is provided with metal wiring on the surface on which the photosensitive film is formed. In the above-mentioned aspect, as the material of the base material, the above-mentioned semiconductor production base material is preferable. In addition, the metal wiring in the above aspect can be exemplified by copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and wiring based on alloys containing these metals, and wiring based on copper, aluminum and containing the Wiring of alloys of the same metals is more preferable, and wiring based on alloys containing copper or copper is further preferable.
作為將感光性組成物適用於基材上之方法,塗佈為較佳。As a method for applying the photosensitive composition to a substrate, coating is preferable.
作為所適用之方法,具體而言,可以例示浸塗法、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、噴墨法等。從感光性膜的厚度的均勻性的觀點考慮,更佳為旋塗法、狹縫塗佈法、噴塗法或噴墨法,從感光性膜的厚度的均勻性的觀點及生產率的觀點考慮,旋塗法及狹縫塗佈法為較佳。依據方法調整感光性組成物的固體成分濃度或塗佈條件,從而能夠獲得所期望的厚度的感光性膜。又,亦能夠依據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、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。在為旋塗法的情況下,例如能夠以500~3,500rpm的轉速適用10秒鐘~3分鐘左右。 又,亦能夠適用將藉由上述賦予方法預先賦予至偽支撐體上而形成之塗膜轉印到基材上之方法。 關於轉印方法,本發明中亦能夠較佳地使用日本特開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。 又,可以進行在基材的端部中去除多餘的感光性膜的步驟。在該種步驟的例子中,可以舉出邊珠沖洗(EBR)、背面沖洗(Back rinse)等。 又,亦可以採用預濕步驟,該預濕步驟在將感光性組成物塗佈於基材上之前,對基材塗佈各種溶劑以提高基材的潤濕性之後,塗佈感光性組成物。 Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive film, the spin coating method, the slit coating method, the spray method or the inkjet method is more preferable, and from the viewpoint of the uniformity of the thickness of the photosensitive film and the viewpoint of productivity, The spin coating method and the slit coating method are preferable. By adjusting the solid content concentration and coating conditions of the photosensitive composition according to the method, a photosensitive film of a desired thickness can be obtained. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an inkjet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . Moreover, the process of removing the excess photosensitive film in the edge part of a base material can be performed. Examples of such a step include edge bead rinse (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step can also be adopted, in which, before the photosensitive composition is coated on the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the photosensitive composition is applied. .
感光性膜的膜厚(在硬化物的製造方法包括後述乾燥步驟之情況下為乾燥步驟後的膜厚)並無特別限定,但是1μm以上為較佳,1~100μm為更佳,2~40μm為進一步較佳。 膜厚只要在上述範圍內,則在後述電磁波照射步驟中抑制膜中的位置上之加熱不均勻之效果顯著,並且能夠快速進行加熱。 The film thickness of the photosensitive film (the film thickness after the drying step when the method for producing the cured product includes the drying step described later) is not particularly limited, but is preferably 1 μm or more, more preferably 1 to 100 μm, and 2 to 40 μm for further better. As long as the film thickness is within the above-mentioned range, the effect of suppressing heating unevenness at positions in the film in the electromagnetic wave irradiation step described later is remarkable, and heating can be performed quickly.
<乾燥步驟> 上述感光性膜在膜形成步驟(層形成步驟)之後,為了去除溶劑,可以供於乾燥所形成之感光性膜(層)之步驟(乾燥步驟)中。 亦即,本發明的硬化物的製造方法可以包括乾燥步驟,該乾燥步驟乾燥藉由膜形成步驟而形成之感光性膜。 又,上述乾燥步驟在膜形成步驟之後且在曝光步驟之前進行為較佳。 乾燥步驟中之感光性膜的乾燥溫度為50~150℃為較佳,70℃~130℃為更佳,90℃~110℃為進一步較佳。又,亦可以藉由減壓來進行乾燥。作為乾燥時間,可以例示30秒鐘~20分鐘,1分鐘~10分鐘為較佳,2分鐘~7分鐘為更佳。 <Drying step> The said photosensitive film can be used for the process (drying process) of drying the photosensitive film (layer) formed after a film formation process (layer formation process), in order to remove a solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the photosensitive film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the photosensitive film in the drying step is preferably 50 to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
<曝光步驟> 上述感光性膜供於選擇性地曝光感光性膜之曝光步驟中。 亦即,本發明的硬化物的製造方法包括曝光步驟,該曝光步驟選擇性地曝光藉由膜形成步驟而形成之感光性膜。 選擇性地曝光表示對感光性膜的一部分進行曝光。又,藉由選擇性地曝光,在感光性膜上形成經曝光之區域(曝光部)和未經曝光的區域(非曝光部)。 關於曝光量,只要能夠感光感光性膜,則並無特別規定,例如以在波長365nm下的曝光能量換算為50~10,000mJ/cm 2為較佳,200~8,000mJ/cm 2為更佳。 <Exposure step> The said photosensitive film is used for the exposure step of selectively exposing the photosensitive film. That is, the manufacturing method of the hardened|cured material of this invention includes the exposure process which selectively exposes the photosensitive film formed by the film formation process. Selectively exposing means exposing a part of the photosensitive film. Moreover, by selectively exposing, the exposed area (exposed part) and the unexposed area (non-exposed part) are formed on the photosensitive film. The exposure amount is not particularly limited as long as the photosensitive film can be exposed, but for example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm.
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 within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.
關於曝光波長,若以與光源的關係進行說明,則可以舉出(1)半導體雷射(波長830nm、532nm、488nm、405nm、375nm、355nm 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、(7)YAG雷射的第二諧波532nm且第三諧波355nm等。關於感光性組成物,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,可以獲得尤其高的曝光靈敏度。 又,曝光的方式並無特別限定,只要為曝光由感光性組成物形成之感光性膜的至少一部分之方式即可,但是可以舉出使用了光罩之曝光、基於雷射直接成像法之曝光等。 Regarding the exposure wavelength, if the relationship with the light source is explained, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) ) High pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and the third harmonic is 355nm, etc. With regard to the photosensitive composition, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the photosensitive film formed from the photosensitive composition, and exposure using a mask and exposure by direct laser imaging can be mentioned. Wait.
<曝光後加熱步驟> 上述感光性膜可以供於在曝光後進行加熱之步驟(曝光後加熱步驟)中。 亦即,本發明的硬化物的製造方法可以包括曝光後加熱步驟,該曝光後加熱步驟加熱藉由曝光步驟進行曝光之感光性膜。 曝光後加熱步驟能夠在曝光步驟之後且在顯影步驟之前進行。 曝光後加熱步驟中之加熱溫度為50℃~140℃為較佳,60℃~120℃為更佳。 曝光後加熱步驟中之加熱時間為30秒鐘~300分鐘為較佳,1分鐘~10分鐘為更佳。 關於曝光後加熱步驟中之升溫速度,從加熱開始時的溫度至最高加熱溫度為1~12℃/分鐘為較佳,2~10℃/分鐘為更佳,3~10℃/分鐘為進一步較佳。 又,升溫速度可以在加熱過程中適當變更。 作為曝光後加熱步驟中之加熱機構,並無特別限定,能夠使用公知的加熱板、烘箱、紅外線加熱器等。 又,藉由在加熱時使氮氣、氦氣、氬氣等非活性氣體流過等而在低氧濃度的環境下進行亦較佳。 <Heating step after exposure> The said photosensitive film can be used for the process (heating process after exposure) of heating after exposure. That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process which heats the photosensitive film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.
<顯影步驟> 曝光後的上述感光性膜供於使用顯影液進行顯影而形成圖案之顯影步驟中。 亦即,本發明的硬化物的製造方法包括顯影步驟,該顯影步驟使用顯影液對藉由曝光步驟進行曝光之感光性膜進行顯影而形成圖案。 藉由進行顯影來去除感光性膜的曝光部及非曝光部中的一者,並形成圖案。 其中,將藉由顯影步驟去除感光性膜的非曝光部之顯影稱為負型顯影,將藉由顯影步驟去除感光性膜的曝光部之顯影稱為正型顯影。 <Development step> The said photosensitive film after exposure is used for the image development process which develops using a developing solution and forms a pattern. That is, the manufacturing method of the hardened|cured material of this invention includes the developing process which develops the photosensitive film exposed by the exposure process using a developing solution, and forms a pattern. By performing development, one of the exposed part and the non-exposed part of the photosensitive film is removed, and a pattern is formed. Among them, the development of removing the non-exposed portion of the photosensitive film by the development step is called negative development, and the development of removing the exposed portion of the photosensitive film by the development step is called positive development.
〔顯影液〕 作為在顯影步驟中所使用之顯影液,可以舉出鹼性水溶液或包含有機溶劑之顯影液。 [Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.
在顯影液為鹼性水溶液之情況下,作為鹼性水溶液能夠包含之鹼性化合物,可以舉出無機鹼類、一級胺類、二級胺類、三級胺類、四級銨鹽,TMAH(氫氧化四甲銨)、氫氧化鉀、碳酸鈉、氫氧化鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二正丁胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、氫氧化四乙基銨、氫氧化四丙銨(Tetrapropylammonium Hydroxide)、氫氧化四丁基銨、氫氧化四戊基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化乙基三甲基銨、氫氧化丁基三甲基銨、氫氧化甲基三戊基銨、氫氧化二丁基二戊基銨、氫氧化二甲基雙(2-羥乙基)銨、氫氧化三甲基苯基銨、氫氧化三甲基苄基銨、氫氧化三乙基苄基銨、吡咯、哌啶為較佳,更佳為TMAH。例如在使用TMAH之情況下,顯影液中之鹼性化合物的含量在顯影液總質量中為0.01~10質量%為較佳,0.1~5質量%為更佳,0.3~3質量%為進一步較佳。When the developing solution is an alkaline aqueous solution, examples of the alkaline compounds that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH ( Tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium oxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis(hydroxide) 2-hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass in the total mass of the developer. good.
在顯影液包含有機溶劑之情況下,關於有機溶劑,作為酯類,例如可以較佳地舉出乙酸乙酯、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,例如可以較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、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***、二乙二醇單丁醚、丙二醇單甲醚(PGME)、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等,以及作為酮類,例如可以較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等,以及作為環狀烴類,例如可以較佳地舉出甲苯、二甲苯、苯甲醚等芳香族烴類、檸檬烯等環式萜烯類、作為亞碸類,可以較佳地舉出二甲基亞碸以及作為醇類,可以較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等以及作為醯胺類,可以較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the developing solution contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc., for example. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc.) (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxy Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionic acid) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane Ethyl acid, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), 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 can be preferably used ketone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Preferable examples of the sulfites include dimethylsulfoxide, and as the alcohols, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylenediol. Alcohol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are preferably used. Wait.
在顯影液包含有機溶劑之情況下,有機溶劑能夠使用1種或混合使用2種以上。在本發明中,尤其包含選自包括環戊酮、γ-丁內酯、二甲基亞碸、N-甲基-2-吡咯啶酮及環己酮之群組中的至少1種之顯影液為較佳,包含選自包括環戊酮、γ-丁內酯及二甲基亞碸之群組中的至少1種之顯影液為更佳,包含環戊酮之顯影液為最佳。When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, development of at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly included The solution is preferred, and the developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and the developing solution including cyclopentanone is the most preferred.
在顯影液包含有機溶劑之情況下,有機溶劑的含量相對於顯影液的總質量為50質量%以上為較佳,70質量%以上為更佳,80質量%以上為進一步較佳,90質量%以上為特佳。又,上述含量可以為100質量%。When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more relative to the total mass of the developer solution. The above are excellent. Moreover, the said content may be 100 mass %.
顯影液可以進一步包含其他成分。 作為其他成分,例如可以舉出公知的界面活性劑和公知的消泡劑等。 The developer may further contain other components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.
〔顯影液的供給方法〕 關於顯影液的供給方法,只要能夠形成所期望的圖案,則並無特別限制,存在將形成有感光性膜之基材浸漬於顯影液中之方法、使用噴嘴向形成於基材上之感光性膜供給顯影液以進行旋覆浸沒顯影或連續供給顯影液之方法。噴嘴的種類並無特別限制,可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 從顯影液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮,使用直式噴嘴供給顯影液之方法或使用噴霧噴嘴連續供給之方法為較佳,從顯影液向圖像部的滲透性的觀點考慮,使用噴霧噴嘴進行供給之方法為更佳。 又,可以採用在使用直式噴嘴連續供給顯影液之後,旋轉基材以從基材上去除顯影液,在旋轉乾燥之後再次使用直式噴嘴連續供給之後,旋轉基材以從基材上去除顯影液之步驟,亦可以反覆進行複數次該步驟。 又,作為顯影步驟中之顯影液的供給方法,能夠採用將顯影液連續地供給至基材之步驟、在基材上使顯影液保持大致靜止狀態之步驟、在基材上利用超聲波等使顯影液振動之步驟及組合了該等之步驟等。 [How to supply developer] The supply method of the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate on which the photosensitive film is formed in the developer, and a method of immersing a photosensitive film formed on the substrate using a nozzle. The film is supplied with a developer for spin-on immersion development or a method of continuously supplying the developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate. The step of liquid solution can also be repeated several times. In addition, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.
作為顯影時間,10秒鐘~10分鐘為較佳,20秒鐘~5分鐘為更佳。顯影時的顯影液的溫度並無特別規定,能夠較佳為在10~45℃下進行,更較佳為在18℃~30℃下進行。The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.
在顯影步驟中,在使用了顯影液之處理之後,可以進一步進行使用沖洗液之圖案的清洗(沖洗)。又,可以採用與圖案接觸之顯影液沒有完全乾燥之前供給沖洗液等的方法。In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.
〔沖洗液〕 在顯影液為鹼性水溶液之情況下,作為沖洗液,例如能夠使用水。在顯影液為包含有機溶劑之顯影液之情況下,作為沖洗液,例如能夠使用與顯影液中所包含之溶劑不同之溶劑(例如,水、與顯影液中所包含之有機溶劑不同之有機溶劑)。 [Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).
作為沖洗液包含有機溶劑時的有機溶劑,作為酯類,例如可以較佳地舉出乙酸乙酯、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,例如可以較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、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***、二乙二醇單丁醚、丙二醇單甲醚(PGME)、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等,以及作為酮類,例如可以較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等,以及作為環狀烴類,例如可以較佳地舉出甲苯、二甲苯、苯甲醚等芳香族烴類、檸檬烯等環式萜烯類、作為亞碸類,可以較佳地舉出二甲基亞碸以及作為醇類,可以較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等以及作為醯胺類,可以較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。As the organic solvent when the rinsing liquid contains an organic solvent, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, Isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate ( Example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, etc.), 3-alkoxypropionic acid alkyl esters (for example: methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxypropionic acid Alkyl esters (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy-2- Methyl methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate acid ethyl ester, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve can be preferably mentioned. Agent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), 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 cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, octanol, diethylene glycol, and propylene glycol. , methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. are preferably mentioned.
在沖洗液包含有機溶劑之情況下,有機溶劑能夠使用1種或混合使用2種以上。在本發明中,尤其環戊酮、γ-丁內酯、二甲基亞碸、N-甲基吡咯啶酮、環己酮、PGMEA、PGME為較佳,環戊酮、γ-丁內酯、二甲基亞碸、PGMEA、PGME為更佳,環己酮、PGMEA為進一步較佳。When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.
在沖洗液包含有機溶劑之情況下,沖洗液的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,亦可以為沖洗液的100質量%為有機溶劑。When the rinsing liquid contains an organic solvent, preferably 50% by mass or more of the rinsing liquid 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. Moreover, 100 mass % of the rinse liquid may be an organic solvent.
沖洗液可以進一步包含其他成分。 作為其他成分,例如可以舉出公知的界面活性劑和公知的消泡劑等。 The rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.
〔沖洗液的供給方法〕 關於沖洗液的供給方法,只要能夠形成所期望的圖案,則並無特別限制,存在將基材浸漬於沖洗液中之方法、在基材上的旋覆浸沒顯影、以噴淋形式將沖洗液供給至基材之方法、藉由直式噴嘴等機構將顯影液連續供給至基材之方法。 從沖洗液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮,存在使用噴淋噴嘴、直式噴嘴、噴霧噴嘴等供給沖洗液之方法,使用噴霧噴嘴連續供給之方法為較佳,從沖洗液向圖像部的滲透性的觀點考慮,使用噴霧噴嘴進行供給之方法為更佳。噴嘴的種類並無特別限制,可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 亦即,沖洗步驟為藉由直式噴嘴將沖洗液供給或連續供給至上述曝光後的感光性膜中之步驟為較佳,藉由噴霧噴嘴供給沖洗液之步驟為更佳。 又,作為沖洗步驟中之沖洗液的供給方法,能夠採用將沖洗液連續地供給至基材之步驟、在基材上使沖洗液保持大致靜止狀態之步驟、在基材上利用超聲波等使沖洗液振動之步驟及組合了該等之步驟等。 [How to supply the rinse solution] The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate in the rinse liquid, spin immersion development on the substrate, and spraying the rinse liquid The method of supplying to the substrate and the method of continuously supplying the developer to the substrate by a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the photosensitive film after exposure through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.
作為沖洗時間,10秒鐘~10分鐘為較佳,20秒鐘~5分鐘為更佳。沖洗時的沖洗液的溫度並無特別規定,能夠較佳為在10~45℃下進行,更較佳為在18℃~30℃下進行。The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be performed preferably at 10 to 45°C, and more preferably at 18 to 30°C.
<電磁波照射步驟> 本發明的硬化物的製造方法包括電磁波照射步驟,該電磁波照射步驟向藉由上述顯影步驟而獲得之圖案照射780nm以上且5μm以下的波長的電磁波。 例如,在感光性膜包含後述特定樹脂之情況下,藉由電磁波照射步驟而圖案被加熱以進行特定樹脂的硬化。 <Electromagnetic wave irradiation procedure> The manufacturing method of the hardened|cured material of this invention includes the electromagnetic wave irradiation process which irradiates the electromagnetic wave of the wavelength of 780 nm or more and 5 micrometers or less to the pattern obtained by the said developing process. For example, when a photosensitive film contains specific resin mentioned later, the pattern is heated by an electromagnetic wave irradiation process, and hardening of specific resin is performed.
在電磁波照射步驟中,電磁波只要向藉由顯影步驟而獲得之圖案的至少一部分照射即可,但是向圖案的全部照射為較佳。 照射量並無特別限定,只要設為感光性膜的溫度及電磁波的照射時間在後述範圍內之照射量即可。 In the electromagnetic wave irradiation step, the electromagnetic wave may be irradiated to at least a part of the pattern obtained in the developing step, but it is preferable to irradiate the entire pattern. The irradiation amount is not particularly limited, and the temperature of the photosensitive film and the irradiation time of the electromagnetic wave may be the irradiation amount within the range described later.
電磁波照射步驟中之電磁波為780nm以上且5μm以下的波長的電磁波,900nm以上且4μm以下的波長的電磁波為較佳,1000nm以上且3.5μm以下的波長的電磁波為更佳。 在上述電磁波包含複數個波長的電磁波之情況下,只要至少1個電磁波的波長在上述範圍內即可。 在感光性組成物包含光聚合起始劑之情況下,上述電磁波不包含550nm以下的波長的電磁波的態樣亦為本發明的較佳態樣之一。 又,在感光性組成物包含光鹼產生劑之情況下,促進源自光鹼產生劑的鹼的產生,因此上述電磁波包含550nm以下的波長的電磁波之態樣亦為本發明的較佳態樣之一。 又,上述電磁波包含各種波長的電磁波(所謂之寬的電磁波)對感光性膜的組成之容許度高,有時為較佳。 The electromagnetic wave in the electromagnetic wave irradiation step is an electromagnetic wave with a wavelength of 780 nm or more and 5 μm or less, preferably an electromagnetic wave with a wavelength of 900 nm or more and 4 μm or less, and more preferably an electromagnetic wave with a wavelength of 1000 nm or more and 3.5 μm or less. In the case where the above-mentioned electromagnetic waves include electromagnetic waves of a plurality of wavelengths, the wavelength of at least one electromagnetic wave may be within the above-mentioned range. When the photosensitive composition contains a photopolymerization initiator, an aspect in which the electromagnetic wave does not include an electromagnetic wave having a wavelength of 550 nm or less is also one of the preferred aspects of the present invention. In addition, when the photosensitive composition contains a photobase generator, the generation of the base derived from the photobase generator is accelerated, so the aspect in which the above-mentioned electromagnetic wave includes an electromagnetic wave having a wavelength of 550 nm or less is also a preferred aspect of the present invention. one. In addition, it may be preferable that the above-mentioned electromagnetic waves include electromagnetic waves of various wavelengths (so-called broad electromagnetic waves) because the tolerance to the composition of the photosensitive film is high.
作為曝光光源,可以舉出公知的紅外線燈、紅外線二極體、紅外線照射裝置等,考慮所照射之電磁波的波長、所照射之電磁波的能量等而能夠無特別限定地使用。在該等之中,使用鹵素加熱器(鹵素燈)為較佳。Examples of the exposure light source include known infrared lamps, infrared diodes, and infrared irradiation devices, and can be used without particular limitations in consideration of the wavelength of the electromagnetic wave to be irradiated, the energy of the electromagnetic wave to be irradiated, and the like. Among these, it is preferable to use a halogen heater (halogen lamp).
作為電磁波照射步驟中之圖案的溫度(最高溫度),並無特別限定,只要考慮感光性膜中所包含之成分等來決定即可,但是400℃以下為較佳,300℃以下為更佳,250℃以下為更佳,亦能夠設為240℃以下。 上述最高溫度的下限為150℃以上為較佳,180℃以上為更佳。 The temperature (maximum temperature) of the pattern in the electromagnetic wave irradiation step is not particularly limited and may be determined in consideration of the components contained in the photosensitive film, but is preferably 400°C or lower, more preferably 300°C or lower. It is more preferable that it is 250 degrees C or less, and 240 degrees C or less can also be set. The lower limit of the maximum temperature is preferably 150°C or higher, more preferably 180°C or higher.
在電磁波照射步驟中,向圖案照射上述電磁波之時間的合計並無特別限定,只要考慮感光性膜的厚度、感光性膜中所包含之成分等來決定即可,但是60分鐘以下為較佳,30分鐘以下為更佳。In the electromagnetic wave irradiation step, the total time for irradiating the pattern with the electromagnetic wave is not particularly limited, and may be determined in consideration of the thickness of the photosensitive film, the components contained in the photosensitive film, and the like, but 60 minutes or less is preferable. 30 minutes or less is better.
電磁波照射步驟在惰性氣體環境下進行為較佳。 作為惰性氣體,可以舉出N 2氣體、Ar氣體等鹵素氣體。 又,電磁波照射步驟在減壓狀態下或在真空狀態下進行亦較佳。 進而,電磁波照射步驟在H 2氣體、甲酸氣體等還元性氣體環境下進行亦較佳。 在該等態樣中,電磁波照射步驟在氧濃度為1,000ppm以下的環境下進行為較佳,在100ppm以下的環境下進行為更佳,在10ppm的環境下進行為進一步較佳。上述氧濃度的下限並無特別限定,只要為0ppm以上即可。 The electromagnetic wave irradiation step is preferably carried out in an inert gas environment. Examples of the inert gas include halogen gases such as N 2 gas and Ar gas. In addition, it is also preferable to perform the electromagnetic wave irradiation step in a reduced pressure state or in a vacuum state. Furthermore, it is also preferable to perform the electromagnetic wave irradiation step in a reducing gas environment such as H 2 gas and formic acid gas. In these aspects, the electromagnetic wave irradiation step is preferably performed in an environment with an oxygen concentration of 1,000 ppm or less, more preferably in an environment of 100 ppm or less, and even more preferably in an environment of 10 ppm. The lower limit of the above-mentioned oxygen concentration is not particularly limited, as long as it is 0 ppm or more.
關於電磁波照射步驟中之圖案的升溫速度,從電磁波照射步驟開始時的溫度至上述最高溫度為止為5℃/min以上為較佳,10℃/min以上為較佳,100℃/min以上為進一步較佳。The heating rate of the pattern in the electromagnetic wave irradiation step is preferably 5°C/min or more, preferably 10°C/min or more, and 100°C/min or more from the temperature at the start of the electromagnetic wave irradiation step to the above-mentioned maximum temperature. better.
電磁波照射步驟開始時的圖案的溫度為20℃~150℃為較佳,20℃~130℃為更佳,25℃~120℃為進一步較佳。電磁波照射步驟開始時的溫度是指在電磁波照射步驟中開始照射電磁波時的溫度。例如,在感光性組成物包含溶劑之情況下,使其從比上述溶劑的沸點低30~200℃的溫度升溫為較佳。The temperature of the pattern at the start of the electromagnetic wave irradiation step is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of the electromagnetic wave irradiation step refers to the temperature when the electromagnetic wave irradiation is started in the electromagnetic wave irradiation step. For example, when the photosensitive composition contains a solvent, it is preferable to raise the temperature from a temperature lower than the boiling point of the solvent by 30 to 200°C.
電磁波照射步驟中之維持上述最高溫度之時間為5~360分鐘為較佳,10~300分鐘為更佳,15~240分鐘為進一步較佳。The time for maintaining the above-mentioned maximum temperature in the electromagnetic wave irradiation step is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
又,在電磁波照射步驟中,還可以藉由其他加熱機構進行加熱。 上述加熱可以與電磁波的照射同時進行,亦可以在電磁波的照射開始之前或結束之後進行。 作為上述加熱機構,例如可以舉出加熱板、電熱式烘箱、熱風式烘箱等。 Moreover, in the electromagnetic wave irradiation process, you may heat by another heating means. The above-mentioned heating may be performed simultaneously with the irradiation of electromagnetic waves, or may be performed before or after the irradiation of electromagnetic waves is started. As said heating means, a hotplate, an electrothermal oven, a hot air oven, etc. are mentioned, for example.
作為電磁波照射步驟中之電磁波照射機構,例如能夠無特別限定地使用紅外線烘箱等公知的紅外線照射裝置等。As the electromagnetic wave irradiation means in the electromagnetic wave irradiation step, for example, a known infrared irradiation device such as an infrared oven can be used without particular limitation.
可以在電磁波照射步驟結束之後,冷卻圖案。The pattern may be cooled after the electromagnetic wave irradiation step is finished.
<顯影後曝光步驟> 除了上述電磁波照射步驟以外,藉由顯影步驟而獲得之圖案(在進行沖洗步驟之情況下為沖洗後的圖案)亦可以供於曝光顯影步驟之後的圖案之顯影後曝光步驟中。 亦即,本發明的硬化物的製造方法可以包括顯影後曝光步驟,該顯影後曝光步驟對藉由顯影步驟而獲得之圖案進行曝光。本發明的硬化物的製造方法可以包括加熱步驟及顯影後曝光步驟,亦可以僅包括加熱步驟及顯影後曝光步驟中的一者。 在顯影後曝光步驟中,例如能夠促進藉由光鹼產生劑的感光而進行聚醯亞胺前驅物等的環化之反應或藉由光酸產生劑的感光而進行酸分解性基的脫離之反應等。 在顯影後曝光步驟中,只要曝光在顯影步驟中所獲得之圖案的至少一部分即可,但是曝光上述圖案的全部為較佳。 顯影後曝光步驟中之曝光量以在感光性化合物具有靈敏度之波長下之曝光能量換算為50~20,000mJ/cm 2為較佳,100~15,000mJ/cm 2為更佳。 顯影後曝光步驟例如能夠使用上述曝光步驟中之光源來進行,使用寬頻帶光為較佳。 <Exposure step after development> In addition to the electromagnetic wave irradiation step described above, the pattern obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used in the post-development exposure step of exposing the pattern after the development step middle. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The manufacturing method of the cured product of the present invention may include a heating step and an exposure step after development, or may include only one of a heating step and an exposure step after development. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator can be accelerated, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.
<金屬層形成步驟> 藉由電磁波照射步驟而獲得之圖案可以供於在圖案上形成金屬層之金屬層形成步驟中。 亦即,本發明的硬化物的製造方法包括金屬層形成步驟為較佳,該金屬層形成步驟在藉由電磁波照射步驟而獲得之圖案上形成金屬層。 <Metal layer formation step> The pattern obtained by the electromagnetic wave irradiation step can be used in a metal layer forming step of forming a metal layer on the pattern. That is, it is preferable that the manufacturing method of the hardened|cured material of this invention includes the metal layer formation process which forms a metal layer on the pattern obtained by the electromagnetic wave irradiation process.
作為金屬層,並無特別限定,能夠使用現有的金屬種類,可以例示銅、鋁、鎳、釩、鈦、鉻、鈷、金、鎢、錫、銀及包含該等金屬之合金,銅及鋁為更佳,銅為進一步較佳。The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, alloys containing these metals, copper and aluminum. More preferred, copper is further preferred.
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、美國專利第7888181B2、美國專利第9177926B2中所記載之方法。例如,可以考慮光微影、PVD(物理蒸鍍法)、CVD(化學氣相沉積法)、剝離、電解電鍍、無電解電鍍、蝕刻、印刷及組合了該等之方法等。更具體而言,可以舉出組合了濺射、光微影及蝕刻之圖案化方法、組合了光微影和電解電鍍之圖案化方法。作為電鍍的較佳態樣,可以舉出使用了硫酸銅或氰化銅電鍍液之電解電鍍。The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution can be mentioned.
作為金屬層的厚度,最厚的壁厚的部分為0.01~50μm為較佳,1~10μm為更佳。The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, in the thickest part.
<硬化物> 藉由本發明的硬化物的製造方法,能夠獲得硬化物。 硬化物的形態並無特別限定,能夠依據用途選擇薄膜狀、棒狀、球狀、顆粒狀等。在本發明中,所獲得之硬化物為薄膜狀為較佳。 又,藉由感光性組成物的圖案加工,亦能夠依據在壁面上形成保護膜,形成用於導通的穴(Beer hall)、調整阻抗或靜電容量或者內部應力、賦予放熱功能等用途選擇該硬化物的形狀。該硬化物(由硬化物形成之膜)的膜厚為0.5μm以上且150μm以下為較佳。 藉由本發明的硬化物的製造方法製造了硬化物時的收縮率為50%以下為較佳,45%以下為更佳,40%以下為進一步較佳。其中,收縮率是指電磁波照射步驟後的圖案相對於顯影步驟後的圖案的體積變化的百分率,並且能夠由下述式計算出。 收縮率[%]=100-(電磁波照射步驟後的圖案的體積÷顯影步驟後的圖案的體積)×100 <hardened product> The hardened|cured material can be obtained by the manufacturing method of the hardened|cured material of this invention. The form of the cured product is not particularly limited, and a film form, a rod form, a spherical form, a granular form, etc. can be selected according to the application. In the present invention, the obtained cured product is preferably in the form of a film. Furthermore, by patterning the photosensitive composition, the curing can also be selected for the purpose of forming a protective film on the wall surface, forming a beer hall for conduction, adjusting resistance, capacitance or internal stress, and imparting a heat release function. shape of things. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less. When the cured product is produced by the method for producing a cured product of the present invention, the shrinkage ratio is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of the volume change of the pattern after the electromagnetic wave irradiation step with respect to the pattern after the development step, and can be calculated by the following formula. Shrinkage rate [%]=100-(volume of pattern after electromagnetic wave irradiation step÷volume of pattern after developing step)×100
<硬化物的特性> 在本發明的硬化物的製造方法中所使用之感光性組成物包含後述環化樹脂的前驅物之情況下,從硬化物的斷裂伸長率的觀點考慮,藉由本發明的硬化物的製造方法而獲得之硬化物中之環化率為70%以上為較佳,80%以上為更佳,90%以上為進一步較佳。 藉由本發明的硬化物的製造方法而獲得之硬化物的斷裂伸長率為40%以上為較佳,50%以上為更佳,60%以上為進一步較佳。 藉由本發明的硬化物的製造方法而獲得之硬化物的玻璃轉移溫度(Tg)超過180℃為較佳,超過200℃為更佳,超過230℃為進一步較佳。 <Characteristics of hardened product> In the case where the photosensitive composition used in the method for producing a cured product of the present invention contains a precursor of a cyclized resin to be described later, from the viewpoint of the elongation at break of the cured product, the method for producing a cured product of the present invention can The cyclization rate in the obtained hardened material is preferably 70% or more, more preferably 80% or more, and further more preferably 90% or more. The elongation at break of the cured product obtained by the method for producing the cured product of the present invention is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. It is preferable that the glass transition temperature (Tg) of the hardened|cured material obtained by the manufacturing method of the hardened|cured material of this invention exceeds 180 degreeC, More preferably, it exceeds 200 degreeC, More preferably, it exceeds 230 degreeC.
<用途> 作為能夠適用本發明的硬化物的製造方法或藉由本發明的硬化物的製造方法而獲得之硬化物的領域,可以舉出半導體元件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外,亦可以舉出密封膜、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。 <Use> Examples of fields to which the method for producing a cured product of the present invention or a cured product obtained by the method for producing a cured product of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for rewiring layers, stress buffer films, and the like. . In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.
又,本發明的硬化物的製造方法或藉由本發明的硬化物的製造方法而獲得之硬化物亦能夠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、電子尤其微電子中之保護漆及介電層的製造等中。In addition, the manufacturing method of the cured product of the present invention or the cured product obtained by the manufacturing method of the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates and screen plates, the use of etching molding components, electronics, especially microelectronics. In the manufacture of protective paint and dielectric layers, etc.
(積層體及積層體的製造方法) 本發明的積層體是指具有複數層由本發明的硬化物形成之層之結構體。 本發明的積層體為包括2層以上的由硬化物形成之層之積層體,並且亦可以設為積層3層以上而成之積層體。 上述積層體中所包括之2層以上的上述由硬化物形成之層中的至少1個為由本發明的硬化物形成之層,從抑制硬化物的收縮或上述收縮所伴隨之硬化物的變形等之觀點考慮,上述積層體中所包括之所有由硬化物形成之層為由本發明的硬化物形成之層亦較佳。 (Laminated body and method for producing the laminated body) The layered product of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers formed of a cured product, and may be a layered body formed by stacking three or more layers. At least one of the two or more layers formed of the cured product included in the above-mentioned layered product is a layer formed of the cured product of the present invention, and suppresses the shrinkage of the cured product or the deformation of the cured product accompanying the shrinkage. From a viewpoint, it is also preferable that all the layers formed of the cured product included in the above-mentioned laminate are layers formed of the cured product of the present invention.
亦即,本發明的積層體的製造方法包括本發明的硬化物的製造方法為較佳,包括重複複數次本發明的積層體的製造方法之步驟為更佳。That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened|cured material of this invention, and it is more preferable to include the process of repeating the manufacturing method of the laminated body of this invention several times.
本發明的積層體包括2層以上的由硬化物形成之層,在上述由硬化物形成之層之間的任一個之間包括金屬層之態樣為較佳。關於上述金屬層,藉由上述金屬層形成步驟而形成為較佳。 亦即,本發明的積層體的製造方法進一步包括在複數次進行之硬化物的製造方法期間,在由硬化物形成之層上形成金屬層之金屬層形成步驟為較佳。金屬層形成步驟的較佳態樣如上所述。 作為上述積層體,例如可以舉出至少包含依次積層有第一個由硬化物形成之層、金屬層、第二個由硬化物形成之層這3個層之層結構之積層體作為較佳者。 上述第一個由硬化物形成之層及上述第二個由硬化物形成之層均為由本發明的硬化物形成之層為較佳。用於形成上述第一個由硬化物形成之層之感光性組成物和用於形成上述第二個由硬化物形成之層之感光性組成物可以為組成相同的組成物,亦可以為組成不同之組成物。本發明的積層體中之金屬層可以較佳地用作再配線層等金屬配線。 The layered product of the present invention includes two or more layers formed of a cured product, and an aspect in which a metal layer is included between any of the layers formed of the cured product is preferred. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation step of forming a metal layer on the layer formed of the hardened|cured material during the manufacturing method of the hardened|cured material performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layer structure in which at least three layers of a first layer made of a cured product, a metal layer, and a second layer of a cured product are laminated in this order can be mentioned as a preferred one. . It is preferable that the above-mentioned first layer formed from the hardened product and the above-mentioned second layer formed from the hardened product are both layers formed from the hardened product of the present invention. The photosensitive composition used to form the above-mentioned first layer formed of the hardened material and the photosensitive composition used to form the above-mentioned second layer formed of the hardened material may have the same composition or may have different compositions. composition. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.
<積層步驟> 本發明的積層體的製造方法包括積層步驟為較佳。 積層步驟為包括在圖案(樹脂層)或金屬層的表面上再次依序進行(a)膜形成步驟(層形成步驟)、(b)曝光步驟、(c)顯影步驟、(d)電磁波照射步驟之一系列步驟。其中,亦可以為重複(a)膜形成步驟及(d)電磁波照射步驟中的至少一者之態樣。又,在(d)電磁波照射步驟之後,還可以包括(e)金屬層形成步驟。在積層步驟中可以進一步適當包括上述乾燥步驟等,這是不言而喻的。 <Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination process. The lamination step includes performing (a) film forming step (layer forming step), (b) exposure step, (c) developing step, (d) electromagnetic wave irradiation step again in sequence on the surface of the pattern (resin layer) or metal layer. a series of steps. However, at least one of the (a) film formation step and the (d) electromagnetic wave irradiation step may be repeated. Also, after (d) the electromagnetic wave irradiation step, (e) a metal layer forming step may be further included. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.
在積層步驟之後進一步進行積層步驟之情況下,可以在上述曝光步驟之後,上述電磁波照射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,可以例示電漿處理。對表面活性化處理的詳細內容將進行後述。When the layering step is further performed after the layering step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned electromagnetic wave irradiation step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.
上述積層步驟進行2~20次為較佳,進行2~9次為更佳。 例如,如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層,將樹脂層設為2層以上且20層以下之構成為較佳,並且設為2層以上且9層以下之構成為進一步較佳。 上述各層的組成、形狀及膜厚等分別可以相同,亦可以不同。 Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.
在本發明中,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由硬化物形成之層之態樣為較佳。具體而言,可以舉出依次重複(a)膜形成步驟、(b)曝光步驟、(c)顯影步驟、(d)電磁波照射步驟(e)金屬層形成步驟之態樣或依次重複(a)膜形成步驟、(d)電磁波照射步驟、(e)金屬層形成步驟之態樣。藉由交替進行積層由硬化物形成之層之積層步驟和金屬層形成步驟,能夠交替積層由本發明的硬化物形成之層和金屬層。In the present invention, it is particularly preferable to form a layer formed of a cured product so as to cover the above-mentioned metal layer after the metal layer is provided. Specifically, (a) film forming step, (b) exposure step, (c) developing step, (d) electromagnetic wave irradiation step (e) metal layer forming step are sequentially repeated, or (a) A state of the film forming step, (d) the electromagnetic wave irradiation step, and (e) the metal layer forming step. By alternately performing the lamination step of laminating the layer formed of the cured product and the metal layer forming step, the layer formed of the cured product of the present invention and the metal layer can be alternately laminated.
(表面活性化處理步驟) 本發明的積層體的製造方法包括對上述金屬層及由硬化物形成之層的至少一部分進行表面活性化處理之表面活性化處理步驟為較佳。 表面活性化處理步驟通常在金屬層形成步驟之後進行,但是亦可以在上述顯影步驟之後,對由硬化物形成之層進行表面活性化處理步驟之後進行金屬層形成步驟。 關於表面活性化處理,可以僅對金屬層的至少一部分進行,亦可以僅對由硬化物形成之層的至少一部分進行,亦可以分別對金屬層及由硬化物形成之層這兩者的至少一部分進行。對金屬層的至少一部分進行表面活性化處理為較佳,對金屬層中在表面上形成由硬化物形成之層之區域的一部分或全部進行表面活性化處理為較佳。如此,藉由對金屬層的表面進行表面活性化處理,能夠提高與設置於其表面上之由硬化物形成之層的密接性。 又,對由硬化物形成之層的一部分或全部亦進行表面活性化處理為較佳。如此,藉由對由硬化物形成之層的表面進行表面活性化處理,能夠提高與設置於經表面活性化處理之表面上之金屬層和樹脂層的密接性。尤其,在進行負型顯影之情況等使由硬化物形成之層硬化之情況下,不易受到表面處理之損壞,從而容易提高密接性。 作為表面活性化處理,具體而言,選自各種原料氣體(氧氣、氫氣、氬氣、氮氣、氮氣/氫氣混合氣體、氬氣/氧氣混合氣體等)的電漿處理、電暈放電處理、基於CF 4/O 2、NF 3/O 2、SF 6、NF 3、NF 3/O 2之蝕刻處理、基於紫外線(UV)臭氧法之表面處理、浸漬於鹽酸水溶液中以去除氧化皮膜之後浸漬於包含具有至少1種胺基和硫醇基之化合物之有機表面處理劑中的浸漬處理、使用了刷子之機械粗面化處理,電漿處理為較佳,尤其使用氧氣作為原料氣體之氧氣電漿處理為較佳。在進行電暈放電處理之情況下,能量為500~200,000J/m 2為較佳,1000~100,000J/m 2為更佳,10,000~50,000J/m 2為最佳。 (Surface activation treatment step) It is preferable that the manufacturing method of the layered body of the present invention includes a surface activation treatment step of subjecting at least a part of the metal layer and the layer formed of the cured product to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step for the layer formed of the cured product after the above-mentioned development step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the layer formed of the hardened material, or may be performed on at least a part of both the metal layer and the layer formed of the hardened material. conduct. It is preferable to perform surface activation treatment on at least a part of the metal layer, and it is preferable to perform surface activation treatment on a part or the whole of the region of the metal layer where the layer formed of the hardened material is formed on the surface. In this way, by subjecting the surface of the metal layer to the surface activation treatment, the adhesion to the layer formed of the cured product provided on the surface can be improved. Moreover, it is preferable to also perform a surface activation process with respect to a part or all of the layer which consists of hardened|cured material. In this way, by subjecting the surface of the layer formed of the cured product to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activation treatment can be improved. In particular, when a layer formed of a cured product is hardened, such as in the case of performing negative development, it is less likely to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment, corona discharge treatment, corona discharge treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) Etching treatment of CF 4 /O 2 , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in Immersion treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma using oxygen as a raw material gas Handling is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , and most preferably 10,000-50,000 J/m 2 .
(半導體元件的製造方法) 本發明還揭示包括本發明的硬化物的製造方法或本發明的積層體的製造方法之半導體元件的製造方法。作為將本發明的硬化物的製造方法用於再配線層用層間絕緣膜的形成中之半導體元件的具體例,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,並將該等內容編入本說明書中。 (Manufacturing method of semiconductor element) The present invention also discloses a method for producing a semiconductor element including the method for producing the cured product of the present invention or the method for producing the laminate of the present invention. As a specific example of a semiconductor element in which the method for producing the cured product of the present invention is used in the formation of the interlayer insulating film for rewiring layers, reference can be made to the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the paragraphs of FIG. 1 . record, and incorporate these contents into this manual.
(感光性組成物) 感光性組成物為在本發明的硬化物的製造方法中之膜形成步驟中用於形成感光性膜之組成物。 感光性組成物包含硬化性樹脂為較佳,包含熱硬化性樹脂為更佳。 又,感光性組成物包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物、環氧樹脂及酚樹脂之群組中的至少1種樹脂(以下,亦稱為“特定樹脂”。)為較佳,包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物及聚醯胺醯亞胺前驅物之群組中的至少1種樹脂為更佳。 感光性組成物包含後述聚合性化合物為較佳。 又,感光性組成物包含後述光聚合起始劑或光酸產生劑為較佳。 以下,對感光性組成物中所包含之各成分的詳細內容進行說明。 (photosensitive composition) The photosensitive composition is a composition for forming a photosensitive film in the film forming step in the method for producing the cured product of the present invention. It is preferable that the photosensitive composition contains a curable resin, and it is more preferable that it contains a thermosetting resin. In addition, the photosensitive composition includes at least one resin ( Hereinafter, it is also referred to as "specific resin".) Preferably, at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyimide imide precursor is included. Resin is better. It is preferable that the photosensitive composition contains the polymerizable compound mentioned later. Moreover, it is preferable that the photosensitive composition contains a photopolymerization initiator or a photoacid generator described later. Hereinafter, the details of each component contained in the photosensitive composition will be described.
<特定樹脂> 感光性組成物包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物、環氧樹脂及酚樹脂之群組中的至少1種樹脂(“特定樹脂”)為較佳。 感光性組成物包含選自包括聚醯亞胺前驅物、聚苯并噁唑前驅物及聚醯胺醯亞胺前驅物之群組中的至少1種樹脂作為特定樹脂為較佳,包含聚醯亞胺前驅物作為特定樹脂為更佳。 又,特定樹脂具有聚合性基為較佳,包含自由基聚合性基為更佳。 尤其,在特定樹脂具有自由基聚合性基之情況下,感光性組成物包含後述自由基聚合起始劑為較佳,包含後述自由基聚合起始劑且包含後述自由基交聯劑為更佳。進而,依據需要,能夠包含後述敏化劑。由該種感光性組成物例如形成負型感光性膜。 又,特定樹脂可以具有酸分解性基等極性轉換基。 在特定樹脂具有酸分解性基之情況下,感光性組成物包含後述光酸產生劑為較佳。由該種感光性組成物例如形成作為化學增幅型之正型感光性膜或負型感光性膜。 <Specific resin> The photosensitive composition comprises at least one resin (“Specific resin") is preferred. The photosensitive composition preferably includes at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyimide imide precursors as the specific resin, including polyimide precursors. The imine precursor is more preferable as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. In particular, when the specific resin has a radically polymerizable group, it is preferable that the photosensitive composition contains a radical polymerization initiator described later, and it is more preferable that the photosensitive composition includes a radical polymerization initiator described later and a radical crosslinking agent described later. . Furthermore, the sensitizer mentioned later can be contained as needed. From such a photosensitive composition, for example, a negative photosensitive film is formed. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the photosensitive composition contains the photoacid generator mentioned later. From such a photosensitive composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.
〔聚醯亞胺前驅物〕 本發明中所使用之聚醯亞胺前驅物的其種類等並無特別規定,但是包含下述式(2)所表示之重複單元為較佳。 【化學式1】 式(2)中,A 1及A 2分別獨立地表示氧原子或-NH-,R 111表示2價的有機基,R 115表示4價的有機基,R 113及R 114分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 1] In formula (2), 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 hydrogen Atom or a monovalent organic group.
式(2)中之A 1及A 2分別獨立地表示氧原子或-NH-,氧原子為較佳。 式(2)中之R 111表示2價的有機基。作為2價的有機基,可以例示包含直鏈或支鏈的脂肪族基、環狀脂肪族基及芳香族基之基團,包括碳數2~20的直鏈或支鏈的脂肪族基、碳數3~20的環狀脂肪族基、碳數3~20的芳香族基或該等組合之基團為較佳,包含碳數6~20的芳香族基之基團為更佳。上述直鏈或支鏈的脂肪族基可以經鏈中的烴基包含雜原子之基團取代,並且上述環狀的脂肪族基及芳香族基可以經環員的烴基包含雜原子之基團取代。作為本發明的較佳的實施形態,可以例示-Ar-及-Ar-L-Ar-所表示之基團,特佳為-Ar-L-Ar-所表示之基團。其中,Ar分別獨立地為芳香族基,L為包括單鍵、可以經氟原子取代的碳數1~10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-或上述中的2個以上的組合之基團。該等較佳範圍如上所述。 A 1 and A 2 in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R 111 in formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond and may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.
R 111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,可以舉出直鏈或支鏈的脂肪族、環狀脂肪族或芳香族二胺等。二胺可以僅使用1種,亦可以使用2種以上。 具體而言,包含包括碳數2~20的直鏈或支鏈的脂肪族基、碳數3~20的環狀脂肪族基、碳數3~20的芳香族基或該等組合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。上述直鏈或支鏈的脂肪族基可以經鏈中的烴基包含雜原子之基團取代,並且上述環狀的脂肪族基及芳香族基可以經環員的烴基包含雜原子之基團取代。作為包含芳香族基之基團的例子,可以舉出下述。 Preferably R 111 is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, the group includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. The diamine is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.
【化學式2】 式中,A表示單鍵或2價的連接基,選自單鍵或可以經氟原子取代的碳數1~10的脂肪族烴基、-O-、-C(=O)-、-S-、-SO 2-、-NHCO-或該等組合中之基團為較佳,選自單鍵、可以經氟原子取代的碳數1~3的伸烷基、-O-、-C(=O)-、-S-或-SO 2-中之基團為更佳,-CH 2-、-O-、-S-、-SO 2-、-C(CF 3) 2-或-C(CH 3) 2-為進一步較佳。 式中,*表示與其他結構的鍵結部位。 [Chemical formula 2] In the formula, A represents a single bond or a divalent linking group, and is selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C(=O)-, and -S- which may be substituted by a fluorine atom. , -SO 2 -, -NHCO- or groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- or -SO 2 - is more preferred, -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - or -C ( CH 3 ) 2 - is further preferred. In the formula, * represents a bonding site with other structures.
作為二胺,具體而言,可以舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷及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’-二甲基環己基甲烷及異佛爾酮二胺;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’-二胺基二苯基甲烷及3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸及3,3-二胺基二苯基碸、4,4’-二胺基二苯醚及3,3’-二胺基二苯醚、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、3,3’-二甲氧基-4,4’-二胺基聯苯、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、2,4-二胺基枯烯及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、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、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’-二胺基四聯苯中的至少1種二胺。Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine 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'-di Methylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenylene and 3,3-diaminodiphenylene, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4 ,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 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-amine) phenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane 3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine bis[4-(4-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(2 -Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene -Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diamine Amino biphenyl, 9,9'-bis(4-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octa Methylpentasiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, bis Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminobenzene) base) octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 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(trifluoropropane) Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) diphenyl bismuth, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl bismuth, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least 1 of ,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl a diamine.
又,國際公開第2017/038598號的0030~0031段中所記載的二胺(DA-1)~(DA-18)亦較佳。Moreover, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.
又,亦可以較佳地使用在主鏈上具有國際公開第2017/038598號的0032~0034段中所記載的2個以上的伸烷基二醇單元之二胺。Moreover, the diamine which has two or more alkylene glycol units described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain can also be preferably used.
從所獲得之有機膜的柔軟性的觀點考慮,R 111由-Ar-L-Ar-表示為較佳。其中,Ar分別獨立地為芳香族基,L為包括可以經氟原子取代的碳數1~10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-或上述中的2個以上的組合之基團。Ar為伸苯基為較佳,L為可以經氟原子取代的碳數1或2的脂肪族烴基、-O-、-CO-、-S-或-SO 2-為較佳。此處的脂肪族烴基為伸烷基為較佳。 From the viewpoint of the flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO 2 - or -NHCO- which may be substituted by a fluorine atom. or a combination of two or more of the above. Preferably, Ar is a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO 2 - which may be substituted by a fluorine atom. The aliphatic hydrocarbon group here is preferably an alkylene group.
又,從i射線透射率的觀點考慮,R 111為下述式(51)或式(61)所表示之2價的有機基為較佳。尤其,從i射線透射率、易獲得性的觀點考慮,式(61)所表示之2價的有機基為更佳。 式(51) 【化學式3】 式(51)中,R 50~R 57分別獨立地為氫原子、氟原子或1價的有機基,R 50~R 57中的至少1個為氟原子、甲基或三氟甲基,*分別獨立地表示與式(2)中的氮原子的鍵結部位。 作為R 50~R 57的1價的有機基,可以舉出碳數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。 【化學式4】 式(61)中,R 58及R 59分別獨立地為氟原子、甲基或三氟甲基,*分別獨立地表示與式(2)中的氮原子的鍵結部位。 作為提供式(51)或式(61)的結構之二胺,可以舉出2,2’-二甲基聯苯胺、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。該等可以使用1種或組合使用2種以上。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R 111 is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 3] In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the formula (2). Examples of the monovalent organic groups of R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 6), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 4] In the formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in the formula (2). As the diamine which provides the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.
式(2)中之R 115表示4價的有機基。作為4價的有機基,包含芳香環之4價的有機基為較佳,下述式(5)或式(6)所表示之基團為更佳。式(5)或式(6)中,*分別獨立地表示與其他結構的鍵結部位。 【化學式5】 式(5)中,R 112為單鍵或2價的連接基,選自單鍵或可以經氟原子取代的碳數1~10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-及-NHCO-以及該等組合中之基團為較佳,選自單鍵、可以經氟原子取代的碳數1~3的伸烷基、-O-、-CO-、-S-及-SO 2-中之基團為更佳,選自包括-CH 2-、-C(CF 3) 2-、-C(CH 3) 2-、-O-、-CO-、-S-及-SO 2-之群組中的2價的基團為進一步較佳。 R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 5] In formula (5), R 112 is a single bond or a divalent linking group, selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, which may be substituted by a fluorine atom , -SO 2 - and -NHCO- and the groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO 2 - are more preferably selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, The divalent group in the group of -S- and -SO 2 - is more preferable.
關於R 115,具體而言,可以舉出從四羧酸二酐去除酐基之後所殘存之四羧酸殘基等。作為與R 115對應之結構,聚醯亞胺前驅物可以僅包含1種四羧酸二酐殘基,亦可以包含2種以上。 四羧酸二酐由下述式(O)表示為較佳。 【化學式6】 式(O)中,R 115表示4價的有機基。R 115的較佳範圍與式(2)中之R 115的含義相同,較佳範圍亦相同。 Specific examples of R 115 include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride. As a structure corresponding to R 115 , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 6] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.
作為四羧酸二酐的具體例,可以舉出均苯四甲酸二酐(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碳數1~6的烷基及碳數1~6的烷氧基衍生物。Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone 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'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic 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-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -Tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
又,亦可以舉出國際公開第2017/038598號的0038段中所記載的四羧酸二酐(DAA-1)~(DAA-5)作為較佳例。Moreover, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned as a preferable example.
式(2)中,R 111和R 115中的至少一者亦能夠具有OH基。更具體而言,作為R 111,可以舉出雙胺基苯酚衍生物的殘基。 In formula (2), at least one of R 111 and R 115 may also have an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
式(2)中之R 113及R 114分別獨立地表示氫原子或1價的有機基。作為1價的有機基,包含直鏈或支鏈的烷基、環狀烷基、芳香族基或聚伸烷氧基為較佳。又,R 113及R 114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。R 113及R 114中的至少一者包含2個以上的聚合性基亦較佳。作為聚合性基為能夠藉由熱、自由基等的作用而進行交聯反應的基團,自由基聚合性基為較佳。作為聚合性基的具體例,可以舉出具有乙烯性不飽和鍵之基團、烷氧基甲基、羥甲基、醯氧基甲基、環氧基、氧環丁烷基、苯并噁唑基、嵌段異氰酸酯基、胺基。作為聚醯亞胺前驅物所具有之自由基聚合性基,具有乙烯性不飽和鍵之基團為較佳。 作為具有乙烯性不飽和鍵之基團,可以舉出乙烯基、烯丙基、異烯丙基、2-甲基烯丙基、具有與乙烯基直接鍵結之芳香環之基團(例如,乙烯基苯基等)、(甲基)丙烯醯胺基、(甲基)丙烯醯氧基、下述式(III)所表示之基團等,下述式(III)所表示之基團為較佳。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkoxy group. Moreover, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, or the like, a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxane group. azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.
【化學式7】 [Chemical formula 7]
式(III)中,R 200表示氫原子、甲基、乙基或羥甲基,氫原子或甲基為較佳。 式(III)中,*表示與其他結構的鍵結部位。 式(III)中,R 201表示碳數2~12的伸烷基、-CH 2CH(OH)CH 2-、伸環烷基或聚伸烷氧基。 較佳的R 201的例子可以舉出伸乙基、伸丙基、三亞甲基、四亞甲基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基等伸烷基、1,2-丁二基、1,3-丁二基、-CH 2CH(OH)CH 2-、聚伸烷氧基,伸乙基、伸丙基等伸烷基、-CH 2CH(OH)CH 2-、環己基、聚伸烷氧基為更佳,伸乙基、伸丙基等伸烷基或聚伸烷氧基為進一步較佳。 在本發明中,聚伸烷氧基是指伸烷氧基直接鍵結2個以上之基團。聚伸烷氧基中所包含之複數個伸烷氧基中之伸烷基可以分別相同,亦可以不同。 在聚伸烷氧基包含伸烷基不同之複數種伸烷氧基之情況下,聚伸烷氧基中之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(在伸烷基具有取代基之情況下,包含取代基的碳數)為2以上為較佳,2~10為更佳,2~6為更佳,2~5為進一步較佳,2~4為更進一步較佳,2或3為特佳,2為最佳。 又,上述伸烷基可以具有取代基。作為較佳的取代基,可以舉出烷基、芳基、鹵素原子等。 又,聚伸烷氧基中所包含之伸烷氧基的數量(聚伸烷氧基的重複數)為2~20為較佳,2~10為更佳,2~6為進一步較佳。 作為聚伸烷氧基,從溶劑溶解性及耐溶劑性的觀點考慮,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而獲得之基團為較佳,聚乙烯氧基或聚伸丙氧基為更佳,聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個伸丙氧基鍵結而獲得之基團中,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。該等基團中之乙烯氧基等重複數個較佳態樣如上所述。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkeneoxy group. Preferred examples of R 201 include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and the like. base, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH(OH) CH 2 -, polyalkyleneoxy, ethylidene, propylidene and other alkylene groups, -CH 2 CH(OH)CH 2 -, cyclohexyl, and polyalkeneoxy groups are more preferred, and alkylene groups such as ethylidene and propylidene groups or polyalkeneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, it is preferable that the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group obtained by bonding two propeneoxy groups is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately, etc. patterned. Several preferred aspects such as vinyloxy in these groups are repeated as described above.
式(2)中,在R 113為氫原子之情況或在R 114為氫原子之情況下,聚醯亞胺前驅物可以與具有乙烯性不飽和鍵之三級胺化合物形成共軛鹼。作為該種具有乙烯性不飽和鍵之三級胺化合物的例子,可以舉出甲基丙烯酸N,N-二甲基胺基丙酯。 In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.
式(2)中,R 113及R 114中的至少一者可以為酸分解性基等極性轉換基。作為酸分解性基,只要為在酸的作用下分解而產生酚性羥基、羧基等鹼可溶性基者,則並無特別限定,但是縮醛基、縮酮基、甲矽烷基、甲矽烷基醚基、三級烷基酯基等為較佳,從曝光靈敏度的觀點考慮,縮醛基或縮酮基為更佳。 作為酸分解性基的具體例,可以舉出第三丁氧基羰基、異丙氧基羰基、四氫吡喃基、四氫呋喃基、乙氧基乙基、甲氧基乙基、乙氧基甲基、三甲基甲矽烷基、第三丁氧基羰基甲基、三甲基甲矽烷基醚基等。從曝光靈敏度的觀點考慮,乙氧基乙基或四氫呋喃基為較佳。 In formula (2), at least one of R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
又,聚醯亞胺前驅物在結構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,並且20質量%以下為較佳。Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
又,為了提高與基板的密接性,聚醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言,作為二胺,可以舉出使用雙(3-胺基丙基)四甲基二矽氧烷、雙(對胺基苯基)八甲基五矽氧烷等之態樣。Moreover, in order to improve the adhesiveness with a board|substrate, a polyimide precursor may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as the diamine, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.
式(2)所表示之重複單元為式(2-A)所表示之重複單元為較佳。亦即,本發明中所使用之聚醯亞胺前驅物中的至少1種為具有式(2-A)所表示之重複單元之前驅物為較佳。藉由使聚醯亞胺前驅物包含式(2-A)所表示之重複單元,能夠加大曝光寬容度的寬度。 式(2-A) 【化學式8】 式(2-A)中,A 1及A 2表示氧原子,R 111及R 112分別獨立地表示2價的有機基,R 113及R 114分別獨立地表示氫原子或1價的有機基,R 113及R 114中的至少一者為包含聚合性基之基團,兩者為包含聚合性基之基團為較佳。 Preferably, the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain the repeating unit represented by the formula (2-A), the width of the exposure latitude can be increased. Formula (2-A) [Chemical Formula 8] In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, At least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably a group containing a polymerizable group.
A 1、A 2、R 111、R 113及R 114分別獨立地與式(2)中之A 1、A 2、R 111、R 113及R 114的含義相同,較佳範圍亦相同。 R 112與式(5)中之R 112的含義相同,較佳範圍亦相同。 A 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meanings as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred ranges are also the same. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
聚醯亞胺前驅物可以包含1種式(2)所表示之重複單元,亦可以包含2種以上。又,亦可以包含式(2)所表示之重複單元的結構異構物。又,聚醯亞胺前驅物除了上述式(2)的重複單元以外,亦可以包含其他種類的重複單元,這是不言而喻的。The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).
作為本發明中之聚醯亞胺前驅物的一實施形態,可以舉出式(2)所表示之重複單元的含量為所有重複單元的50莫耳%以上之態樣。上述合計含量為70莫耳%以上為更佳,90莫耳%以上為進一步較佳,超過90莫耳%為特佳。上述合計含量的上限並無特別限定,除了末端以外的聚醯亞胺前驅物中之所有重複單元亦可以為式(2)所表示之重複單元。As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be repeating units represented by formula (2).
聚醯亞胺前驅物的重量平均分子量(Mw)較佳為5,000~100,000,更佳為10,000~50,000,進一步較佳為15,000~40,000。又,數量平均分子量(Mn)較佳為2,000~40,000,更佳為3,000~30,000,進一步較佳為4,000~20,000。 上述聚醯亞胺前驅物的分子量的分散度為1.5以上為較佳,1.8以上為更佳,2.0以上為進一步較佳。聚醯亞胺前驅物的分子量的分散度的上限值並無特別規定,例如為7.0以下為較佳,6.5以下為更佳,6.0以下為進一步較佳。 在本說明書中,分子量的分散度為利用重量平均分子量/數量平均分子量計算出之值。 又,在感光性組成物包含複數種聚醯亞胺前驅物作為特定樹脂之情況下,至少1種聚醯亞胺前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又,將上述複數種聚醯亞胺前驅物作為1個樹脂計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦較佳。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. In addition, when the photosensitive composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polyimide precursor are within the above-mentioned ranges. . Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.
〔聚苯并噁唑前驅物〕 關於本發明中所使用之聚苯并噁唑前驅物的其結構等,並無特別規定,但是較佳為包含下述式(3)所表示之重複單元。 【化學式9】 式(3)中,R 121表示2價的有機基,R 122表示4價的有機基,R 123及R 124分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] Although the structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 9] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
式(3)中,R 123及R 124分別與式(2)中之R 113的含義相同,較佳範圍亦相同。亦即,至少一者為聚合性基為較佳。 式(3)中,R 121表示2價的有機基。作為2價的有機基,包含脂肪族基及芳香族基中的至少一者之基團為較佳。作為脂肪族基,直鏈的脂肪族基為較佳。R 121為二羧酸殘基為較佳。二羧酸殘基可以僅使用1種,亦可以使用2種以上。 In formula (3), R 123 and R 124 have the same meanings as R 113 in formula (2), respectively, and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
作為二羧酸殘基,包含脂肪族基之二羧酸及包含芳香族基之二羧酸殘基為較佳,包含芳香族基之二羧酸殘基為更佳。 作為包含脂肪族基之二羧酸,包含直鏈或支鏈(較佳為直鏈)脂肪族基之二羧酸為較佳,包括直鏈或支鏈(較佳為直鏈)脂肪族基和2個-COOH之二羧酸為更佳。直鏈或支鏈(較佳為直鏈)的脂肪族基的碳數為2~30為較佳,2~25為更佳,3~20為進一步較佳,4~15為進一步較佳,5~10為特佳。直鏈的脂肪族基為伸烷基為較佳。 作為包含直鏈的脂肪族基之二羧酸,可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二正丁基丙二酸、丁二酸、四氟丁二酸、甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、二甲基甲基丁二酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸(diglycolic acid)以及下述式所表示之二羧酸等。 As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, including a linear or branched (preferably linear) aliphatic group and 2 -COOH dicarboxylic acids are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and further preferably 4 to 15, 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexanoic acid Fluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoroic acid Suberic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid , hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tridecanedioic acid acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacosanedioic acid, Tridecanedioic acid, tridecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.
【化學式10】 (式中,Z為碳數1~6的烴基,n為1~6的整數。) [Chemical formula 10] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)
作為包含芳香族基之二羧酸,以下具有芳香族基之二羧酸為較佳,以下僅包括具有芳香族基之基團和2個-COOH之二羧酸為更佳。As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acid having an aromatic group is preferred, and the following dicarboxylic acid including only a group having an aromatic group and two -COOH is more preferred.
【化學式11】 式中,A表示選自包括-CH 2-、-O-、-S-、-SO 2-、-CO-、-NHCO-、-C(CF 3) 2-及-C(CH 3) 2-的群組中之2價的基團,*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 11] In the formula, A represents selected from the group consisting of -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 - and -C(CH 3 ) 2 A divalent group in the group of -, * each independently represents a bonding site with other structures.
作為包含芳香族基之二羧酸的具體例,可以舉出4,4’-羰基二苯甲酸及4,4’-二羧基二苯醚、鄰苯二甲酸。Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.
式(3)中,R 122表示4價的有機基。作為4價的有機基,與上述式(2)中之R 115的含義相同,較佳範圍亦相同。 R 122為源自雙胺基苯酚衍生物之基團亦較佳,作為源自雙胺基苯酚衍生物之基團,例如可以舉出3,3’-二胺基-4,4’-二羥基聯苯、4,4’-二胺基-3,3’-二羥基聯苯、3,3’-二胺基-4,4’-二羥基二苯碸、4,4’-二胺基-3,3’-二羥基二苯碸、雙-(3-胺基-4-羥基苯基)甲烷、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、2,2-雙-(4-胺基-3-羥基苯基)六氟丙烷、雙-(4-胺基-3-羥基苯基)甲烷、2,2-雙-(4-胺基-3-羥基苯基)丙烷、4,4’-二胺基-3,3’-二羥基二苯甲酮、3,3’-二胺基-4,4’-二羥基二苯甲酮、4,4’-二胺基-3,3’-二羥基二苯醚、3,3’-二胺基-4,4’-二羥基二苯醚、1,4-二胺基-2,5-二羥基苯、1,3-二胺基-2,4-二羥基苯、1,3-二胺基-4,6-二羥基苯等。該等雙胺基苯酚可以單獨使用或者混合使用。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as that of R 115 in the above formula (2), and the preferred range is also the same. R 122 is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-diaminophenol. Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- 3-Hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 ,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.
在雙胺基苯酚衍生物中,下述具有芳香族基之雙胺基苯酚衍生物為較佳。Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.
【化學式12】 式中,X 1表示-O-、-S-、-C(CF 3) 2-、-CH 2-、-SO 2-、-NHCO-,*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基,氫原子或烴基為較佳,氫原子或烷基為更佳。又,R 122為上述式所表示之結構亦較佳。在R 122為上述式所表示之結構之情況下,在共計4個*及#中,任意2個為與式(3)中的R 122所鍵結之氮原子的鍵結部位且其他2個為與式(3)中的R 122所鍵結之氧原子的鍵結部位為較佳,2個*為與式(3)中的R 122所鍵結之氧原子的鍵結部位且2個#為與式(3)中的R 122所鍵結之氮原子的鍵結部位,或者2個*為與式(3)中的R 122所鍵結之氮原子的鍵結部位且2個#為與式(3)中的R 122所鍵結之氧原子的鍵結部位為更佳,2個*為與式(3)中的R 122所鍵結之氧原子的鍵結部位且2個#為與式(3)中的R 122所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 12] In the formula, X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Moreover, it is also preferable that R 122 is a structure represented by the above formula. In the case where R 122 is a structure represented by the above formula, among the total of 4 * and #, any two are the bonding site to the nitrogen atom to which R 122 in the formula (3) is bonded, and the other two are Preferably, it is the bonding site of the oxygen atom bonded to R 122 in the formula (3), and two * are the bonding sites of the oxygen atom bonded to R 122 in the formula (3), and 2 # is the bonding site with the nitrogen atom bonded to R 122 in the formula (3), or two * are the bonding sites with the nitrogen atom bonded with R 122 in the formula (3) and two # More preferably, it is the bonding site of the oxygen atom bonded to R 122 in the formula (3), and 2 * are the bonding sites of the oxygen atom bonded to R 122 in the formula (3), and 2 It is more preferable that # is the bonding site to the nitrogen atom bonded to R 122 in the formula (3).
雙胺基苯酚衍生物為式(A-s)所表示之化合物亦較佳。 【化學式13】 It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 13]
式(A-s)中,R 1為選自氫原子、伸烷基、取代伸烷基、-O-、-S-、-SO 2-、-CO-、-NHCO-、單鍵或下述式(A-sc)的群組中之有機基。R 2為氫原子、烷基、烷氧基、醯氧基、環狀烷基中的任一個,其可以相同亦可以不同。R 3為氫原子、直鏈或支鏈烷基、烷氧基、醯氧基、環狀烷基中的任一個,其可以相同亦可以不同。 In formula (As), R 1 is selected from hydrogen atom, alkylene group, substituted alkylene group, -O-, -S-, -SO 2 -, -CO-, -NHCO-, single bond or the following formula An organic group in the group of (A-sc). R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R 3 is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.
【化學式14】 (式(A-sc)中,*表示與上述式(A-s)所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。) [Chemical formula 14] (In the formula (A-sc), * represents a bond with the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)
上述式(A-s)中,認為在酚性羥基的鄰位亦即在R 3上亦具有取代基會使醯胺鍵的羰基碳與羥基的距離更靠近,在進一步提高在低溫下硬化時成為高環化率之效果之方面而言為特佳。 In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, also on R 3 will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it will be higher when hardening at a low temperature is further improved. It is particularly preferable in terms of the effect of the cyclization rate.
又,上述式(A-s)中,R 2為烷基且R 3為烷基時能夠維持對i射線的高透明性和在低溫下硬化時為高環化率之效果,因此為較佳。 In addition, in the above formula (As), when R 2 is an alkyl group and R 3 is an alkyl group, the effect of maintaining high transparency to i-rays and high cyclization rate during curing at low temperature is preferable.
又,上述式(A-s)中,R 1為伸烷基或取代伸烷基為進一步較佳。作為R 1之伸烷基及取代伸烷基的具體例,可以舉出碳數1~8的直鏈狀或支鏈狀烷基,其中,在一邊維持對i射線的高透明性和在低溫下硬化時為高環化率之效果一邊能夠獲得對溶劑具有充分的溶解性之平衡優異之聚苯并噁唑前驅物之方面而言,-CH 2-、-CH(CH 3)-、-C(CH 3) 2-為更佳。 In addition, in the above formula (As), it is more preferable that R 1 is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for R 1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, wherein high transparency to i-rays and low temperature are maintained while maintaining high transparency. -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - C(CH 3 ) 2 - is better.
作為上述式(A-s)所表示之雙胺基苯酚衍生物的製造方法,例如能夠參閱日本特開2013-256506號公報的0085~0094段及實施例1(0189~0190段),並將該等內容編入本說明書中。As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Laid-Open No. 2013-256506, and these The contents are incorporated into this manual.
作為上述式(A-s)所表示之雙胺基苯酚衍生物的結構的具體例,可以舉出日本特開2013-256506號公報的0070~0080段中所記載者,並將該等內容編入本說明書中。當然,並不限定於該等,這是不言而喻的。Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Laid-Open No. 2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these, it goes without saying.
除了上述式(3)的重複單元以外,聚苯并噁唑前驅物還可以包含其他種類的重複單元。 在能夠抑制伴隨閉環而產生翹曲之方面而言,聚苯并噁唑前驅物包含下述式(SL)所表示之二胺殘基作為其他種類的重複單元為較佳。 In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may contain other kinds of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in terms of suppressing the occurrence of warpage accompanying ring closure.
【化學式15】 式(SL)中,Z具有a結構和b結構,R 1s為氫原子或碳數1~10的烴基,R 2s為碳數1~10的烴基,R 3s、R 4s、R 5s、R 6s中的至少1個為芳香族基,其餘為氫原子或碳數1~30的有機基,其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合,亦可以為無規聚合。關於Z部分的莫耳%,a結構為5~95莫耳%、b結構為95~5莫耳%,a+b為100莫耳%。 [Chemical formula 15] In formula (SL), Z has a structure and b structure, R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R 2s is a hydrocarbon group with 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and a+b is 100 mol %.
式(SL)中,作為較佳的Z,可以舉出b結構中的R 5s及R 6s為苯基者。又,式(SL)所示之結構的分子量為400~4,000為較佳,500~3,000為更佳。藉由將上述分子量設在上述範圍內,能夠更有效地減小聚苯并噁唑前驅物在脫水閉環後的彈性模數,能夠兼顧能夠抑制翹曲之效果和提高溶劑溶解性之效果。 In the formula (SL), as preferable Z, those in which R 5s and R 6s in the structure b are phenyl groups can be mentioned. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.
在包含式(SL)所表示之二胺殘基作為其他種類的重複單元之情況下,進一步包含從四羧酸二酐中去除酐基之後殘存之四羧酸殘基作為重複單元亦較佳。作為該種四羧酸殘基的例子,可以舉出式(2)中的R 115的例子。 When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. Examples of such tetracarboxylic acid residues include R 115 in the formula (2).
聚苯并噁唑前驅物的重量平均分子量(Mw)例如較佳為18,000~30,000,更佳為20,000~29,000,進一步較佳為22,000~28,000。又,數量平均分子量(Mn)較佳為7,200~14,000,更佳為8,000~12,000,進一步較佳為9,200~11,200。 上述聚苯并噁唑前驅物的分子量的分散度為1.4以上為較佳,1.5以上為更佳,1.6以上為進一步較佳。聚苯并噁唑前驅物的分子量的分散度的上限值並無特別規定,例如2.6以下為較佳,2.5以下為更佳,2.4以下為進一步較佳,2.3以下為進一步較佳,2.2以下為更進一步較佳。 又,在感光性組成物包含複數種聚苯并噁唑前驅物作為特定樹脂之情況下,至少1種聚苯并噁唑前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又,將上述複數種聚苯并噁唑前驅物作為1個樹脂計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦較佳。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is further preferred, and 2.2 or less is preferred. for further better. Moreover, in the case where the photosensitive composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polybenzoxazole precursor are within the above ranges: better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.
〔聚醯胺醯亞胺前驅物〕 聚醯胺醯亞胺前驅物包含下述式(PAI-2)所表示之重複單元為較佳。 【化學式16】 式(PAI-2)中,R 117表示3價的有機基,R 111表示2價的有機基,A 2表示氧原子或-NH-,R 113表示氫原子或1價的有機基。 [Polyamide imide precursor] It is preferable that the polyamide imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 16] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.
式(PAI-2)中,R 117可以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、雜芳族基團或者單鍵或藉由連接基將該等連接2個以上而獲得之基團,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的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團為較佳,碳數6~20的芳香族基或者單鍵或藉由連接基將碳數6~20的芳香族基組合2個以上而獲得之基團為更佳。 作為上述連接基,-O-、-S-、-C(=O)-、-S(=O) 2-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為較佳,-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為更佳。 作為上述伸烷基,碳數1~20的伸烷基為較佳,碳數1~10的伸烷基為更佳,碳數1~4的伸烷基為進一步較佳。 作為上述鹵化伸烷基,碳數1~20的鹵化伸烷基為較佳,碳數1~10的鹵化伸烷基為更佳,碳數1~4的鹵化伸烷基為更佳。又,作為上述鹵化伸烷基中之鹵素原子,可以舉出氟原子、氯原子、溴原子、碘原子等,氟原子為較佳。上述鹵化伸烷基可以具有氫原子,亦可以使所有氫原子經鹵素原子取代,但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子,可以舉出(二三氟甲基)亞甲基等。 作為上述伸芳基,伸苯基或伸萘基為較佳,伸苯基為更佳,1,3-伸苯基或1,4-伸苯基為進一步較佳。 In the formula (PAI-2), R 117 can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.
又,R 117從至少1個羧基可以被鹵化的三羧酸化合物衍生為較佳。作為上述鹵化,氯化為較佳。 在本發明中,將具有3個羧基之化合物稱為三羧酸化合物。 上述三羧酸化合物的3個羧基中的2個羧基可以被酸酐化。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的三羧酸化合物,可以舉出支鏈狀的脂肪族、環狀的脂肪族或芳香族的三羧酸化合物等。 該等三羧酸化合物可以僅使用1種,亦可以使用2種以上。 Further, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two carboxyl groups among the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamide imide precursor, a branched aliphatic, cyclic, or aromatic tricarboxylic acid compound, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.
具體而言,作為三羧酸化合物,包含碳數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的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團之三羧酸化合物為較佳,包含碳數6~20的芳香族基或者單鍵或藉由連接基將碳數6~20的芳香族基組合2個以上而獲得之基團之三羧酸化合物為更佳。Specifically, the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, A tricarboxylic acid compound of an aromatic group having 6 to 20 carbon atoms, a single bond, or a group obtained by combining two or more of these through a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond is preferable. A bond or a tricarboxylic acid compound of a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group is more preferable.
又,作為三羧酸化合物的具體例,可以舉出藉由單鍵、-O-、-CH 2-、-C(CH 3) 2-、-C(CF 3) 2-、-SO 2-或伸苯基連接1,2,3-丙烷三羧酸、1,3,5-戊烷三羧酸、檸檬酸、偏苯三甲酸、2,3,6-萘三羧酸、鄰苯二甲酸(或者,鄰苯二甲酸酐)與苯甲酸之化合物等。 該等化合物可以為2個羧基被酐化之化合物(例如,偏苯三甲酸酐),亦可以為至少1個羧基被鹵化之化合物(例如,偏苯三酸酐醯氯)。 In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride ammonium chloride).
式(PAI-2)中,R 111、A 2、R 113分別與上述式(2)中之R 111、A 2、R 113的含義相同,較佳態樣亦相同。 In formula (PAI-2), R 111 , A 2 , and R 113 have the same meanings as R 111 , A 2 , and R 113 in the above formula (2), respectively, and the preferred embodiments are also the same.
聚醯胺醯亞胺前驅物可以進一步包含其他重複單元。 作為其他重複單元,可以舉出上述式(2)所表示之重複單元、下述式(PAI-1)所表示之重複單元等。 【化學式17】 The polyamidoimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [Chemical formula 17]
式(PAI-1)中,R 116表示2價的有機基,R 111表示2價的有機基。 式(PAI-1)中,R 116可以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、雜芳族基團或者單鍵或藉由連接基將該等連接2個以上而獲得之基團,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的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團為較佳,碳數6~20的芳香族基或者單鍵或藉由連接基將碳數6~20的芳香族基組合2個以上而獲得之基團為更佳。 作為上述連接基,-O-、-S-、-C(=O)-、-S(=O) 2-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為較佳,-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為更佳。 作為上述伸烷基,碳數1~20的伸烷基為較佳,碳數1~10的伸烷基為更佳,碳數1~4的伸烷基為進一步較佳。 作為上述鹵化伸烷基,碳數1~20的鹵化伸烷基為較佳,碳數1~10的鹵化伸烷基為更佳,碳數1~4的鹵化伸烷基為更佳。又,作為上述鹵化伸烷基中之鹵素原子,可以舉出氟原子、氯原子、溴原子、碘原子等,氟原子為較佳。上述鹵化伸烷基可以具有氫原子,亦可以使所有氫原子經鹵素原子取代,但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子,可以舉出(二三氟甲基)亞甲基等。 作為上述伸芳基,伸苯基或伸萘基為較佳,伸苯基為更佳,1,3-伸苯基或1,4-伸苯基為進一步較佳。 In formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In formula (PAI-1), R 116 can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.
又,R 116從二羧酸化合物或二羧酸二鹵化物衍生為較佳。 在本發明中,將具有2個羧基之化合物稱為二羧酸化合物,且將具有2個被鹵化之羧基之化合物稱為二羧酸二鹵化物。 二羧酸二鹵化物中之羧基只要被鹵化即可,例如被氯化為較佳。亦即,二羧酸二鹵化物為二羧酸二氯化物化合物為較佳。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的二羧酸化合物或二羧酸二鹵化物,可以舉出直鏈狀或支鏈狀的脂肪族、環狀的脂肪族或芳香族二羧酸化合物或二羧酸二鹵化物等。 該等二羧酸化合物或二羧酸二鹵化物可以僅使用1種,亦可以使用2種以上。 Further, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.
具體而言,作為二羧酸化合物或二羧酸二鹵化物,包含碳數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的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團之二羧酸化合物或二羧酸二鹵化物為較佳,包含碳數6~20的芳香族基或者單鍵或藉由連接基將碳數6~20的芳香族基組合2個以上而獲得之基團之二羧酸化合物或二羧酸二鹵化物為更佳。Specifically, the dicarboxylic acid compound or the dicarboxylic acid dihalide includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a A cyclic aliphatic group, an aromatic group having 6 to 20 carbon atoms, a single bond, or a dicarboxylic acid compound or a dicarboxylic acid dihalide of a group obtained by combining two or more of these groups by a linking group is relatively Preferably, a dicarboxylic acid compound or dicarboxylic acid dihalogenation containing an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms through a linking group Things are better.
又,作為二羧酸化合物的具體例,可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、4,4’-聯苯羧酸、4,4’-聯苯羧酸、4,4’-二羧基二苯醚、二苯甲酮-4,4’-二羧酸等。 作為二羧酸二鹵化物的具體例,可以舉出將上述二羧酸化合物的具體例中之2個羧基進行鹵化而形成之結構的化合物。 Further, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.
式(PAI-1)中,R 111與上述式(2)中之R 111的含義相同,較佳態樣亦相同。 In formula (PAI-1), R 111 has the same meaning as R 111 in the above formula (2), and the preferred aspects are also the same.
又,聚醯胺醯亞胺前驅物在結構中具有氟原子亦較佳。聚醯胺醯亞胺前驅物中的氟原子含量為10質量%以上為較佳,並且20質量%以下為較佳。Moreover, it is also preferable that the polyamide imide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
又,為了提高與基板的密接性,聚醯胺醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言,作為二胺成分,可以舉出使用雙(3-胺基丙基)四甲基二矽氧烷、雙(對胺基苯基)八甲基五矽氧烷等之態樣。Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure may be copolymerized with a polyamide imide precursor. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.
作為本發明中之聚醯胺醯亞胺前驅物的一實施形態,可以舉出式(PAI-2)所表示之重複單元、式(PAI-1)所表示之重複單元及式(2)所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量為70莫耳%以上為更佳,90莫耳%以上為進一步較佳,超過90莫耳%為特佳。上述合計含量的上限並無特別限定,除了末端以外的聚醯胺醯亞胺前驅物中之所有重複單元可以為式(PAI-2)所表示之重複單元、式(PAI-1)所表示之重複單元及式(2)所表示之重複單元中的任一個。 又,作為本發明中之聚醯胺醯亞胺前驅物的另一實施形態,可以舉出式(PAI-2)所表示之重複單元及式(PAI-1)所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量為70莫耳%以上為更佳,90莫耳%以上為進一步較佳,超過90莫耳%為特佳。上述合計含量的上限並無特別限定,除了末端以外的聚醯胺醯亞胺前驅物中之所有重複單元可以為式(PAI-2)所表示之重複單元或式(PAI-1)所表示之重複單元中的任一個。 As one embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) can be mentioned. The total content of the indicated repeating units is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamide imide precursor except the terminal may be repeating units represented by formula (PAI-2), and formula (PAI-1). Any one of the repeating unit and the repeating unit represented by formula (2). Moreover, as another embodiment of the polyamide imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned In the form of more than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal may be the repeating units represented by the formula (PAI-2) or the formula (PAI-1). Any of the repeating units.
聚醯胺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。 聚醯胺醯亞胺前驅物的分子量的分散度為1.5以上為較佳,1.8以上為更佳,2.0以上為進一步較佳。聚醯胺醯亞胺前驅物的分子量的分散度的上限值並無特別規定,例如為7.0以下為較佳,6.5以下為更佳,6.0以下為進一步較佳。又,在感光性組成物包含複數種聚醯胺醯亞胺前驅物作為特定樹脂之情況下,至少1種聚醯胺醯亞胺前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又,將上述複數種聚醯胺醯亞胺前驅物作為1個樹脂計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦較佳。 The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable. The molecular weight of the polyamide imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, when the photosensitive composition includes a plurality of polyamide imide precursors as the specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges Inside is better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imide precursors as one resin are respectively within the above ranges.
〔聚醯亞胺前驅物等的製造方法〕 聚醯亞胺前驅物等例如能夠利用如下方法而獲得:在低溫下使四羧酸二酐和二胺進行反應之方法、在低溫下使四羧酸二酐和二胺進行反應而獲得聚醯胺酸並使用縮合劑或烷化劑使其酯化之方法、藉由四羧酸二酐和醇而獲得二酯,之後在二胺和縮合劑的存在下使其進行反應之方法、藉由四羧酸二酐和醇而獲得二酯,之後使用鹵化劑使其餘的二羧酸鹵化,並使其與二胺進行反應之方法等。在上述製造方法中,藉由四羧酸二酐和醇而獲得二酯,之後使用鹵化劑使其餘的二羧酸鹵化,並使其與二胺進行反應之方法為更佳。 作為上述縮合劑,例如可以舉出二環己基碳二醯亞胺、二異丙基碳二醯亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰基二氧基-二-1,2,3-苯并***、N,N’-二琥珀醯亞胺基碳酸酯(Disuccinimidyl carbonate)、三氟乙酸酐等。 作為上述烷化劑,可以舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二烷基甲醯胺二烷基縮醛、原甲酸三甲酯、原甲酸三乙酯等。 作為上述鹵化劑,可以舉出硫醯氯、草醯氯、***等。 在聚醯亞胺前驅物等的製造方法中,在進行反應時,使用有機溶劑為較佳。有機溶劑可以為1種,亦可以為2種以上。 作為有機溶劑,能夠依據原料適當設定,但是可以例示吡啶、二乙二醇二甲醚(二甘二甲醚)、N-甲基吡咯啶酮、N-乙基吡咯啶酮、丙酸乙酯、二甲基乙醯胺、二甲基甲醯胺、四氫呋喃、γ-丁內酯等。 在聚醯亞胺前驅物等的製造方法中,在進行反應時,添加鹼性化合物為較佳。鹼性化合物可以為1種,亦可以為2種以上。 鹼性化合物能夠依據原料適當設定,但是可以例示三乙胺、二異丙基乙胺、吡啶、1,8-二氮雜雙環[5.4.0]十一碳-7-烯、N,N-二甲基-4-胺基吡啶等。 [Production method of polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide A method of esterifying an amine acid with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by A method in which tetracarboxylic dianhydride and alcohol are used to obtain a diester, and the remaining dicarboxylic acid is halogenated using a halogenating agent, followed by a method of reacting it with a diamine. In the above-mentioned production method, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated using a halogenating agent and reacted with a diamine is more preferable. As the above-mentioned condensing agent, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is performed. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. , dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine and the like.
-封端劑- 在聚醯亞胺前驅物等的製造方法中,為了進一步提高保存穩定性,密封殘存於聚醯亞胺前驅物等樹脂末端之羧酸酐、酸酐衍生物或胺基為較佳。在密封殘存於樹脂末端之羧酸酐及酸酐衍生物時,作為封端劑,可以舉出一元醇、酚、硫醇、苯硫酚、單胺等,從反應性、膜的穩定性的觀點考慮,使用一元醇、酚類或單胺為更佳。作為一元醇的較佳化合物,可以舉出甲醇、乙醇、丙醇、丁醇、己醇、辛醇、十二醇、苯甲醇、2-苯基乙醇、2-甲氧基乙醇、2-氯甲醇、糠醇等一級醇、異丙醇、2-丁醇、環己醇、環戊醇、1-甲氧基-2-丙醇等二級醇、第三丁醇、金剛烷醇等三級醇。作為酚類的較佳化合物,可以舉出酚、甲氧基酚、甲基酚、萘-1-醇、萘-2-醇、羥基苯乙烯等酚類等。又,作為單胺的較佳化合物,可以舉出苯胺、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺、5-胺基-8-羥基喹啉、1-羥基-7-胺基萘、1-羥基-6-胺基萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、1-羧基-7-胺基萘、1-羧基-6-胺基萘、1-羧基-5-胺基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基酚、3-胺基酚、4-胺基酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。該等可以使用2種以上,藉由使複數種封端劑進行反應,可以導入複數個不同之末端基。 又,在密封樹脂末端的胺基時,能夠用具有能夠與胺基進行反應的官能基之化合物進行密封。對胺基之較佳的密封劑為羧酸酐、羧酸氯化物、羧酸溴化物、磺酸氯化物、磺酸酐、磺酸羧酸酐等為較佳,羧酸酐、羧酸氯化物為更佳。作為羧酸酐的較佳化合物,可以舉出乙酸酐、丙酸酐、草酸酐、琥珀酸酐、順丁烯二酸酐、鄰苯二甲酸酐、苯甲酸酐、5-降莰烯-2,3-二羧酸酐等。又,作為羧酸氯化物的較佳化合物,可以舉出乙醯氯、丙烯醯氯、丙醯氯、甲基丙烯醯氯、三甲基乙醯氯、環己烷甲醯氯、2-乙基己醯氯、桂皮醯氯、1-金剛烷甲醯氯、七氟丁醯氯、硬脂酸醯氯、苯甲醯氯等。 -Capping agent- In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amine group remaining at the resin end of the polyimide precursor or the like. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin end, examples of the blocking agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, from the viewpoint of reactivity and film stability. , it is better to use monohydric alcohols, phenols or monoamines. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloroethanol Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6- aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7- aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminowater Sylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred sealants for amine groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., carboxylic acid anhydrides, carboxylic acid chlorides are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic acid anhydride, etc. In addition, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, trimethyl acetyl chloride, cyclohexane methyl chloride, 2-ethyl chloride can be mentioned. Hexyl chloride, cinnamon chloride, 1-adamantanecarboxy chloride, heptafluorobutane chloride, stearate chloride, benzyl chloride, etc.
-固體析出- 在製造聚醯亞胺前驅物等時,可以包括使固體析出之步驟。具體而言,依據需要過濾出在反應液中共存之脫水縮合劑的吸水副產物之後,向水、脂肪族低級醇或其混合液等的不良溶劑投入所獲得之聚合物成分,使聚合物成分析出以作為固體析出並使其乾燥,從而能夠獲得聚醯亞胺前驅物等。為了提高純化度,可以重複將聚醯亞胺前驅物等再溶解、再沉澱、乾燥等的操作。進而,可以包括使用離子交換樹脂來去除離子性雜質之步驟。 -Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof to make the polymer into a It is possible to obtain a polyimide precursor or the like by precipitation as a solid by analysis and drying. In order to improve the degree of purification, operations such as redissolving, reprecipitating, and drying the polyimide precursor and the like may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.
〔環氧樹脂〕 作為環氧樹脂,並無特別限定,但是可以舉出酚醛清漆型環氧樹脂、雙酚型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油醚型環氧樹脂、三酚甲烷型環氧樹脂、三酚丙烷型環氧樹脂、烷基改質三酚甲烷型環氧樹脂、含三𠯤核的環氧樹脂、二環戊二烯改質酚型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、具有伸苯基骨架及亞聯苯基骨架中的至少任一個之酚醛芳烷基型環氧樹脂、具有伸苯基骨架及亞聯苯基骨架中的至少任一個之萘酚芳烷基(naphthol aralkyl)型環氧樹脂等的芳烷基型環氧樹脂以及脂肪族環氧樹脂等。 又,在特定樹脂包含環氧樹脂之情況下,可以將後述聚合性化合物中所記載的環氧化合物用作特定樹脂。 [Epoxy resin] The epoxy resin is not particularly limited, and examples thereof include novolak-type epoxy resins, bisphenol-type epoxy resins, glycidylamine-type epoxy resins, glycidyl-ether-type epoxy resins, and trisphenolmethane-type epoxy resins. Resin, triphenol propane type epoxy resin, alkyl modified triphenol methane type epoxy resin, epoxy resin containing three nuclei, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin , Naphthalene type epoxy resin, novolac aralkyl type epoxy resin having at least any one of a phenylene skeleton and a biphenylene skeleton, and at least any one of a phenylene skeleton and a biphenylene skeleton Aralkyl-type epoxy resins such as naphthol aralkyl-type epoxy resins, aliphatic epoxy resins, and the like. Moreover, when a specific resin contains an epoxy resin, the epoxy compound described in the polymerizable compound mentioned later can be used as a specific resin.
〔酚樹脂〕 作為酚樹脂,例如可以舉出酚醛清漆樹脂或乙烯基聚合物等。 作為上述酚醛清漆樹脂,例如可以舉出在酸觸媒的存在下使酚類和醛類縮合而獲得者。作為上述酚類,例如可以舉出酚、甲酚、乙基酚、丁基酚、二甲酚、苯基酚、鄰苯二酚、間苯二酚、五倍子酚、萘酚或雙酚A等。 作為上述醛類,例如可以舉出甲醛、多聚甲醛、乙醛、丙醛或苯甲醛等。 上述酚類及醛類能夠單獨使用或組合使用2種以上。 作為上述酚醛清漆樹脂的具體例,例如可以舉出間甲酚、對甲酚或該等混合物與福馬林的縮合產物。 上述酚醛清漆樹脂可以使用分類等方法來調節分子量分佈。又,可以將具有雙酚C或雙酚A等酚系羥基之低分子量成分與上述酚醛清漆樹脂進行混合。 [Phenolic resin] As a phenol resin, a novolac resin, a vinyl polymer, etc. are mentioned, for example. As said novolak resin, the thing obtained by condensing phenols and aldehydes in the presence of an acid catalyst is mentioned, for example. Examples of the above-mentioned phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, gallic phenol, naphthol, and bisphenol A. . As said aldehyde, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, etc. are mentioned, for example. The above-mentioned phenols and aldehydes can be used alone or in combination of two or more. As a specific example of the said novolak resin, the condensation product of m-cresol, p-cresol, or these mixtures, and formalin is mentioned, for example. The molecular weight distribution of the above-mentioned novolak resin can be adjusted by methods such as classification. Moreover, the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, can be mixed with the said novolak resin.
〔含量〕 感光性組成物中之特定樹脂的含量相對於感光性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,50質量%以上為更進一步較佳。又,感光性組成物中之樹脂的含量相對於感光性組成物的總固體成分為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%以下為又更進一步較佳。 感光性組成物可以僅包含1種特定樹脂,亦可以包含2種以上。在包含2種以上之情況下,合計量在上述範圍內為較佳。 〔content〕 The content of the specific resin in the photosensitive composition is preferably 20 mass % or more, more preferably 30 mass % or more, more preferably 40 mass % or more, and 50 mass % or more with respect to the total solid content of the photosensitive composition for further better. In addition, the content of the resin in the photosensitive composition is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % with respect to the total solid content of the photosensitive composition. The following is still more preferable, and 95 mass % or less is still more preferable. The photosensitive composition may contain only 1 type of specific resin, or may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.
又,感光性組成物包含至少2種樹脂亦較佳。 具體而言,感光性組成物可以合計包含2種以上的特定樹脂和後述其他樹脂,亦可以包含2種以上的特定樹脂,但是包含2種以上的特定樹脂為較佳。 在感光性組成物包含2種以上的特定樹脂之情況下,例如包含為聚醯亞胺前驅物且源自二酐的結構(上述式(2)中所述之R 115)不同之2種以上的聚醯亞胺前驅物為較佳。 Moreover, it is also preferable that the photosensitive composition contains at least two kinds of resins. Specifically, the photosensitive composition may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the photosensitive composition contains two or more kinds of specific resins, for example, two or more kinds which are polyimide precursors and are derived from dianhydride-derived structures (R 115 described in the above formula (2)) are contained in two or more kinds The polyimide precursor is preferred.
<其他樹脂> 感光性組成物可以包含上述特定樹脂和與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,可以舉出包含聚醯胺、聚矽氧烷、矽氧烷結構之樹脂、(甲基)丙烯酸樹脂、(甲基)丙烯酸醯胺樹脂、胺甲酸乙酯樹脂、丁醛樹脂、苯乙烯樹脂、聚醚樹脂、聚酯樹脂等。 例如,藉由進一步加入(甲基)丙烯酸樹脂,可以獲得塗佈性優異之感光性組成物,並且可以獲得耐溶劑性優異之圖案(硬化物)。 例如,代替後述聚合性化合物或除了後述聚合性化合物以外,將重量平均分子量為20,000以下的聚合性基值高的(例如,樹脂1g中之聚合性基的含有莫耳量為1×10 -3莫耳/g以上)(甲基)丙烯酸樹脂添加至感光性組成物中,從而能夠提高感光性組成物的塗佈性、圖案(硬化物)的耐溶劑性等。 <Other resins> The photosensitive composition may contain the above-mentioned specific resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include polyamides, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, urethane resins, butyral resins, Styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a photosensitive composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 -3 ) molar/g or more) (meth)acrylic resin is added to the photosensitive composition, whereby the coatability of the photosensitive composition, the solvent resistance of the pattern (hardened product), and the like can be improved.
在感光性組成物包含其他樹脂之情況下,其他樹脂的含量相對於感光性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%以上為又更進一步較佳,10質量%以上為再更進一步較佳。 又,感光性組成物中之其他樹脂的含量相對於感光性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%以下為又更進一步較佳。 又,作為感光性組成物的較佳的一態樣,亦能夠設為其他樹脂的含量為低含量之態樣。在上述態樣中,其他樹脂的含量相對於感光性組成物的總固體成分為20質量%以下為較佳,15質量%以下為更佳,10質量%以下為進一步較佳,5量%以下為更進一步較佳,1質量%以下為又更進一步較佳。上述含量的下限並無特別限定,只要為0質量%以上即可。 感光性組成物可以僅包含1種其他樹脂,亦可以包含2種以上。在包含2種以上之情況下,合計量在上述範圍內為較佳。 When the photosensitive composition contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 1% by mass or more with respect to the total solid content of the photosensitive composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. The content of other resins in the photosensitive composition is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, and 60% by mass or less with respect to the total solid content of the photosensitive composition. % or less is still more preferable, and 50 mass % or less is still more preferable. Moreover, as a preferable aspect of a photosensitive composition, the aspect which content of other resin is low content can also be used. In the above aspect, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, and 5% by mass or less with respect to the total solid content of the photosensitive composition. For still more preferable, 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The photosensitive composition may contain only 1 type of other resin, or may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.
<聚合性化合物> 感光性組成物包含聚合性化合物為較佳。 又,感光性組成物包含2官能以上的聚合性化合物為較佳,包含3官能以上的聚合性化合物亦為較佳態樣之一。 作為聚合性化合物,可以舉出自由基交聯劑或其他交聯劑。 <Polymerizable compound> It is preferable that the photosensitive composition contains a polymerizable compound. Moreover, it is preferable that the photosensitive composition contains a bifunctional or more polymerizable compound, and it is also one of preferable aspects that a trifunctional or more polymerizable compound is contained. As a polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned.
〔自由基交聯劑〕 感光性組成物包含自由基交聯劑為較佳。 自由基交聯劑為具有自由基聚合性基之化合物。作為自由基聚合性基,包含乙烯性不飽和鍵之基團為較佳。作為上述包含乙烯性不飽和鍵之基團,可以舉出乙烯基、烯丙基、乙烯基苯基、(甲基)丙烯醯基、順丁烯二醯亞胺基、(甲基)丙烯醯胺基等具有乙烯性不飽和鍵之基團。 在該等之中,作為上述包含乙烯性不飽和鍵之基團,(甲基)丙烯醯基、(甲基)丙烯醯胺基、乙烯基苯基為較佳,從反應性的觀點考慮,(甲基)丙烯醯基為更佳。 [Radical crosslinking agent] It is preferable that the photosensitive composition contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloyl. Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.
自由基交聯劑為具有1個以上的乙烯性不飽和鍵之化合物為較佳,但是具有2個以上之化合物為更佳。自由基交聯劑可以具有3個以上的乙烯性不飽和鍵。 作為上述具有2個以上的乙烯性不飽和鍵之化合物,具有2~15個乙烯性不飽和鍵之化合物為較佳,具有2~10個乙烯性不飽和鍵之化合物為更佳,具有2~6個之化合物為進一步較佳。 又,從所獲得之圖案(硬化物)的膜強度的觀點考慮,感光性組成物包含具有2個乙烯性不飽和鍵之化合物和上述具有3個以上的乙烯性不飽和鍵之化合物亦較佳。 The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the photosensitive composition contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. .
自由基交聯劑的分子量為2,000以下為較佳,1,500以下為更佳,900以下為進一步較佳。自由基交聯劑的分子量的下限為100以上為較佳。The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
作為自由基交聯劑的具體例,可以舉出不飽和羧酸(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,亦可以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多官能醇類、胺類、硫醇類的取代反應物亦較佳。又,作為另一例,亦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來代替上述不飽和羧酸。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,並將該等內容編入本說明書中。Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used, Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.
又,自由基交聯劑為在常壓下具有100℃以上的沸點之化合物亦較佳。作為其例,可以舉出聚乙二醇二(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、己二醇二(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)丙烯酸酯化而獲得之化合物、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丙烯酸酯或甲基丙烯酸酯及該等混合物。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,亦可以舉出使(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進行反應而獲得之多官能(甲基)丙烯酸酯等。Moreover, it is also preferable that the radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris (acryloyloxypropyl) ether, tris (acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane etc. Compounds obtained by adding ethylene oxide or propylene oxide to alcohol followed by (meth)acrylic esterification, such as Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication Sho 51 - Urethane (meth)acrylates described in each publication of No. 037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490 Polyester acrylates, polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, or methacrylates, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.
又,作為除了上述以外的較佳的自由基交聯劑物,亦能夠使用日本特開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2個以上的含有乙烯性不飽和鍵之基團之化合物或卡多(cardo)樹脂。Moreover, as preferable radical crosslinking agent substances other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. A compound having a perylene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo resin.
進而,作為其他例,亦可以舉出日本特公昭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,亦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之化合物。進而,亦能夠使用在“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, the specific unsaturated compounds described in JP 46-043946 A, JP 01-040337 A, JP 01-040336 A, or JP 02 - Vinylphosphonic acid-based compounds and the like described in Gazette 025493. Moreover, the compound containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300 to 308 (1984) can also be used.
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,並將該等內容編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the etc. are incorporated into this manual.
又,在日本特開平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交聯劑,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)丙烯酸酯化而獲得之化合物。In addition, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds, which are described as formula (1) and formula (2) together with specific examples thereof, can also be used as a radical crosslinking agent in a polyfunctional alcohol. A compound obtained by adding ethylene oxide or propylene oxide and then (meth)acrylated.
進而,亦能夠使用日本特開2015-187211號公報的0104~0131段中所記載的化合物作為自由基交聯劑,並將該等內容編入本說明書中。Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radical crosslinking agent, and these contents are incorporated in the present specification.
作為自由基交聯劑,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(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。亦能夠使用該等寡聚物類型。As a radical crosslinking agent, dipeotaerythritol triacrylate (a commercial product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipeotaerythritol tetraacrylate (a commercial product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipivaloerythritol penta(meth)acrylate (commercially available as KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.
作為自由基交聯劑的市售品,例如可以舉出Sartomer Company, Inc製的作為具有4個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有4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6個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有3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。Commercially available products of the radical crosslinking agent include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 TPA-330 of trifunctional acrylate of isobutyloxy 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.
作為自由基交聯劑,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,作為自由基交聯劑,亦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 the radical crosslinking agent, for example, carbamic acid described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Ethyl acrylates, those described in 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 ethylene oxide. Urethane compounds of the skeleton are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.
自由基交聯劑可以為具有羧基、磷酸基等酸基之自由基交聯劑。具有酸基之自由基交聯劑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進行反應而具有酸基之自由基交聯劑為更佳。特佳為在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進行反應而具有酸基之自由基交聯劑中,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.製的多元酸改質丙烯酸類寡聚物,可以舉出M-510、M-520等。The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example.
具有酸基之自由基交聯劑的較佳酸值為0.1~300mgKOH/g,特佳為1~100mgKOH/g。只要自由基交聯劑的酸值在上述範圍內,則製造上的操作性優異,進而顯影性優異。又,聚合性良好。關於上述酸值,依據JIS K 0070:1992的記載來測定。The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.
從圖案的解析性和膜的伸縮性的觀點考慮,感光性組成物使用2官能的甲基丙烯酸酯或丙烯酸酯為較佳。 作為具體的化合物,能夠使用三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、PEG(聚乙二醇)200二丙烯酸酯、PEG200二甲基丙烯酸酯、PEG600二丙烯酸酯、PEG600二甲基丙烯酸酯、聚四乙二醇二丙烯酸酯、聚四乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、3-甲基-1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6己二醇二甲基丙烯酸酯、二羥甲基三環癸烷二丙烯酸酯、二羥甲基三環癸烷二甲基丙烯酸酯、雙酚A的EO(環氧乙烷)加成物二丙烯酸酯、雙酚A的EO加成物二甲基丙烯酸酯、雙酚A的PO(環氧丙烷)加成物二丙烯酸酯、雙酚A的PO加成物二甲基丙烯酸酯、2羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、異三聚氰酸EO改質二丙烯酸酯、異三聚氰酸改質二甲基丙烯酸酯、具有其他胺甲酸乙酯鍵之2官能丙烯酸酯、具有胺甲酸乙酯鍵之2官能甲基丙烯酸酯。該等依據需要能夠混合使用2種以上。 再者,例如PEG200二丙烯酸酯是指為聚乙二醇二丙烯酸酯且聚乙二醇鏈的式量為200左右者。 關於感光性組成物,從伴隨圖案(硬化物)的彈性模數控制而抑制翹曲的觀點考慮,能夠較佳地使用單官能自由基交聯劑作為自由基交聯劑。作為單官能自由基交聯劑,可以較佳地使用正丁基(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、環氧丙基(甲基)丙烯酸酯、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、烯基環氧丙醚等。作為單官能自由基交聯劑,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。 除此以外,作為2官能以上的自由基交聯劑,可以舉出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。 From the viewpoints of pattern analysis properties and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate as the photosensitive composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bond, with urethane bond The 2-functional methacrylate. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the photosensitive composition, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (cured product). As the monofunctional radical crosslinking agent, 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 derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable. In addition, as a bifunctional or more than bifunctional radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.
在含有自由基交聯劑之情況下,其含量相對於感光性組成物的總固體成分超過0質量%且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。When a radical crosslinking agent is contained, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of a photosensitive composition. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.
自由基交聯劑可以單獨使用1種,亦可以混合使用2種以上。在同時使用2種以上之情況下,其合計量在上述範圍內為較佳。A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount is in the said range.
〔其他交聯劑〕 感光性組成物包含與上述自由基交聯劑不同之其他交聯劑亦較佳。 在本發明中,其他交聯劑是指除了上述自由基交聯劑以外的交聯劑,在分子內具有複數個藉由上述光酸產生劑或光鹼產生劑的感光而促進在與組成物中的其他化合物或其反應產物之間形成共價鍵之反應之基團之化合物為較佳,在分子內具有複數個藉由酸或鹼的作用而促進在與組成物中的其他化合物或其反應產物之間形成共價鍵之反應之基團之化合物為較佳。 上述酸或鹼為在曝光步驟中從光酸產生劑或光鹼產生劑產生之酸或鹼為較佳。 作為其他交聯劑,具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中的至少1種基團之化合物為較佳,具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中的至少1種基團與氮原子直接鍵結之結構之化合物為更佳。 作為其他交聯劑,例如可以舉出具有使甲醛或甲醛和醇與三聚氰胺、甘脲、脲、伸烷基脲、苯并胍胺等含有胺基之化合物進行反應而經醯氧基甲基、羥甲基或烷氧基甲基取代上述胺基的氫原子之結構之化合物。該等化合物的製造方法並無特別限定,只要為具有與藉由上述方法製造的化合物相同之結構之化合物即可。又,亦可以為該等化合物的羥甲基彼此自縮合而成之寡聚物。 將作為上述含有胺基之化合物而使用了三聚氰胺之交聯劑稱為三聚氰胺系交聯劑,將使用了甘脲、脲或伸烷基脲之交聯劑稱為脲系交聯劑,將使用了伸烷基脲之交聯劑稱為伸烷基脲系交聯劑,將使用了苯并胍胺之交聯劑稱為苯并胍胺系交聯劑。 在該等之中,感光性組成物包含選自包括脲系交聯劑及三聚氰胺系交聯劑之群組中的至少1種化合物為較佳,包含選自包括後述甘脲系交聯劑及三聚氰胺系交聯劑之群組中的至少1種化合物為更佳。 [Other cross-linking agents] It is also preferable that the photosensitive composition contains another crosslinking agent different from the above-mentioned radical crosslinking agent. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and has a plurality of crosslinking agents in the molecule, which are promoted by the above-mentioned photoacid generator or photobase generator to facilitate interaction with the composition. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the photosensitive composition contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and the photosensitive composition preferably contains at least one compound selected from the group consisting of the glycoluril-based crosslinking agent described below and At least one compound in the group of the melamine-based crosslinking agent is more preferable.
作為含有本發明中之烷氧基甲基及醯氧基甲基中的至少1個之化合物,可以舉出烷氧基甲基或醯氧基甲基直接在芳香族基或下述脲結構的氮原子上或三𠯤上取代之化合物作為結構例。 上述化合物所具有之烷氧基甲基或醯氧基甲基為碳數2~5為較佳,碳數2或3為較佳,碳數2為更佳。 上述化合物所具有之烷氧基甲基及醯氧基甲基的總數為1~10為較佳,更佳為2~8,特佳為3~6。 上述化合物的分子量較佳為1500以下,180~1200為較佳。 As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group directly in the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trisium are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.
【化學式18】 [Chemical formula 18]
R 100表示烷基或醯基。 R 101及R 102分別獨立地表示1價的有機基,並且可以相互鍵結而形成環。 R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.
作為烷氧基甲基或醯氧基甲基直接在芳香族基上取代之化合物,例如可以舉出下述通式的各種化合物。Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include various compounds of the following general formula.
【化學式19】 [Chemical formula 19]
式中,X表示單鍵或2價的有機基,每個R 104分別獨立地表示烷基或醯基,R 103表示氫原子、烷基、烯基、芳基、芳烷基或藉由酸的作用進行分解而產生鹼可溶性基之基團(例如,藉由酸的作用進行脫離之基團、-C(R 4) 2COOR 5所表示之基團(R 4分別獨立地表示氫原子或碳數1~4的烷基,R 5表示藉由酸的作用進行脫離之基團。))。 R 105各自獨立地表示烷基或烯基,a、b及c各自獨立地為1~3,d為0~4,e為0~3,f為0~3,a+d為5以下,b+e為4以下,c+f為4以下。 關於藉由酸的作用進行分解而產生鹼可溶性基之基團、藉由酸的作用進行脫離之基團、-C(R 4) 2COOR 5所表示之基團中之R 5,例如可以舉出-C(R 36)(R 37)(R 38)、-C(R 36)(R 37)(OR 39)、-C(R 01)(R 02)(OR 39)等。 式中,R 36~R 39分別獨立地表示烷基、環烷基、芳基、芳烷基或烯基。R 36與R 37可以相互鍵結而形成環。 作為上述烷基,碳數1~10的烷基為較佳,碳數1~5的烷基為更佳。 上述烷基可以為直鏈狀、支鏈狀中的任一個。 作為上述環烷基,碳數3~12的環烷基為較佳,碳數3~8的環烷基為更佳。 上述環烷基可以為單環結構,亦可以為縮合環等多環結構。 上述芳基為碳數6~30的芳香族烴基為較佳,苯基為更佳。 作為上述芳烷基,碳數7~20的芳烷基為較佳,碳數7~16的芳烷基為更佳。 上述芳烷基是指經烷基取代之芳基,該等烷基及芳基的較佳態樣與上述烷基及芳基的較佳態樣相同。 上述烯基為碳數3~20的烯基為較佳,碳數3~16的烯基為更佳。 又,該等基團在可以獲得本發明的效果之範圍內還可以具有公知的取代基。 In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R 4 ) 2 COOR 5 (R 4 independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R 5 represents a group that can be removed by the action of an acid.)). R 105 each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R 5 in the group represented by -C(R 4 ) 2 COOR 5 include a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is released by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 . Out-C(R 36 )(R 37 )(R 38 ),-C(R 36 )(R 37 )(OR 39 ),-C(R 01 )(R 02 )(OR 39 ), etc. In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may have a well-known substituent within the range which can obtain the effect of this invention.
R 01及R 02分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基或烯基。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
作為該等基團,較佳為三級烷基酯基、縮醛酯基、枯基酯基、烯醇酯基等。進一步較佳為三級烷基酯基、縮醛酯基。As these groups, a tertiary alkyl ester group, an acetal ester group, a cumyl ester group, an enol ester group, and the like are preferable. Further preferred are tertiary alkyl ester groups and acetal ester groups.
作為具有烷氧基甲基之化合物,具體而言,可以舉出以下結構。關於具有醯氧基甲基之化合物,可以舉出將下述化合物的烷氧基甲基變更為醯氧基甲基之化合物。作為在分子內具有烷氧基甲基或醯氧基甲基之化合物,可以舉出以下各種化合物,但是並不限定於該等。As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an acyloxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an acyloxymethyl group is mentioned. As a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, the following various compounds are mentioned, However, It is not limited to these.
【化學式20】 [Chemical formula 20]
【化學式21】 [Chemical formula 21]
關於含有烷氧基甲基及醯氧基甲基中的至少1個之化合物,可以使用市售者,亦可以使用藉由公知的方法合成者。 從耐熱性的觀點考慮,烷氧基甲基或醯氧基甲基直接在芳香環或三𠯤環上取代之化合物為較佳。 As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is preferable.
作為三聚氰胺系交聯劑的具體例,可以舉出六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲基三聚氰胺、六丁氧基丁基三聚氰胺等。Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.
作為脲系交聯劑的具體例,例如可以舉出單羥甲基化甘脲、二羥甲基化甘脲、三羥甲基化甘脲、四羥甲基化甘脲、單甲氧基甲基化甘脲,二甲氧基甲基化甘脲、三甲氧基甲基化甘脲、四甲氧基甲基化甘脲、單甲氧基甲基化甘脲、二甲氧基甲基化甘脲、三甲氧基甲基化甘脲、四乙氧基甲基化甘脲、單丙氧基甲基化甘脲、二丙氧基甲基化甘脲、三丙氧基甲基化甘脲、四丙氧基甲基化甘脲、單丁氧基甲基化甘脲、二丁氧基甲基化甘脲、三丁氧基甲基化甘脲或四丁氧基甲基化甘脲等甘脲系交聯劑; 雙甲氧基甲基脲、雙乙氧基甲基脲、雙丙氧基甲基脲、雙丁氧基甲基脲等脲系交聯劑、 單羥甲基化伸乙脲或二羥甲基化伸乙脲、單甲氧基甲基化伸乙脲、二甲氧基甲基化伸乙脲、單乙氧基甲基化伸乙脲、二乙氧基甲基化伸乙脲、單丙氧基甲基化伸乙脲、二丙氧基甲基化伸乙脲、單丁氧基甲基化伸乙脲或二丁氧基甲基化伸乙脲等伸乙脲系交聯劑、 單羥甲基化伸丙脲、二羥甲基化伸丙脲、單甲氧基甲基化伸丙脲、二甲氧基甲基化伸丙脲、單乙氧基甲基化伸丙脲、二乙氧基甲基化伸丙脲、單丙氧基甲基化伸丙脲、二丙氧基甲基化伸丙脲、單丁氧基甲基化伸丙脲或二丁氧基甲基化伸丙脲等伸丙脲系交聯劑、 1,3-二(甲氧基甲基)4,5-二羥基-2-咪唑啶酮、1,3-二(甲氧基甲基)-4,5-二甲氧基-2-咪唑啶酮等。 Specific examples of the urea-based crosslinking agent include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril Methylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril and other glycoluril-based cross-linking agents; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents, Monomethylolated Propylene Urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.
作為苯并胍胺系交聯劑的具體例,例如可以舉出單羥甲基化苯并胍胺、二羥甲基化苯并胍胺、三羥甲基化苯并胍胺、四羥甲基化苯并胍胺、單甲氧基甲基化苯并胍胺、二甲氧基甲基化苯并胍胺、三甲氧基甲基化苯并胍胺、四甲氧基甲基化苯并胍胺、單甲氧基甲基化苯并胍胺、二甲氧基甲基化苯并胍胺、三甲氧基甲基化苯并胍胺、四乙氧基甲基化苯并胍胺、單丙氧基甲基化苯并胍胺、二丙氧基甲基化苯并胍胺、三丙氧基甲基化苯并胍胺、四丙氧基甲基化苯并胍胺、單丁氧基甲基化苯并胍胺、二丁氧基甲基化苯并胍胺、三丁氧基甲基化苯并胍胺、四丁氧基甲基化苯并胍胺等。Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine , monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, mono Butoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
除此以外,作為具有選自包括羥甲基及烷氧基甲基之群組中的至少1種基團之化合物,亦可以較佳地使用在芳香環(較佳為苯環)上直接鍵結有選自包括羥甲基及烷氧基甲基之群組中的至少1種基團之化合物。 作為該種化合物的具體例,可以舉出苯二甲醇、雙(羥甲基)甲酚、雙(羥甲基)二甲氧基苯、雙(羥甲基)二苯醚、雙(羥甲基)二苯甲酮、羥甲基苯甲酸羥甲基苯酯、雙(羥甲基)聯苯、二甲基雙(羥甲基)聯苯、雙(甲氧基甲基)苯、雙(甲氧基甲基)甲酚、雙(甲氧基甲基)二甲氧基苯、雙(甲氧基甲基)二苯醚、雙(甲氧基甲基)二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯酯、雙(甲氧基甲基)聯苯、二甲基雙(甲氧基甲基)聯苯、4,4’,4’’-亞乙基三[2,6-雙(甲氧基甲基)苯酚]、5,5’-[2,2,2‐三氟‐1‐(三氟甲基)亞乙基]雙[2‐羥基‐1,3‐苯二甲醇]、3,3’,5,5’-四(甲氧基甲基)-1,1’-聯苯-4,4’-二醇等。 In addition, as a compound having at least one group selected from the group consisting of methylol and alkoxymethyl, a direct bond on an aromatic ring (preferably a benzene ring) can also be preferably used A compound having at least one group selected from the group consisting of methylol and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.
作為其他交聯劑,亦可以使用市售品,作為較佳的市售品,可以舉出46DMOC、46DMOEP(以上為ASAHI YUKIZAI CORPORATION製)、DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DMLBisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP(以上為Honshu Chemical Industry Co.,Ltd.製)、NIKARAC(註冊商標,以下相同)MX-290、NIKARAC MX-280、NIKARAC MX-270、NIKARAC MX-279、NIKARAC MW-100LM、NIKARAC MX-750LM(以上為Sanwa Chemical Co.,Ltd.製)等。Commercially available products can also be used as other crosslinking agents, and preferred commercialized products include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML- OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML- BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (the above are Sanwa Chemical Co., Ltd.) and the like.
又,感光性組成物包含選自包括環氧化合物、氧環丁烷化合物及苯并噁𠯤化合物之群組中的至少1種化合物作為其他交聯劑亦較佳。Moreover, it is also preferable that the photosensitive composition contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.
-環氧化合物(具有環氧基之化合物)- 作為環氧化合物,在一分子中具有2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,並且不會產生由交聯引起之脫水反應,因此不易引起膜收縮。因此,含有環氧化合物對抑制感光性組成物的低溫硬化及翹曲係有效的。 -Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature curing and warpage of the photosensitive composition.
環氧化合物含有聚環氧乙烷基為較佳。藉此,彈性模數進一步下降,並且能夠抑制翹曲。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 elastic modulus is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
作為環氧化合物的例子,可以舉出雙酚A型環氧樹脂;雙酚F型環氧樹脂;丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、乙二醇二縮水甘油醚、丁二醇二縮水甘油醚、六亞甲基二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚等伸烷基二醇型環氧樹脂或多元醇烴型環氧樹脂;聚丙二醇二縮水甘油醚等聚伸烷基二醇型環氧樹脂;聚甲基(縮水甘油氧基丙基)矽氧烷等環氧環氧基之矽酮等,但是並不限定於該等。具體而言,可以舉出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)HP-4770、EPICLON(註冊商標)EXA-830LVP、EPICLON(註冊商標)EXA-8183、EPICLON(註冊商標)EXA-8169、EPICLON(註冊商標)N-660、EPICLON(註冊商標)N-665-EXP-S、EPICLON(註冊商標)N-740(以上為產品名稱,DIC CORPORATION製)、Rika Resin(註冊商標)BEO-20E、Rika Resin(註冊商標)BEO-60E、Rika Resin(註冊商標)HBE-100、Rika Resin(註冊商標)DME-100、Rika Resin(註冊商標)L-200(產品名稱,New Japan Chemical Co.,Ltd.)、EP-4003S、EP-4000S、EP-4088S、EP-3950S(以上為產品名稱,ADEKA CORPORATION製)、CELLOXIDE(註冊商標)2021P、CELLOXIDE(註冊商標)2081、CELLOXIDE(註冊商標)2000、EHPE3150、EPOLEAD(註冊商標)GT401、EPOLEAD(註冊商標)PB4700、EPOLEAD(註冊商標)PB3600(以上為產品名稱,Daicel Corporation製)、NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000-L、XD-1000、NC-7000L、NC-7300L、EPPN-501H、EPPN-501HY、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、BREN-S、BREN-10S(以上為產品名稱,Nippon Kayaku Co.,Ltd.製)等。又,亦可以較佳地使用以下化合物。Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy epoxy silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but 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) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (product names above, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD ( Registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the product names above, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN- 104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.
【化學式22】 [Chemical formula 22]
式中,n為1~5的整數、m為1~20的整數。In the formula, n is an integer of 1-5, and m is an integer of 1-20.
在上述結構之中,從兼顧耐熱性和伸長率的提高之觀點考慮,n為1~2、m為3~7為較佳。Among the above-mentioned structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.
-氧雜環丁烷化合物(具有氧環丁烷基之化合物)- 作為氧雜環丁烷化合物,可以舉出在一分子中具有2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-氧環丁烷基)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-氧環丁烷基)甲基]酯等。作為具體的例子,能夠較佳地使用TOAGOSEI CO.,LTD.製的ARON OXETANE系列(例如,OXT-121、OXT-221),該等可以單獨使用或混合使用2種以上。 -Oxetane compounds (compounds with an oxetane group)- Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxy oxetane, 1,4-bis{ [(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. As a specific example, ARON OXETANE series (for example, OXT-121 and OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.
-苯并噁𠯤化合物(具有苯并噁唑基之化合物)- 由於由開環加成反應引起交聯反應,苯并噁𠯤化合物在硬化時不產生脫氣,從而進一步減少熱收縮以抑制產生翹曲,因此為較佳。 -Benzoxazole compounds (compounds having a benzoxazolyl group)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzoxazine compound is preferred without degassing during hardening, thereby further reducing thermal shrinkage and suppressing the occurrence of warpage.
作為苯并噁𠯤化合物的較佳例,可以舉出P-d型苯并噁𠯤、F-a型苯并噁𠯤、(以上為產品名稱,Shikoku Chemicals Corporation製)、聚羥基苯乙烯樹脂的苯并噁𠯤加成物、酚醛清漆型二氫苯并噁𠯤化合物。該等可以單獨使用或者混合使用2種以上。Preferable examples of the benzoxazine compound include P-d-type benzoxazine, F-a-type benzoxazine, (the above are the product names, manufactured by Shikoku Chemicals Corporation), and benzoxazine of polyhydroxystyrene resin. Adduct, novolac-type dihydrobenzoxazine compound. These can be used individually or in mixture of 2 or more types.
其他交聯劑的含量相對於感光性組成物的總固體成分為0.1~30質量%為較佳,0.1~20質量%為更佳,0.5~15質量%為進一步較佳,1.0~10質量%為特佳。其他交聯劑可以僅含有1種,亦可以含有2種以上。在含有2種以上的其他交聯劑之情況下,其合計在上述範圍內為較佳。The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and 1.0 to 10% by mass relative to the total solid content of the photosensitive composition. Excellent. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.
<有機金屬錯合物> 從耐藥品性的觀點考慮,感光性組成物包含有機金屬錯合物為較佳。 有機金屬錯合物只要為包含金屬原子之有機錯合物即可,但是包含金屬原子及有機基之錯合物為較佳,有機基對金屬原子進行配位之化合物為更佳,茂金屬化合物為進一步較佳。 在本發明中,茂金屬化合物是指具有2個可以具有取代基的環戊二烯基陰離子衍生物作為η5-配位體之有機金屬錯合物。 作為上述有機基,並無特別限定,但是由烴基或烴基與雜原子的組合組成之基團為較佳。作為雜原子,氧原子、硫原子及氮原子為較佳。 在本發明中,有機基團中的至少1個為環狀基為較佳,至少2個為環狀基為更佳。 上述環狀基選自5員環的環狀基及6員環的環狀基為較佳,5員環的環狀基為更佳。 上述環狀基可以為烴環,亦可以為雜環,但是烴環為較佳。 作為5員環的環狀基,環戊二烯基為較佳。 又,本發明中所使用之有機金屬錯合物在1分子中包含2~4個環狀基為較佳。 <Organometallic complex> From the viewpoint of chemical resistance, it is preferable that the photosensitive composition contains an organometallic complex. Organometallic complexes only need to be organic complexes containing metal atoms, but complexes containing metal atoms and organic groups are preferred, and compounds in which organic groups coordinate metal atoms are more preferred, and metallocene compounds are preferred. for further better. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. Although it does not specifically limit as said organic group, The group which consists of a hydrocarbon group or a combination of a hydrocarbon group and a hetero atom is preferable. As the hetero atom, an oxygen atom, a sulfur atom and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
作為有機金屬錯合物中所包含之金屬,並無特別限定,但是與第4族元素對應之金屬為較佳,選自包括鈦、鋯及鉿之群組中的至少1種金屬為更佳,選自包括鈦及鋯之群組中的至少1種金屬為進一步較佳,鈦為特佳。The metal contained in the organometallic complex is not particularly limited, but a metal corresponding to a Group 4 element is preferred, and at least one metal selected from the group consisting of titanium, zirconium and hafnium is more preferred , at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.
有機金屬錯合物可以包含2個以上的金屬原子,亦可以僅包含1個金屬原子,但是僅包含1個金屬原子為較佳。在有機金屬錯合物包含2個以上的金屬原子之情況下,可以僅包含1種金屬原子,亦可以包含2種以上的金屬原子。The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one type of metal atom may be contained, or two or more types of metal atoms may be contained.
有機金屬錯合物為二茂鐵化合物、二茂鈦化合物、二茂鋯(Zirconocene)化合物或二茂鉿(Hafnocene)化合物為較佳,二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳,二茂鈦化合物或二茂鋯化合物為進一步較佳,二茂鈦化合物為特佳。The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound, a zirconocene compound or a hafnocene compound is More preferably, titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.
有機金屬錯合物具有光自由基聚合起始能之態樣亦為本發明的較佳態樣之一。 在本發明中,具有光自由基聚合起始能表示能夠藉由光的照射而產生能夠起始自由基聚合之自由基。例如,在對包含自由基交聯劑和有機金屬錯合物之組成物照射了有機金屬錯合物吸收光之波長區域且自由基交聯劑不吸收光的波長區域中的光時,能夠藉由確認自由基交聯劑有無消失來確認有無光自由基聚合起始能。在確認有無消失時,能夠依據自由基交聯劑的種類來選擇適當的方法,例如只要藉由IR測定(紅外分光測定)或HPLC測定(高效液相層析法)來確認即可。 在有機金屬錯合物具有光自由基聚合起始能之情況下,有機金屬錯合物為茂金屬化合物為較佳,二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳,二茂鈦化合物或二茂鋯化合物為進一步較佳,二茂鈦化合物為特佳。 在有機金屬錯合物不具有光自由基聚合起始能的情況下,有機金屬錯合物為選自包括二茂鈦化合物、四烷氧基鈦化合物、醯化鈦化合物、鈦螯合物、二茂鋯化合物及二茂鉿化合物之群組中的至少1種化合物為較佳,選自包括二茂鈦化合物、二茂鋯化合物及二茂鉿化合物之群組中的至少1種化合物為更佳,選自包括二茂鈦化合物及二茂鋯化合物之群組中的至少1種化合物為進一步較佳,二茂鈦化合物為特佳。 The aspect that the organometallic complex has the initiation energy of photo-radical polymerization is also one of the preferred aspects of the present invention. In the present invention, having photoradical polymerization initiation energy means that a radical capable of initiating radical polymerization can be generated by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, it can be The presence or absence of photoradical polymerization initiation energy was confirmed by confirming the disappearance of the radical crosslinking agent. When confirming the disappearance or not, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it may be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). In the case that the organometallic complex has the initiation energy of photo-radical polymerization, it is preferred that the organometallic complex is a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and two Titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. In the case where the organometallic complex does not have the initiation energy of photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, titanium chelates, At least one compound selected from the group consisting of a zirconocene compound and a hafnocene compound is preferred, and at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound and a hafnocene compound is more preferred. Preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.
有機金屬錯合物的分子量為50~2,000為較佳,100~1,000為更佳。The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
作為有機金屬錯合物,可以較佳地舉出下述式(P)所表示之化合物。 【化學式23】 式(P)中,M為金屬原子,R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [Chemical formula 23] In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.
式(P)中,作為M所表示之金屬原子,鐵原子、鈦原子、鋯原子或鉿原子為較佳,鈦原子、鋯原子或鉿原子為更佳,鈦原子或鋯原子為進一步較佳,鈦原子為特佳。 作為式(P)的R中之芳香族基,可以舉出碳數6~20的芳香族基,碳數6~20的芳香族烴基為較佳,可以舉出苯基、1-萘基或2-萘基等。 作為式(P)的R中之烷基,碳數1~20的烷基為較佳,碳數1~10的烷基為更佳,可以舉出甲基、乙基、丙基、辛基、異丙基、第三丁基、異戊基、2-乙基己基、2-甲基己基及環戊基等。 作為上述R中之鹵素原子,可以舉出F、Cl、Br及I。 作為構成上述R中之烷基磺醯氧基之烷基,碳數1~20的烷基為較佳,碳數1~10的烷基為更佳,可以舉出甲基、乙基、丙基、辛基、異丙基、第三丁基、異戊基、2-乙基己基、2-甲基己基及環戊基等。 上述R還可以具有取代基。作為取代基的例子,可以舉出鹵素原子(F、Cl、Br、I)、羥基、羧基、胺基、氰基、芳基、烷氧基、芳氧基、醯基、烷氧羰基、芳氧羰基、醯氧基、單烷基胺基、二烷基胺基、單芳胺基及二芳基胺基等。 In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, and a titanium atom or a zirconium atom is further preferable , titanium atoms are particularly good. Examples of the aromatic group in R of the formula (P) include aromatic groups having 6 to 20 carbon atoms, and preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl, etc. As the alkyl group in R of the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl group, ethyl group, propyl group, and octyl group are mentioned. , isopropyl, tert-butyl, isoamyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. As the halogen atom in the above-mentioned R, F, Cl, Br and I can be mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, and propyl groups are mentioned. base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. The above R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryl Oxycarbonyl, acyloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.
作為有機金屬錯合物的具體例,並無特別限定,但是可以例示四異丙氧基鈦、四(2-乙基己氧基)鈦、二異丙氧基雙(乙醯乙酸乙酯)鈦、二異丙氧基雙(乙醯丙酮)鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦、五甲基環戊二烯基三甲醇鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟苯基)鈦及下述化合物。 【化學式24】 Specific examples of the organometallic complex are not particularly limited, but tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate) can be exemplified. Titanium, diisopropoxybis(acetoacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl) base)phenyl)titanium, pentamethylcyclopentadienyltrimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following said compound. [Chemical formula 24]
除此以外,亦能夠使用國際公開第2018/025738號的0078~0088段中所記載的化合物,但是並不限定於此。In addition to this, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.
有機金屬錯合物的含量相對於感光性組成物的總固體成分為0.1~30質量%為較佳。下限為1.0質量%以上為更佳,1.5質量%以上為進一步較佳,3.0質量%以上為特佳。上限為25質量%以下為更佳。 有機金屬錯合物能夠使用1種或2種以上。在使用2種以上之情況下,合計量在上述範圍內為較佳。 The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the photosensitive composition. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that the total amount is in the said range.
〔聚合起始劑〕 感光性組成物包含能夠藉由光和/或熱而開始聚合之聚合起始劑為較佳。尤其,包含光聚合起始劑為較佳。 又,從硬化物的耐藥品性及斷裂伸長率的觀點考慮,本發明的感光性組成物包含後述茂金屬化合物作為聚合起始劑為較佳。 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而生成活性自由基之活性劑。 [Polymerization initiator] It is preferable that the photosensitive composition contains a polymerization initiator capable of starting polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Moreover, it is preferable that the photosensitive composition of this invention contains the metallocene compound mentioned later as a polymerization initiator from the viewpoint of the chemical resistance of a hardened|cured material and elongation at break. Preferably, the photopolymerization initiator is a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer of photoexcitation.
光自由基聚合起始劑至少含有1種在波長約240~800nm(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。關於化合物的莫耳吸光係數,能夠使用公知的方法來測定。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的濃度下進行測定為較佳。 Preferably, the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L/mol -1 /cm -1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent.
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,可以舉出鹵化烴衍生物(例如具有三𠯤骨架之化合物、具有噁二唑骨架之化合物、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、胺基苯乙酮等α-胺基酮化合物、羥基苯乙酮等α-羥基酮化合物、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。關於該等詳細內容,能夠參閱日本特開2016-027357號公報的0165~0182段、國際公開第2015/199219號的0138~0151段的記載,並將該內容編入本說明書中。又,可以舉出日本特開2014-130173號公報的0065~0111段、日本專利第6301489號公報中所記載之化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019中所記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中所記載的光聚合起始劑、國際公開第2018/110179號中所記載的光聚合起始劑、日本特開2019-043864號公報中所記載的光聚合起始劑、日本特開2019-044030號公報中所記載的光聚合起始劑、日本特開2019-167313號公報中所記載的過酸化物系起始劑,並將該等內容亦編入本說明書中。As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in JP 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in JP 2019-044030 A, the peracid-based initiator described in JP 2019-167313 A, These contents are also incorporated into this manual.
作為酮化合物,例如可以例示日本特開2015-087611號公報的0087段中所記載的化合物,並將該內容編入本說明書中。在市售品中,亦可以較佳地使用KAYACURE DETX-S(Nippon Kayaku Co.,Ltd.製)。As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and this content is incorporated in the present specification. Among the commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.
在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,並將該內容編入本說明書中。In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the This content is incorporated into this manual.
作為α-羥基酮系起始劑,能夠使用Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上為IGM Resins B.V.公司製)、IRGACURE 184(IRGACURE為註冊商標)、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127(產品名稱:均為BASF公司製)。As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE- 2959, IRGACURE 127 (product name: all made by BASF).
作為α-胺基酮系起始劑,能夠使用Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上為IGM Resins B.V.公司製)、IRGACURE 907、IRGACURE 369及IRGACURE 379(產品名稱:均為BASF公司製)。As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are BASF Corporation) can be used system).
作為胺基苯乙酮系起始劑,亦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,並將該內容編入本說明書中。As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength is matched to a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in the present specification.
作為醯基膦系起始劑,可以舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又,能夠使用Omnirad 819、Omnirad TPO(以上為IGM Resins B.V.公司製)、IRGACURE-819或IRGACURE-TPO(產品名稱:均為BASF公司製)。As an acylphosphine-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation) can be used.
作為茂金屬化合物,可以例示IRGACURE-784、IRGACURE-784EG(均為BASF公司製)、Keycure VIS 813(King Brother Chem公司製)等。Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF Corporation), Keycure VIS 813 (manufactured by King Brother Chem Corporation), and the like.
作為光自由基聚合起始劑,可以更佳地舉出肟化合物。藉由使用肟化合物,能夠更有效地提高曝光寬容度。肟化合物的曝光寬容度(曝光餘量)較廣,並且亦作為光硬化促進劑而起作用,因此為特佳。As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, so it is particularly preferable.
作為肟化合物的具體例,可以舉出日本特開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、J.C.S.Perkin II(1979年,pp.1653-1660)中所記載的化合物、J.C.S.Perkin II(1979年,pp.156-162)中所記載的化合物、Journal of Photopolymer Science and Technology(1995年,pp.202-232)中所記載的化合物、日本特開2000-066385號公報中所記載的化合物、日本特表2004-534797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、日本特開2017-019766號公報中所記載的化合物、日本專利第6065596號公報中所記載的化合物、國際公開第2015/152153號中所記載的化合物、國際公開第2017/051680號中所記載的化合物、日本特開2017-198865號公報中所記載的化合物、國際公開第2017/164127號的0025~0038段中所記載的化合物、國際公開第2013/167515號中所記載的化合物等,並將該內容編入本說明書中。Specific examples of the oxime compound include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, and compounds described in JP 2006-342166 A. Compounds, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP 2000-066385 A, compounds described in JP 2004-534797 A, JP 2006-342166 A Compounds described, compounds described in JP 2017-019766 A, compounds described in JP 6065596 A, compounds described in International Publication No. 2015/152153, International Publication No. 2017/051680 The compounds described in JP 2017-198865 A, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and the compounds described in International Publication No. 2013/167515 etc., and the contents are incorporated into this manual.
作為較佳的肟化合物,例如可以舉出下述結構的化合物、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。在感光性組成物中,尤其使用肟化合物(肟系的光自由基聚合起始劑)作為光自由基聚合起始劑為較佳。肟系光自由基聚合起始劑在分子內具有>C=N-O-C(=O)-的連接基。Examples of preferable oxime compounds include compounds having the following structures, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1- Ketone, 2-Benzyloxyimino-1-phenylpropan-1-one, 3-(4-Tosyloxy)iminobutan-2-one and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the photosensitive composition, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.
【化學式25】 [Chemical formula 25]
市售品中,亦可以較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04(以上為BASF公司製)、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,亦能夠使用TR-PBG-304、TR-PBG-305(Changzhou Tronly New Electronic Materials CO., LTD.製)、ADEKA ARKLS NCI-730、NCI-831及ADEKA ARKLS NCI-930(ADEKA CORPORATION製)。又,能夠使用DFI-091(DAITO CHEMIX Co.,Ltd.製)、SpeedCure PDO(SARTOMER ARKEMA製)。又,亦能夠使用下述結構的肟化合物。 【化學式26】 Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japanese Patent Laid-Open No. 2012-014052) can also be preferably used. Photo-radical polymerization initiator 2) described in Gazette No. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, 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.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 26]
作為光自由基聚合起始劑,亦能夠使用具有茀環之肟化合物。作為具有茀環之肟化合物的具體例,可以舉出日本特開2014-137466號公報中所記載的化合物、日本專利06636081號中所記載的化合物,並將該內容編入本說明書中。As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in Japanese Patent Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in the present specification.
作為光自由基聚合起始劑,亦能夠使用具有咔唑環中的至少1個苯環成為萘環之骨架之肟化合物。作為該種肟化合物的具體例,可以舉出國際公開第2013/083505號中所記載的化合物,並將該內容編入本說明書中。As the photoradical polymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 is mentioned, and the content is incorporated in this specification.
又,亦能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例,可以舉出日本特開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,並將該內容編入本說明書中。Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471, and the contents thereof are incorporated into the present specification.
作為光聚合起始劑,能夠使用具有硝基之肟化合物。具有硝基之肟化合物設為二聚體亦較佳。作為具有硝基之肟化合物的具體例,可以舉出日本特開2013-114249號公報的0031~0047段、日本特開2014-137466號公報的0008~0012段、0070~0079段中所記載之化合物、日本專利4223071號公報的0007~0025段中所記載之化合物,並將該內容編入本說明書中。又,作為具有硝基之肟化合物,亦可以舉出ADEKA ARKLS NCI-831(ADEKA CORPORATION製)。As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A. The compound is the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated into the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.
作為光自由基聚合起始劑,亦能夠使用具有苯并呋喃骨架之肟化合物。作為具體例,可以舉出國際公開第2015/036910號中所記載之OE-01~OE-75。As a photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
作為光自由基聚合起始劑,亦能夠使用在咔唑骨架上具有羥基之取代基鍵結而獲得之肟化合物。作為該種光聚合起始劑,可以舉出國際公開第2019/088055號中所記載之化合物等,並將該內容編入本說明書中。As the photoradical polymerization initiator, an oxime compound obtained by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.
作為光聚合起始劑,亦能夠使用具有在芳香族環上導入有拉電子基團之芳香族環基Ar OX1之肟化合物(以下,亦稱為肟化合物OX)。作為上述芳香族環基Ar OX1所具有之拉電子基團,可以舉出醯基、硝基、三氟甲基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、氰基,醯基及硝基為較佳,從容易形成耐光性優異之膜等理由考慮,醯基為更佳,苯甲醯基為進一步較佳。苯甲醯基可以具有取代基。作為取代基,鹵素原子、氰基、硝基、羥基、烷基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烯基、烷基硫基、芳基硫基、醯基或胺基為較佳,烷基、烷氧基、芳基、芳氧基、雜環氧基、烷基硫基、芳基硫基或胺基為更佳,烷氧基、烷基硫基或胺基為進一步較佳。 As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar OX1 into which an electron withdrawing group is introduced can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, and an acyl group is more preferable, and a benzyl group is still more preferable because of the ease of forming a film excellent in light resistance. The benzyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkenyl group, alkylthio group, arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio group or an amine group is further preferred.
肟化合物OX為選自式(OX1)所表示之化合物及式(OX2)所表示之化合物中的至少1種為較佳,式(OX2)所表示之化合物為更佳。 【化學式27】 式中,R X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、亞膦醯基、胺甲醯基或胺磺醯基, R X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基硫基、芳基硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基, R X3~R X14分別獨立地表示氫原子或取代基; 其中,R X10~R X14中的至少1個為拉電子基團。 The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [Chemical formula 27] In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphonide group, carbamoyl group or sulfamoyl group, R X2 represents alkyl, alkene alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl group, arylsulfonyl group, aryloxy group or amine group, R X3 to R X14 each independently represent a hydrogen atom or a substituent; wherein, at least one of R X10 to R X14 is an electron withdrawing group.
在上述式中,R X12為拉電子基團,R X10、R X11、R X13、R X14為氫原子為較佳。 In the above formula, R X12 is an electron withdrawing group, and R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
作為肟化合物OX的具體例,可以舉出日本專利第4600600號公報的0083~0105段中所記載的化合物,並將該內容編入本說明書中。Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated in the present specification.
作為最佳的肟化合物,可以舉出日本特開2007-269779號公報中所示之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示之具有硫芳基之肟化合物等,並將該內容編入本說明書中。As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group shown in JP-A No. 2009-191061 can be mentioned. , and incorporate it into this manual.
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、鹵甲基噁二唑化合物、3-芳基取代香豆素化合物之群組中的化合物為較佳。From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl groups Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl -Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
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、茂金屬化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中的至少1種化合物為更進一步較佳,使用茂金屬化合物為特佳。Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is more preferable to use at least one compound in the group of ketone compounds, and it is especially preferable to use a metallocene compound.
又,光自由基聚合起始劑亦能夠使用二苯甲酮、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-嗎啉基苯基)-丁酮-1,2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環縮環而形成之醌類、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,亦能夠使用下述式(I)所表示之化合物。In addition, as the photoradical polymerization initiator, N, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by condensed with aromatic rings, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.
【化學式28】 [Chemical formula 28]
式(I)中,R I00為碳數1~20的烷基、藉由1個以上的氧原子而中斷之碳數2~20的烷基、碳數1~12的烷氧基或苯基或碳數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、經藉由1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1個取代的苯基或聯苯基,R I01為式(II)所表示之基團或為與R I00相同的基團,R I02~R I04分別獨立地為碳數1~12的烷基、碳數1~12的烷氧基或鹵素原子。 In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms or a phenyl group or C1-20 alkyl, C1-12 alkoxy, halogen atom, cyclopentyl, cyclohexyl, C2-12 alkenyl, interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of the alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II) or the same as R I00 R I02 to R I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons or a halogen atom.
【化學式29】 [Chemical formula 29]
式中,R I05~R I07與上述式(I)的R I02~R I04相同。 In the formula, R I05 to R I07 are the same as R I02 to R I04 of the above formula (I).
又,光自由基聚合起始劑亦能夠使用國際公開第2015/125469號的0048~0055段中所記載的化合物,並將該內容編入本說明書中。In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in the present specification.
作為光自由基聚合起始劑,可以使用2官能或3官能以上的光自由基聚合起始劑。藉由使用該種光自由基聚合起始劑,從光自由基聚合起始劑的1分子產生2個以上的自由基,因此可以獲得良好的靈敏度。又,在使用非對稱結構的化合物之情況下,結晶性降低而在溶劑等中的溶解性提高,變得難以經時析出,從而能夠提高感光性組成物的經時穩定性。作為2官能或3官能以上的光自由基聚合起始劑的具體例,可以舉出日本特表2010-527339號公報、日本特表2011-524436號公報、國際公開第2015/004565號、日本特表2016-532675號公報的0407~0412段、國際公開第2017/033680號的0039~0055段中所記載之肟化合物的二聚體、日本特表2013-522445號公報中所記載之化合物(E)及化合物(G)、國際公開第2016/034963號中所記載之Cmpd1~7、日本特表2017-523465號公報的0007段中所記載之肟酯類光起始劑、日本特開2017-167399號公報的0020~0033段中所記載之光起始劑、日本特開2017-151342號公報的0017~0026段中所記載之光聚合起始劑(A)、日本專利第6469669號公報中所記載之肟酯光起始劑等,並將該內容編入本說明書中。As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation over time becomes difficult, so that the stability over time of the photosensitive composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The oxime ester photoinitiator and the like described, and the contents are incorporated into this specification.
在包含光聚合起始劑之情況下,其含量相對於感光性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1種,亦可以含有2種以上。在含有2種以上的光聚合起始劑之情況下,合計量在上述範圍內為較佳。 再者,光聚合起始劑有時亦作為熱聚合起始劑而發揮功能,因此有時藉由烘箱或加熱板等的加熱而進一步進行基於光聚合起始劑之交聯。 When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass % with respect to the total solid content of the photosensitive composition, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass % %, more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.
〔敏化劑〕 感光性組成物可以包括敏化劑。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自由基聚合起始劑、光自由基聚合起始劑等接觸,從而產生電子轉移、能量轉移、發熱等作用。藉此,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,並生成自由基、酸或鹼。 作為能夠使用的敏化劑,能夠使用乙醇胺系、二苯甲酮系、米其勒酮系、香豆素系、吡唑偶氮系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、蒽系、蒽吡啶酮系、亞苄基系、氧雜菁系、吡唑并***偶氮系、吡啶酮偶氮系、花青系、啡噻𠯤系、吡咯并吡唑偶氮次甲基系、口山口星系、酞菁系、苯并吡喃系、靛藍系等化合物。 作為敏化劑,例如可以舉出米其勒酮、4,4’-雙(二乙胺基)二苯甲酮、2,5-雙(4’-二乙胺基亞苄基)環戊烷、2,6-雙(4’-二乙胺基亞苄基)環己酮、2,6-雙(4’-二乙胺基亞苄基)-4-甲基環己酮、4,4’-雙(二甲基胺基)查耳酮、4,4’-雙(二乙胺基)查耳酮、對二甲基胺基苯亞烯丙基二氫茚酮、對二甲基胺基亞苄基二氫茚酮、2-(對二甲基胺基苯基亞聯苯基)-苯并噻唑、2-(對二甲基胺基苯基亞乙烯基)苯并噻唑、2-(對二甲基胺基苯基亞乙烯基)異萘并噻唑、1,3-雙(4’-二甲基胺基亞苄基)丙酮、1,3-雙(4’-二乙胺基亞苄基)丙酮、3,3’-羰基-雙(7-二乙胺基香豆素)、3-乙醯基-7-二甲基胺基香豆素、3-乙氧基羰基-7-二甲基胺基香豆素、7-二乙胺基-4-甲基香豆素、3-苄氧基羰基-7-二甲基胺基香豆素、3-甲氧基羰基-7-二乙胺基香豆素、3-乙氧基羰基-7-二乙胺基香豆素(7-(二乙胺基)香豆素-3-羧酸乙酯)、N-苯基-N’-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯基二乙醇胺、N-苯基乙醇胺、4-嗎啉基二苯甲酮、二甲基胺基苯甲酸異戊酯、二乙胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-(對二甲基胺基苯乙烯基)苯并噁唑、2-(對二甲基胺基苯乙烯基)苯并噻唑、2-(對二甲基胺基苯乙烯基)萘并(1,2-d)噻唑、2-(對二甲基胺基苯甲醯基)苯乙烯、二苯基乙醯胺、苯甲醯苯胺、N-甲基乙醯苯胺、3’,4’-二甲基乙醯苯胺等。 又,可以使用其他敏化色素。 關於敏化色素的詳細內容,能夠參閱日本特開2016-027357號公報的0161~0163段的記載,並將該內容編入本說明書中。 [Sensitizer] The photosensitive composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with the thermal radical polymerization initiator, the photoradical polymerization initiator, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator are decomposed by chemical change, and a radical, an acid, or a base is generated. As sensitizers that can be used, ethanolamine-based, benzophenone-based, Michler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, and anthraquinone-based sensitizers can be used series, anthracene series, anthrapyridone series, benzylidene series, oxocyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azo series Compounds such as methine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series, etc. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4' -diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3 -Methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, dimethylamine isoamyl benzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylamine) styryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole , 2-(p-dimethylaminobenzyl)styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide Wait. In addition, other sensitizing dyes can be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.
在感光性組成物包含敏化劑之情況下,敏化劑的含量相對於感光性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1種,亦可以同時使用2種以上。When the photosensitive composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the photosensitive composition. The mass % is more preferable. A sensitizer may be used individually by 1 type, and may use 2 or more types together.
〔鏈轉移劑〕 感光性組成物可以含有鏈轉移劑。關於鏈轉移劑,例如在高分子詞典第三版(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,例如可以使用在分子內具有-S-S-、-SO 2-S-、-N-O-、SH、PH、SiH及GeH之化合物群組、具有用於RAFT(Reversible Addition Fragmentation chain Transfer:可逆加成鏈轉移聚合)聚合之硫羰硫基之二硫代苯甲酸酯、三硫代碳酸酯、二硫代胺基甲酸酯、黃原酸酯(Xanthate)化合物等。該等對低活性自由基供給氫而生成自由基或者在被氧化之後可以藉由去質子來生成自由基。尤其,能夠較佳地使用硫醇化合物。 [Chain Transfer Agent] The photosensitive composition may contain a chain transfer agent. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, for example, a group of compounds having -SS-, -SO 2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule, a compound having a compound for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) polymerized thiocarbonylthio dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. These can generate free radicals by supplying hydrogen to the less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.
又,鏈轉移劑亦能夠使用國際公開第2015/199219號的0152~0153段中所記載的化合物,並將該內容編入本說明書中。In addition, as a chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. WO 2015/199219 can also be used, and the contents are incorporated in the present specification.
在感光性組成物具有鏈轉移劑之情況下,鏈轉移劑的含量相對於感光性組成物的總固體成分100質量份為0.01~20質量份為較佳,0.1~10質量份為更佳,0.5~5質量份為進一步較佳。鏈轉移劑可以為僅1種,亦可以為2種以上。在鏈轉移劑為2種以上之情況下,其合計在上述範圍內為較佳。When the photosensitive composition has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive composition, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.
〔光酸產生劑〕 感光性組成物包含光酸產生劑為較佳。 光酸產生劑表示藉由200nm~900nm的光照射而產生布忍斯特酸及路易斯酸中的至少一者之化合物。所照射之光較佳為波長300nm~450nm的光,更佳為330nm~420nm的光。在單獨使用光酸產生劑或與敏化劑的同時使用時,能夠藉由感光而產生酸的光酸產生劑為較佳。 作為所產生之酸的例子,可以較佳地舉出鹵化氫、羧酸、磺酸、亞磺酸、硫代亞磺酸、磷酸、磷酸單酯、磷酸二酯、硼衍生物、磷衍生物、銻衍生物、過氧化鹵素、磺酸醯胺等。 [Photoacid generator] It is preferable that the photosensitive composition contains a photoacid generator. The photoacid generator represents a compound that generates at least one of a Brynster acid and a Lewis acid by irradiation with light of 200 nm to 900 nm. The light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm. When a photoacid generator is used alone or in combination with a sensitizer, a photoacid generator capable of generating an acid by exposure to light is preferred. Preferable examples of the acid to be generated include hydrogen halide, carboxylic acid, sulfonic acid, sulfinic acid, thiosulfinic acid, phosphoric acid, phosphoric acid monoester, phosphoric acid diester, boron derivatives, and phosphorus derivatives. , Antimony derivatives, halogen peroxides, sulfonamides, etc.
作為感光性組成物中所使用之光酸產生劑,例如可以舉出醌二疊氮化合物、肟磺酸鹽化合物、有機鹵化化合物、有機硼酸鹽化合物、二磺酸化合物、鎓鹽化合物等。 從靈敏度、保存穩定性的觀點考慮,有機鹵素化合物、肟磺酸鹽化合物、鎓鹽化合物為較佳,從所形成之膜的機械特性等之觀點考慮,肟酯為較佳。 Examples of the photoacid generator used in the photosensitive composition include quinonediazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonic acid compounds, onium salt compounds, and the like. From the viewpoints of sensitivity and storage stability, organohalogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of mechanical properties of the formed film, oxime esters are preferred.
作為醌二疊氮化合物,可以舉出醌二疊氮的磺酸酯鍵於1價或多元的羥基化合物而獲得者,醌二疊氮的磺酸磺醯胺鍵於1價或多元的胺化合物而獲得者,醌二疊氮的磺酸酯鍵和/或磺醯胺鍵於聚羥基聚胺化合物而獲得者等。該等聚羥基化合物、聚胺基化合物、聚羥基聚胺基化合物的所有官能基可以未經醌二疊氮取代,但是進行平均而官能基整體的40莫耳%以上經醌二疊氮取代為較佳。藉由含有該種醌二疊氮化合物,能夠獲得對作為通常的紫外線之水銀燈的i射線(波長365nm)、h射線(波長405nm)、g射線(波長436nm)進行感光之感光性組成物。Examples of the quinonediazide compound include a sulfonic acid ester bond of quinonediazide to a monovalent or polyvalent hydroxy compound, and a sulfonic acid sulfonamide bond of quinonediazide to a monovalent or polyvalent amine compound. On the other hand, those obtained are those obtained by the sulfonate bond of quinonediazide and/or the sulfonamide bond to the polyhydroxypolyamine compound. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinonediazide, but on average, more than 40 mol% of the total functional groups are substituted with quinonediazide as better. By containing such a quinonediazide compound, it is possible to obtain a photosensitive composition that is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) of a mercury lamp, which are normal ultraviolet rays.
作為羥基化合物,具體而言,可以舉出酚、三羥基二苯甲酮、4甲氧基酚、異丙醇、辛醇、第三丁醇、環己醇、萘酚、Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、TrisP-SA、TrisOCR-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、亞甲基三-FR-CR、BisRS-26X、DML-MBPC、DML-MBOC、DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、二羥甲基-BisOC-P、DML-PFP、DML-PSBP、DML-MTrisPC、TriML-P、TriML-35XL、TML-BP、TML-HQ、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP(以上為產品名稱,Honshu Chemical Industry Co.,Ltd.製)、BIR-OC、BIP-PC、BIR-PC、BIR-PTBP、BIR-PCHP、BIP-BIOC-F、4PC、BIR-BIPC-F、TEP-BIP-A、46DMOC、46DMOEP、TM-BIP-A(以上為產品名稱,ASAHI YUKIZAI CORPORATION製)、2,6-二甲氧基甲基-4-第三丁基酚、2,6-二甲氧基甲基-對甲酚、2,6-二乙醯氧基甲基-對甲酚、萘酚、四羥基二苯甲酮、沒食子酸甲基酯、雙酚A、雙酚E、亞甲基雙酚、BisP-AP(產品名稱,Honshu Chemical Industry Co.,Ltd.製)、酚醛清漆樹脂等,但是並不限定於該等。Specific examples of the hydroxy compound include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, tert-butanol, cyclohexanol, naphthol, Bis-Z, and BisP. -EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P , BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF , TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the product name above, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR -PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are the product names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethylacetate Oxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxydiol Benzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolak resin, etc., but It is not limited to these.
作為胺基化合物,具體而言,可以舉出苯胺、甲基苯胺、二乙胺、丁胺、1,4-伸苯基二胺、1,3-伸苯基二胺、4,4’-二胺基二苯醚、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、4,4’-二胺基二苯醚等,但是並不限定於該等。Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc., but not limited on such.
又,作為聚羥基聚胺基化合物,具體而言,可以舉出2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、3,3’-二羥基聯苯胺等,但是並不限定於該等。In addition, specific examples of the polyhydroxypolyamine compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3′-dihydroxybenzidine, and the like, but It is not limited to these.
在該等之中,包含酚化合物及與4-萘醌二疊氮磺醯基的酯作為醌二疊氮化合物為較佳。藉此,能夠獲得對i射線曝光之更高的靈敏度和更高的解析度。Among these, it is preferable to contain a phenol compound and an ester with a 4-naphthoquinonediazidesulfonyl group as the quinonediazide compound. Thereby, higher sensitivity and higher resolution to i-ray exposure can be obtained.
感光性組成物中所使用之醌二疊氮化合物的含量相對於樹脂100質量份為1~50質量份為較佳,10~40質量份為更佳。藉由將醌二疊氮化合物的含量設在該範圍內,可以獲得曝光部和未曝光部的對比度,從而能夠實現更高靈敏度化,因此為較佳。進而,可以依據需要添加敏化劑等。The content of the quinonediazide compound used in the photosensitive composition is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, with respect to 100 parts by mass of the resin. By setting the content of the quinonediazide compound within this range, the contrast between the exposed portion and the unexposed portion can be obtained, and thus higher sensitivity can be achieved, which is preferable. Furthermore, a sensitizer etc. can be added as needed.
光酸產生劑為包含肟磺酸鹽基之化合物(以下,亦簡稱為“肟磺酸鹽化合物”)為較佳。 肟磺酸鹽化合物只要具有肟磺酸鹽基,則並無特別限制,但是下述式(OS-1)、後述式(OS-103)、式(OS-104)或式(OS-105)所表示之肟磺酸鹽化合物為較佳。 The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the following formula (OS-103), the formula (OS-104), or the formula (OS-105) The represented oxime sulfonate compounds are preferred.
【化學式30】 【Chemical formula 30】
式(OS-1)中,X 3表示烷基、烷氧基或鹵素原子。在存在複數個X 3之情況下,分別可以相同,亦可以不同。上述X 3中之烷基及烷氧基可以具有取代基。作為上述X 3中之烷基,碳數1~4的直鏈狀或支鏈狀烷基為較佳。作為上述X 3中之烷氧基,碳數1~4的直鏈狀或支鏈狀烷氧基為較佳。作為上述X 3中之鹵素原子,氯原子或氟原子為較佳。 式(OS-1)中,m3表示0~3的整數,0或1為較佳。在m3為2或3時,複數個X 3可以相同亦可以不同。 式(OS-1)中,R 34表示烷基或芳基,碳數1~10的烷基、碳數1~10的烷氧基、碳數1~5的鹵化烷基、碳數1~5的鹵化烷氧基、可以經W取代的苯基、可以經W取代的萘基或可以經W取代的蒽基為較佳。W表示鹵素原子、氰基、硝基、碳數1~10的烷基、碳數1~10的烷氧基、碳數1~5的鹵化烷基或碳數1~5的鹵化烷氧基、碳數6~20的芳基、碳數6~20的鹵化芳基。 In formula (OS-1), X 3 represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X 3 exist, they may be the same or different. The alkyl group and the alkoxy group in the above-mentioned X 3 may have a substituent. As the alkyl group in the aforementioned X 3 , a straight-chain or branched-chain alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group in the above-mentioned X 3 , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom in the above-mentioned X 3 , a chlorine atom or a fluorine atom is preferable. In formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X3 may be the same or different. In formula (OS-1), R 34 represents an alkyl group or an aryl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. The halogenated alkoxy group of 5, the phenyl group which may be substituted with W, the naphthyl group which may be substituted with W, or the anthracenyl group which may be substituted with W are preferred. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms. , an aryl group with a carbon number of 6-20, a halogenated aryl group with a carbon number of 6-20.
式(OS-1)中,m3為3,X 3為甲基,X 3的取代位置為鄰位,R 34為碳數1~10的直鏈狀烷基、7,7-二甲基-2-氧代降崁基甲基或對甲苯基的化合物為特佳。 In formula (OS-1), m3 is 3 , X3 is a methyl group, the substitution position of X3 is an ortho position, and R34 is a straight-chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- Compounds of 2-oxonorkanylmethyl or p-tolyl are particularly preferred.
作為式(OS-1)所表示之肟磺酸鹽化合物的具體例,可以例示日本特開2011-209692號公報的0064~0068段、日本特開2015-194674號公報的0158~0167段中所記載之以下化合物,並將該等內容編入本說明書中。Specific examples of the oxime sulfonate compound represented by formula (OS-1) include those in paragraphs 0064 to 0068 of JP 2011-209692 A and 0158 to 0167 in JP 2015-194674 A. The following compounds are described, and these contents are incorporated into this specification.
【化學式31】 [Chemical formula 31]
式(OS-103)~式(OS-105)中,R s1表示烷基、芳基或雜芳基,有時存在複數個之R s2分別獨立地表示氫原子、烷基、芳基或鹵素原子,有時存在複數個之R s6分別獨立地表示鹵素原子、烷基、烷氧基、磺酸基、胺基磺醯基或烷氧基磺醯基,Xs表示O或S,ns表示1或2,ms表示0~6的整數。 式(OS-103)~式(OS-105)中,R s1所表示之烷基(碳數1~30為較佳)、芳基(碳數6~30為較佳)或雜芳基(碳數4~30為較佳)在可以獲得本發明的效果之範圍內可以具有公知的取代基。 In formula (OS-103) to formula (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and sometimes there are plural R s2 which independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen. Atom, sometimes there are plural R s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, and ns represents 1 Or 2, ms represents an integer from 0 to 6. In formulas (OS-103) to (OS-105), the alkyl group (preferably carbon number 1-30), aryl group (preferably carbon number 6-30) or heteroaryl group represented by R s1 ( It is preferable to have 4 to 30 carbon atoms) within a range in which the effects of the present invention can be obtained, and may have a known substituent.
式(OS-103)~式(OS-105)中,R s2為氫原子、烷基(碳數1~12為較佳)或芳基(碳數6~30為較佳)為較佳,氫原子或烷基為更佳。在化合物中有時存在2個以上之R s2中,1個或2個為烷基、芳基或鹵素原子為較佳,1個為烷基、芳基或鹵素原子為更佳,1個為烷基且其餘為氫原子為特佳。R s2所表示之烷基或芳基在可以獲得本發明的效果之範圍內可以具有公知的取代基。 式(OS-103)、式(OS-104)或式(OS-105)中,Xs表示O或S,O為較佳。上述式(OS-103)~(OS-105)中,包含Xs作為環員之環為5員環或6員環。 In formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably with a carbon number of 1-12) or an aryl group (preferably with a carbon number of 6-30), A hydrogen atom or an alkyl group is more preferable. In the compound sometimes there are more than 2 R s2 , one or two is preferably an alkyl group, an aryl group or a halogen atom, one is an alkyl group, an aryl group or a halogen atom, more preferably, one is an alkyl group, an aryl group or a halogen atom Alkyl groups and the remainder are hydrogen atoms are particularly preferred. The alkyl group or aryl group represented by R s2 may have a known substituent within a range in which the effects of the present invention can be obtained. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring including Xs as a ring member is a 5-membered ring or a 6-membered ring.
式(OS-103)~式(OS-105)中,ns表示1或2,在Xs為O之情況下,ns為1為較佳,並且在Xs為S之情況下,ns為2為較佳。 式(OS-103)~式(OS-105)中,R s6所表示之烷基(碳數1~30為較佳)及烷氧基(碳數1~30為較佳)可以具有取代基。 式(OS-103)~式(OS-105)中,ms表示0~6的整數,0~2的整數為較佳,0或1為更佳,0為特佳。 In the formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1, and when Xs is S, ns is 2. good. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by R s6 may have a substituent . In formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
又,上述式(OS-103)所表示之化合物為下述式(OS-106)、式(OS-110)或式(OS-111)所表示之化合物為特佳,上述式(OS-104)所表示之化合物為下述式(OS-107)所表示之化合物為特佳,上述式(OS-105)所表示之化合物為下述式(OS-108)或式(OS-109)所表示之化合物為特佳。 【化學式32】 In addition, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), and the above formula (OS-104) ) represented by the compound represented by the following formula (OS-107) is particularly preferred, and the compound represented by the above formula (OS-105) is represented by the following formula (OS-108) or formula (OS-109) The compounds indicated are particularly preferred. [Chemical formula 32]
式(OS-106)~式(OS-111)中,R t1表示烷基、芳基或雜芳基,R t7表示氫原子或溴原子,R t8表示氫原子、碳數1~8的烷基、鹵素原子、氯甲基、溴甲基、溴乙基、甲氧基甲基、苯基或氯苯基,R t9表示氫原子、鹵素原子、甲基或甲氧基,R t2表示氫原子或甲基。 式(OS-106)~式(OS-111)中,R t7表示氫原子或溴原子,氫原子為較佳。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom or an alkane having 1 to 8 carbon atoms group, halogen atom, chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl or chlorophenyl, R t9 represents hydrogen atom, halogen atom, methyl or methoxy group, R t2 represents hydrogen atom or methyl group. In the formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
式(OS-106)~式(OS-111)中,R t8表示氫原子、碳數1~8的烷基、鹵素原子、氯甲基、溴甲基、溴乙基、甲氧基甲基、苯基或氯苯基,碳數1~8的烷基、鹵素原子或苯基為較佳,碳數1~8的烷基為更佳,碳數1~6的烷基為進一步較佳,甲基為特佳。 In formulas (OS-106) to (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, and a methoxymethyl group , phenyl or chlorophenyl, preferably an alkyl group with 1 to 8 carbon atoms, a halogen atom or a phenyl group, preferably an alkyl group with 1 to 8 carbon atoms, and even more preferably an alkyl group with 1 to 6 carbon atoms , methyl is particularly good.
式(OS-106)~式(OS-111)中,R t9表示氫原子、鹵素原子、甲基或甲氧基,氫原子為較佳。 R t2表示氫原子或甲基,氫原子為較佳。 又,在上述肟磺酸鹽化合物中,關於肟的立體結構(E,Z),可以為其中任一者,亦可以為混合物。 作為上述式(OS-103)~式(OS-105)所表示之肟磺酸鹽化合物的具體例,可以例示日本特開2011-209692號公報的0088~0095段、日本特開2015-194674號公報的0168~0194段中所記載的化合物,並將該等內容編入本說明書中。 In formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a hydrogen atom is preferable. R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z) of the oxime may be any of them, or a mixture may be used. Specific examples of the oxime sulfonate compounds represented by the above formulae (OS-103) to (OS-105) include paragraphs 0088 to 0095 of Japanese Patent Laid-Open No. 2011-209692 and Japanese Patent Laid-Open No. 2015-194674. Compounds described in paragraphs 0168 to 0194 of the gazette, and these contents are incorporated into the present specification.
作為包含至少1個肟磺酸鹽基之肟磺酸鹽化合物的較佳的其他態樣,可以舉出下述式(OS-101)、式(OS-102)所表示之化合物。As another preferable aspect of the oxime sulfonate compound containing at least one oxime sulfonate group, the compound represented by following formula (OS-101) and formula (OS-102) is mentioned.
【化學式33】 [Chemical formula 33]
式(OS-101)或式(OS-102)中,R u9表示氫原子、烷基、烯基、烷氧基、烷氧羰基、醯基、胺甲醯基、胺磺醯基、磺基、氰基、芳基或雜芳基。R u9為氰基或芳基之態樣為更佳,R u9為氰基、苯基或萘基之態樣為進一步較佳。 式(OS-101)或式(OS-102)中,R u2a表示烷基或芳基。 式(OS-101)或式(OS-102)中,Xu表示-O-、-S-、-NH-、-NR u5-、-CH 2-、-CR u6H-或CR u6R u7-,R u5~R u7分別獨立地表示烷基或芳基。 In formula (OS-101) or formula (OS-102), R u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group , cyano, aryl or heteroaryl. The aspect in which R u9 is a cyano group or an aryl group is more preferable, and the aspect in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable. In formula (OS-101) or formula (OS-102), R u2a represents an alkyl group or an aryl group. In formula (OS-101) or formula (OS-102), Xu represents -O-, -S-, -NH-, -NR u5 -, -CH 2 -, -CR u6 H- or CR u6 R u7 - , R u5 to R u7 each independently represent an alkyl group or an aryl group.
式(OS-101)或式(OS-102)中,R u1~R u4分別獨立地表示氫原子、鹵素原子、烷基、烯基、烷氧基、胺基、烷氧羰基、烷基羰基、芳基羰基、醯胺基、磺基、氰基或芳基。R u1~R u4中的2個分別可以相互鍵結而形成環。此時,環可以進行縮環而與苯環一同形成縮合環。作為R u1~R u4,氫原子、鹵素原子或烷基為較佳,並且R u1~R u4中的至少2個相互鍵結而形成芳基之態樣亦較佳。其中,R u1~R u4均為氫原子之態樣為較佳。上述取代基均還可以具有取代基。 In formula (OS-101) or formula (OS-102), R u1 to R u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, and an alkylcarbonyl group , arylcarbonyl, amido, sulfo, cyano or aryl. Two of R u1 to R u4 may each be bonded to each other to form a ring. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. As R u1 to R u4 , a hydrogen atom, a halogen atom or an alkyl group is preferable, and an aspect in which at least two of R u1 to R u4 are bonded to each other to form an aryl group is also preferable. Among them, the aspect in which all of R u1 to R u4 are hydrogen atoms is preferable. All of the above-mentioned substituents may further have a substituent.
上述式(OS-101)所表示之化合物為式(OS-102)所表示之化合物為更佳。 又,在上述肟磺酸鹽化合物中,關於肟或苯并噻唑環的立體結構(E,Z等),分別可以為其中任一者,亦可以為混合物。 作為式(OS-101)所表示之化合物的具體例,可以例示日本特開2011-209692號公報的0102~0106段、日本特開2015-194674號公報的0195~0207段中所記載的化合物,並將該等內容編入本說明書中。 在上述化合物之中,下述b-9、b-16、b-31、b-33為較佳。 【化學式34】 作為市售品,可以舉出WPAG-336(FUJIFILM Wako Pure Chemical Corporation製)、WPAG-443(FUJIFILM Wako Pure Chemical Corporation製)、MBZ-101(Midori Kagaku Co.,Ltd.製)等。 More preferably, the compound represented by the above formula (OS-101) is the compound represented by the formula (OS-102). In addition, among the above-mentioned oxime sulfonate compounds, the three-dimensional structure (E, Z, etc.) of the oxime or benzothiazole ring may be any of them, respectively, or a mixture may be used. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of JP-A No. 2011-209692 and paragraphs 0195-0207 of JP-A No. 2015-194674 can be exemplified. These contents are incorporated into this manual. Among the above-mentioned compounds, the following b-9, b-16, b-31, and b-33 are preferable. [Chemical formula 34] As a commercial item, WPAG-336 (made by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (made by FUJIFILM Wako Pure Chemical Corporation), MBZ-101 (made by Midori Kagaku Co., Ltd.), etc. are mentioned.
又,亦可以舉出下述結構式所表示之化合物作為較佳例。 【化學式35】 Moreover, the compound represented by the following structural formula can also be mentioned as a preferable example. [Chemical formula 35]
作為有機鹵化化合物,具體而言,可以舉出若林等“Bull Chem.Soc Japan”42、2924(1969)、美國專利第3,905,815號說明書、日本特公昭46-4605號、日本特開昭48-36281號公報、日本特開昭55-32070號公報、日本特開昭60-239736號公報、日本特開昭61-169835號公報、日本特開昭61-169837號公報、日本特開昭62-58241號公報、日本特開昭62-212401號公報、日本特開昭63-70243號公報、日本特開昭63-298339號公報、M.P.Hutt“Jurnal of Heterocyclic Chemistry”1(No3),(1970)等中所記載的化合物,並將該等內容編入本說明書中。尤其,可以舉出經三鹵甲基取代之噁唑化合物:S-三𠯤化合物作為較佳例。 更佳地,可以舉出至少1個單、二或三鹵素取代甲基與s-三𠯤環鍵結而成之s-三𠯤衍生物,具體而言,例如可以舉出2,4,6-三(單氯甲基)-s-三𠯤、2,4,6-三(二氯甲基)-s-三𠯤、2,4,6-三(三氯甲基)-s-三𠯤、2-甲基-4,6-雙(三氯甲基)-s-三𠯤、2-正丙基-4,6-雙(三氯甲基)-s-三𠯤、2-(α,α,β-三氯乙基)-4,6-雙(三氯甲基)-s-三𠯤、2-苯基-4,6-雙(三氯甲基)-s-三𠯤、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(3,4-環氧苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(對氯苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-〔1-(對甲氧基苯基)-2,4-丁二烯基〕-4,6-雙(三氯甲基)-s-三𠯤、2-苯乙烯基-4,6-雙(三氯甲基)-s-三𠯤、2-(對甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(對異丙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(對甲苯基)-4,6-雙(三氯甲基)-s-三𠯤、2-(4-萘氧基萘基)-4,6-雙(三氯甲基)-s-三𠯤、2-苯硫基-4,6-雙(三氯甲基)-s-三𠯤、2-苄硫基-4,6-雙(三氯甲基)-s-三𠯤、2,4,6-三(二溴甲基)-s-三𠯤、2,4,6-三(三溴甲基)-s-三𠯤、2-甲基-4,6-雙(三溴甲基)-s-三𠯤、2-甲氧基-4,6-雙(三溴甲基)-s-三𠯤等。 Specific examples of the organic halogenated compound include Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), the specification of U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Laid-Open Japanese Patent Laid-Open No. 48-36281, Japanese Patent Laid-Open No. 55-32070, Japanese Patent Laid-Open No. 60-239736, Japanese Patent Laid-Open No. 61-169835, Japanese Patent Laid-Open No. 61-169837, Japanese Patent Laid-Open No. 61-169837 Sho 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry" 1 (No3), (1970) and the like, and these contents are incorporated into the present specification. In particular, an oxazole compound substituted with a trihalomethyl group: an S-triazole compound can be mentioned as a preferable example. More preferably, at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-tris-s-tris-s-s-s-s-s-s-s-s-s-s-s-s-s-s-s-derivatives, for example, 2,4,6 -Tris(monochloromethyl)-s-tris-tris, 2,4,6-tris(dichloromethyl)-s-tris-tris, 2,4,6-tris(trichloromethyl)-s-tris 𠯤, 2-methyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-n-propyl-4,6-bis(trichloromethyl)-s-tris𠯤, 2-( α,α,β-Trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-phenyl-4,6-bis(trichloromethyl)-s-tris , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) methyl)-s-tris-tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-[1-(p-methoxyphenyl)-2 ,4-butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris, 2-styryl-4,6-bis(trichloromethyl)-s-s-tris, 2 -(p-Methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl) base)-s-tris-tris, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-tris, 2-(4-naphthyloxynaphthyl)-4,6-bis (Trichloromethyl)-s-tris-tris, 2-phenylsulfanyl-4,6-bis(trichloromethyl)-s-tris-tris, 2-benzylsulfanyl-4,6-bis(trichloromethyl) base)-s-tris-tris, 2,4,6-tris (dibromomethyl)-s-tris, 2,4,6-tris (tribromomethyl)-s-tris, 2-methyl -4,6-bis(tribromomethyl)-s-tris-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-s-tris, etc.
作為有機硼酸鹽化合物,例如可以舉出日本特開昭62-143044號公報、日本特開昭62-150242號公報、日本特開平9-188685號公報、日本特開平9-188686號公報、日本特開平9-188710號公報、日本特開2000-131837號公報、日本特開2002-107916號公報、日本專利第2764769號公報、日本特開2002-116539號公報等及Kunz,Martin“Rad Tech'98.Proceeding April 19-22,1998,Chicago”等中所記載之有機硼酸鹽、日本特開平6-157623號公報、日本特開平6-175564號公報、日本特開平6-175561號公報中所記載的有機硼鋶錯合物或有機硼氧代鋶錯合物、日本特開平6-175554號公報、日本特開平6-175553號公報中所記載的有機硼錪錯合物、日本特開平9-188710號公報中所記載的有機硼鏻錯合物、日本特開平6-348011號公報、日本特開平7-128785號公報、日本特開平7-140589號公報、日本特開平7-306527號公報、日本特開平7-292014號公報等有機硼過渡金屬配位錯合物等作為具體例,並將該等內容編入本說明書中。As the organoborate compound, for example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 2000-131837, Japanese Patent Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Laid-Open No. 2002-116539, etc. and Kunz, Martin "Rad Tech'98" .Proceeding April 19-22, 1998, the organic borate described in "Chicago", etc., Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561 Organoboronium complexes or organoboroxonium complexes, Organoboronium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553, Japanese Patent Laid-Open No. 9-188710 The organoboron phosphonium complexes described in Gazette No. 6-348011, JP 7-128785, JP 7-140589, JP 7-306527, JP 7-306527 Organoboron transition metal complex complexes, such as Unexamined-Japanese-Patent No. 7-292014, etc. are taken as specific examples, and these content are incorporated in this specification.
作為二碸化合物,可以舉出日本特開昭61-166544號公報、日本特開2002-328465公報等中所記載之化合物及重氮二碸化合物。The diazonium compound and the diazodione compound described in Japanese Patent Laid-Open No. 61-166544, Japanese Patent Laid-Open No. 2002-328465 and the like can be exemplified as the dioxane compound.
作為上述鎓鹽化合物,例如可以舉出S.I.Schlesinger,Photogr.Sci.Eng.,18,387(1974)、T.S.Bal et al,Polymer,21,423(1980)中所記載的重氮鹽、美國專利第4,069,055號說明書、日本特開平4-365049號公報等中所記載的銨鹽、美國專利第4,069,055號、美國專利第4,069,056號的各說明書中所記載的鏻鹽、歐洲專利第104,143號、美國專利第339,049號、美國專利第410,201號的各說明書、日本特開平2-150848號、日本特開平2-296514號公報中所記載的錪鹽、歐洲專利第370,693號、歐洲專利第390,214號、歐洲專利第233,567號、歐洲專利第297,443號、歐洲專利第297,442號、美國專利第4,933,377號、美國專利第161,811號、美國專利第410,201號、美國專利第339,049號、美國專利第4,760,013號、美國專利第4,734,444號、美國專利第2,833,827號、德國專利第2,904,626號、德國專利第3,604,580號、德國專利第3,604,581號的各說明書中所記載的鋶鹽、J.V.Crivello et al,Macromolecules,10(6),1307(1977)、J.V.Crivello et al,J.Polymer Sci.,Polymer Chem.Ed.,17,1047(1979)中所記載的硒鹽、C.S.Wen et al,Teh,Proc.Conf.Rad.Curing ASIA,p478 Tokyo,Oct(1988)中所記載的砷鹽、吡啶鎓鹽等鎓鹽等,並將該等內容編入本說明書中。Examples of the above-mentioned onium salt compounds include the diazonium salts described in S.I.Schlesinger, Photogr.Sci.Eng., 18, 387 (1974), T.S. Bal et al, Polymer, 21,423 (1980), and U.S. Patent No. 4,069,055 No. specification, ammonium salts described in Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in each specification of US Pat. No. 4,069,055, US Pat. No. 4,069,056, European Patent No. 104,143, US Pat. No., each specification of U.S. Patent No. 410,201, the iodonium salt described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214, European Patent No. 233,567 No., European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, The permalate salts described in the respective specifications of US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, and German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10(6), 1307(1977), Selenium salts, C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct. (1988), arsenic salts, onium salts such as pyridinium salts, etc., and these contents are incorporated into the present specification.
作為鎓鹽,可以舉出下述通式(RI-I)~(RI-III)所表示之鎓鹽。 【化學式36】 式(RI-I)中,Ar 11表示可以具有1~6個取代基之碳數20以下的芳基,作為較佳的取代基,可以舉出碳數1~12的烷基、碳數2~12的烯基、碳數2~12的炔基、碳數6~12的芳基、碳數1~12的烷氧基、碳數1~12的芳氧基、鹵素原子、碳數1~12的烷基胺基、碳數2~12的二烷基胺基、烷基的碳數為1~12的烷基醯胺基或芳基的碳數為6~20的芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1~12的硫代烷基、碳數1~12的硫代芳基。Z 11 -表示1價的陰離子,其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子,從穩定性的方面考慮,過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子為較佳。式(RI-II)中,Ar 21、Ar 22各自獨立地表示可以具有1~6個取代基的碳數1~20的芳基,作為較佳的取代基,可以舉出碳數1~12的烷基、碳數2~12的烯基、碳數2~12的炔基、碳數1~12的芳基、碳數1~12的烷氧基、碳數1~12的芳氧基、鹵素原子、碳數1~12的單烷基胺基、烷基的碳數分別獨立地為1~12的二烷基胺基、烷基的碳數為1~12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1~12的硫代烷基、碳數1~12的硫代芳基。Z 21 -表示1價的陰離子,其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子,從穩定性、反應性的方面考慮,過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。式(RI-III)中,R 31、R 32、R 33各自獨立地表示可以具有1~6個取代基之碳數6~20的芳基或烷基、烯基、炔基,較佳地,從反應性、穩定性的方面考慮,芳基為較佳。作為較佳的取代基,可以舉出碳數1~12的烷基、碳數2~12的烯基、碳數2~12的炔基、碳數1~12的芳基、碳數1~12的烷氧基、碳數1~12的芳氧基、鹵素原子、碳數1~12的單烷基胺基、烷基的碳數分別獨立地為1~12的二烷基胺基、烷基的碳數為1~12的烷基醯胺基或芳基醯胺基、羰基、羧基、氰基、磺醯基、碳數1~12的硫代烷基、碳數1~12的硫代芳基。Z 31 -表示1價的陰離子,其為鹵素離子、過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、硫代磺酸離子、硫酸離子,從穩定性、反應性的方面考慮,過氯酸離子、六氟磷酸鹽離子、四氟硼酸鹽離子、磺酸離子、亞磺酸離子、羧酸離子為較佳。 Examples of the onium salt include those represented by the following general formulae (RI-I) to (RI-III). [Chemical formula 36] In formula (RI-I), Ar 11 represents an aryl group with 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group with 1 to 12 carbons, an alkyl group with 2 carbons Alkenyl group of to 12, alkynyl of carbon number of 2 to 12, aryl group of carbon number of 6 to 12, alkoxy of carbon number of 1 to 12, aryloxy group of carbon number of 1 to 12, halogen atom, carbon number of 1 Alkylamine group of ~12, dialkylamine group of carbon number of 2 to 12, alkylamide of alkyl group of carbon number of 1 to 12, or arylamide of aryl group of carbon number of 6 to 20 group, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, and thioaryl group having 1 to 12 carbon atoms. Z 11 - represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, and sulfinic acid ion are preferable. In formula (RI-II), Ar 21 and Ar 22 each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents, and preferable substituents include 1 to 12 carbon atoms. alkyl, alkenyl with 2-12 carbons, alkynyl with 2-12 carbons, aryl with 1-12 carbons, alkoxy with 1-12 carbons, aryloxy with 1-12 carbons , halogen atom, monoalkylamine group with 1 to 12 carbon atoms, dialkylamine group with 1 to 12 carbon atoms in the alkyl group, and alkylamide group with 1 to 12 carbon atoms in the alkyl group Or an aryl amido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 21 - represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable. In formula (RI-III), R 31 , R 32 , and R 33 each independently represent an aryl group, an alkyl group, an alkenyl group, and an alkynyl group having 1 to 6 substituents having 6 to 20 carbon atoms, preferably , from the viewpoint of reactivity and stability, aryl groups are preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms. alkoxy group having 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom, monoalkylamine group having 1 to 12 carbon atoms, dialkylamine group having 1 to 12 carbon atoms each independently, Alkyl amido group or aryl amido group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, thioalkyl group having 1 to 12 carbon atoms Thioaryl. Z 31 - represents a monovalent anion, which is halogen ion, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, thiosulfonic acid ion, sulfate ion, from From the viewpoint of stability and reactivity, perchloric acid ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinic acid ion, and carboxylate ion are preferable.
作為較佳的光酸產生劑的具體例,可以舉出以下者。 【化學式37】 【化學式38】 【化學式39】 【化學式40】 Specific examples of preferable photoacid generators include the following. [Chemical formula 37] [Chemical formula 38] [Chemical formula 39] 【Chemical formula 40】
光酸產生劑相對於感光性組成物的總固體成分使用0.1~20質量%為較佳,使用0.5~18質量%為更佳,使用0.5~10質量%為進一步較佳,使用0.5~3質量%為更進一步較佳,使用0.5~1.2質量%為又更進一步較佳。 光酸產生劑可以單獨使用1種,亦可以組合使用複數種。在組合使用複數種的情況下,該等合計量在上述範圍內為較佳。 又,為了對所期望的光源賦予感光性,與敏化劑同時使用亦較佳。 The photoacid generator is preferably used in an amount of 0.1 to 20 mass %, more preferably 0.5 to 18 mass %, more preferably 0.5 to 10 mass %, and 0.5 to 3 mass % with respect to the total solid content of the photosensitive composition. % is still more preferable, and it is still more preferable to use 0.5 to 1.2 mass %. A photoacid generator may be used individually by 1 type, and may be used in combination of a plurality of types. When using a plurality of types in combination, it is preferable that these total amounts are within the above-mentioned range. Moreover, in order to provide photosensitivity to a desired light source, it is also preferable to use together with a sensitizer.
<鹼產生劑> 感光性組成物可以包含鹼產生劑。其中,鹼產生劑為能夠藉由物理或化學作用而產生鹼之化合物。作為對感光性組成物來說較佳的鹼產生劑,可以舉出熱鹼產生劑及光鹼產生劑。 尤其,在感光性組成物包含環化樹脂的前驅物之情況下,感光性組成物包含鹼產生劑為較佳。藉由使感光性組成物含有熱鹼產生劑,例如藉由加熱而能夠促進前驅物的環化反應,成為硬化物的機械特性或耐藥品性良好者,例如作為半導體封裝中所包含之再配線層用層間絕緣膜的性能變得良好。 作為鹼產生劑,可以為離子型鹼產生劑,亦可以為非離子型鹼產生劑。作為從鹼產生劑產生之鹼,例如可以舉出二級胺、三級胺。 對本發明之鹼產生劑並無特別限制,能夠使用公知的鹼產生劑。作為公知的鹼產生劑,例如能夠使用胺甲醯基肟化合物、胺甲醯基羥胺化合物、胺甲酸化合物、甲醯胺化合物、乙醯胺化合物、胺基甲酸酯化合物、苄胺基甲酸酯化合物、硝基苄胺基甲酸酯化合物、磺酸醯胺化合物、咪唑衍生物化合物、胺醯亞胺化合物、吡啶衍生物化合物、α-胺基苯乙酮衍生物化合物、四級銨鹽衍生物化合物、吡啶鎓鹽、α-內酯環衍生物化合物、胺醯亞胺化合物、鄰苯二甲醯亞胺衍生物化合物、醯氧基亞胺基化合物等。 作為非離子型鹼產生劑的具體的化合物,可以舉出式(B1)、式(B2)或式(B3)所表示之化合物。 【化學式41】 <Alkali generator> The photosensitive composition may contain an alkali generator. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for a photosensitive composition, a thermal alkali generator and a photobase generator are mentioned. In particular, when the photosensitive composition contains a precursor of a cyclized resin, it is preferable that the photosensitive composition contains an alkali generator. By incorporating a thermal alkali generator into the photosensitive composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties and chemical resistance, for example, as a rewiring included in a semiconductor package. The performance of the interlayer insulating film for layers becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 41]
式(B1)及式(B2)中,Rb 1、Rb 2及Rb 3分別獨立地為不具有三級胺結構的有機基、鹵素原子或氫原子。其中,Rb 1及Rb 2不會同時成為氫原子。又,Rb 1、Rb 2及Rb 3均不具有羧基。再者,在本說明書中,三級胺結構是指3價的氮原子的3個鍵結鍵均與烴系碳原子進行共價鍵之結構。因此,在所鍵結之碳原子為形成羰基之碳原子之情況亦即在與氮原子一同形成醯胺基之情況下,並不限於此。 In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. In addition, none of Rb 1 , Rb 2 and Rb 3 has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three 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 amide group together with a nitrogen atom, it is not limited to this.
式(B1)、式(B2)中,Rb 1、Rb 2及Rb 3中的至少1個包含環狀結構為較佳,至少2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2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員環為較佳。單環為環己烷環及苯環為較佳,環己烷環為更佳。 In formula (B1) and formula (B2), at least one of Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a condensed ring formed by condensing a monocyclic ring or two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The single ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
更具體而言,Rb 1及Rb 2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。該等基團可以在發揮本發明的效果之範圍內具有取代基。Rb 1與Rb 2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,Rb 1及Rb 2為可以具有取代基的直鏈、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,可以具有取代基的環烷基(碳數3~24為較佳,3~18為更佳,3~12為進一步較佳)為更佳,可以具有取代基的環己基為進一步較佳。 More specifically, Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), alkenyl (having 2 to 24 carbon atoms) is better, 2-18 is better, 3-12 is further better), aryl (carbon number 6-22 is better, 6-18 is better, 6-10 is further better) or arane A base (preferably with a carbon number of 7 to 25, more preferably 7 to 19, and further preferably 7 to 12) is preferable. These groups may have a substituent within a 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 to be formed, a nitrogen-containing heterocyclic ring having 4 to 7 members is preferable. In particular, Rb 1 and Rb 2 are linear, branched or cyclic alkyl groups that may have substituents (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12) as Preferably, optionally substituted cycloalkyl (3-24 carbon atoms are preferred, 3-18 are more preferred, 3-12 are further preferred), and optionally substituted cyclohexyl is further preferred. good.
作為Rb 3,可以舉出烷基(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。Rb 3在發揮本發明的效果之範圍內還可以具有取代基。 Examples of Rb 3 include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), and aryl (preferably having 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms). is more preferred, 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 better, 7-19 is better, 7-12 is further better), aralkenyl (carbon number 8-24 is better, 8-20 is better, 8-16 is further better), alkane Oxy group (preferably carbon number 1-24, more preferably 2-18, more preferably 3-12), aryloxy (preferably carbon number 6-22, more preferably 6-18, 6- 12 is more preferred) or aralkoxy (the number of carbon atoms is preferably 7-23, more preferably 7-19, and more preferably 7-12). Among them, cycloalkyl (preferably carbon number of 3 to 24, more preferably 3 to 18, and even more preferably 3 to 12), aralkenyl and aralkoxy are preferred. Rb 3 may have a substituent within the range in which the effects of the present invention are exhibited.
式(B1)所表示之化合物為下述式(B1-1)或下述式(B1-2)所表示之化合物為較佳。 【化學式42】 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 42]
式中,Rb 11及Rb 12和Rb 31及Rb 32分別與式(B1)中之Rb 1及Rb 2的含義相同。 Rb 13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),在發揮本發明的效果之範圍內可以具有取代基。其中,Rb 13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 alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 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 are more preferable, and 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb 13 is preferably an aralkyl group.
Rb 33及Rb 34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 independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 11), and hydrogen atom is more preferred.
Rb 35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,2~10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 alkyl (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 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 are more preferable, 7-12 are more preferable), aryl group is preferable.
又,式(B1-1)所表示之化合物為式(B1-1a)所表示之化合物亦較佳。 【化學式43】 Moreover, it is also preferable that the compound represented by formula (B1-1) is a compound represented by formula (B1-1a). [Chemical formula 43]
Rb 11及Rb 12與式(B1-1)中之Rb 11及Rb 12的含義相同。 Rb 15及Rb 16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。 Rb 17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,2~10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。 Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in formula (B1-1). Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ~6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl group is preferred. Rb 17 is an alkyl group (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 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 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.
【化學式44】 [Chemical formula 44]
式(B3)中,L表示烴基,該烴基為在連接相鄰之氧原子和碳原子之連接鏈的路徑上具有飽和烴基之2價的烴基,並且連接鏈的路徑上的原子數為3個以上。又,R N1及R N2分別獨立地表示1價的有機基。 In the formula (B3), L represents a hydrocarbon group, and the hydrocarbon group is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 above. In addition, R N1 and R N2 each independently represent a monovalent organic group.
在本說明書中,“連接鏈”是指在連接連接對象的2個原子或連接原子群組之間之路徑上的原子鏈中以最短(最小原子數)的方式連接該等連接對象者。例如,在下述式所表示之化合物中,L由伸苯基伸乙基構成,並且具有伸乙基作為飽和烴基,連接鏈由4個碳原子構成,連接鏈的路徑上的原子數(亦即,為構成連接鏈之原子的數量,以下,亦稱為“連接鏈長度”或“連接鏈的長度”。)為4個。 【化學式45】 In this specification, the "connection chain" refers to the one that connects the connection objects in the shortest (minimum number of atoms) among the atomic chains on the path connecting the two atoms of the connection object or the group of connecting atoms. For example, in the compound represented by the following formula, L is composed of phenylene ethylidene, and has ethylidene as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is four. [Chemical formula 45]
式(B3)之L中的碳數(亦包含除了連接鏈中的碳原子以外的碳原子)為3~24為較佳。上限為12以下為更佳,10以下為進一步較佳,8以下為特佳。下限為4以上為更佳。從快速進行上述分子內環化反應之觀點考慮,L的連接鏈長度的上限為12以下為較佳,8以下為更佳,6以下為進一步較佳,5以下為特佳。尤其,L的連接鏈長度為4或5為較佳,4為最佳。作為鹼產生劑的具體的較佳化合物,例如亦可以舉出國際公開第2020/066416號的0102~0168段中所記載的化合物、國際公開第2018/038002號的0143~0177段中所記載的化合物。The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator include, for example, compounds described in Paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in Paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.
又,鹼產生劑包含下述式(N1)所表示之化合物亦較佳。 【化學式46】 Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). [Chemical formula 46]
式(N1)中,R N1及R N2分別獨立地表示1價的有機基,RC1表示氫原子或保護基,L表示2價的連接基。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.
L為2價的連接基,2價的有機基為較佳。連接基的連接鏈長度為1以上為較佳,2以上為更佳。作為上限,12以下為較佳,8以下為更佳,5以下為進一步較佳。連接鏈長度為在式中的2個羰基之間成為最短路程之原子排列中存在之原子的數量。L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.
式(N1)中,R N1及R N2分別獨立地表示1價的有機基(碳數1~24為較佳,2~18為更佳,3~12為進一步較佳),烴基(碳數1~24為較佳,1~12為更佳,1~10為進一步較佳)為較佳,具體而言,可以舉出脂肪族烴基(碳數1~24為較佳,1~12為更佳,1~10為進一步較佳)或芳香族烴基(碳數6~22為較佳,6~18為更佳,6~10為進一步較佳),脂肪族烴基為較佳。若作為R N1及R N2使用脂肪族烴基,則所產生之鹼的鹼性高,因此為較佳。再者,脂肪族烴基及芳香族烴基可以具有取代基,並且脂肪族烴基及芳香族烴基可以在脂肪族烴鏈中或芳香環中,取代基中具有氧原子。尤其,可以例示脂肪族烴基在烴鏈中具有氧原子之態樣。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R N1 and R N2 , since the basicity of the generated base is high, it is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.
作為構成R N1及R N2之脂肪族烴基,可以舉出直鏈或支鏈的鏈狀烷基、環狀烷基、與鏈狀烷基和環狀烷基的組合有關之基團、在鏈中具有氧原子之烷基。直鏈或支鏈的鏈狀烷基為碳數1~24者為較佳,2~18為更佳,3~12為進一步較佳。關於直鏈或支鏈的鏈狀烷基,例如可以舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二烷基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、第三戊基、異己基等。 環狀烷基為碳數3~12者為較佳,3~6為更佳。關於環狀烷基,例如可以舉出環丙基、環丁基、環戊基、環己基、環辛基等。 與鏈狀烷基和環狀烷基的組合有關之基團為碳數4~24者為較佳,4~18為更佳,4~12為進一步較佳。關於與鏈狀烷基和環狀烷基的組合有關之基團,例如可以舉出環己基甲基、環己基乙基、環己基丙基、甲基環己基甲基、乙基環己基乙基等。 在鏈中具有氧原子之烷基為碳數2~12者為較佳,2~6為更佳,2~4為進一步較佳。在鏈中具有氧原子之烷基可以為鏈狀,亦可以為環狀,並且可以為直鏈,亦可以為支鏈。 其中,從提高後述分解生成鹼的沸點之觀點考慮,R N1及R N2為碳數5~12的烷基為較佳。其中,在重視與金屬(例如銅)的層積層時的密接性之配方中,具有環狀的烷基之基團或碳數1~8的烷基為較佳。 Examples of the aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of chain alkyl groups and cyclic alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Groups related to the combination of a chain alkyl group and a cyclic alkyl group include, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, it is preferable that R N1 and R N2 are alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the bases generated by decomposition described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesiveness at the time of lamination with a metal (for example, copper).
R N1及R N2可以相互連接而形成環狀結構。在形成環狀結構時,可以在鏈中具有氧原子等。又,R N1及R N2所形成之環狀結構可以為單環,亦可以為縮合環,但是單環為較佳。作為所形成之環狀結構,式(N1)中的含有氮原子之5員環或6員環為較佳,例如可以舉出吡咯環、咪唑環、吡唑環、吡咯啉環、吡咯啶環、咪唑啶環、吡唑啶環、哌啶環、哌𠯤環、嗎啉環等,可以較佳地舉出吡咯啉環、吡咯啶環、哌啶環、哌𠯤環、嗎啉環。 R N1 and R N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R N1 and R N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.
R C1表示氫原子或保護基,氫原子為較佳。 R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
作為保護基,藉由酸或鹼的作用進行分解之保護基為較佳,可以較佳地舉出用酸進行分解之保護基。As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.
作為保護基的具體例,可以舉出鏈狀或環狀的烷基或在鏈中具有氧原子之鏈狀或環狀的烷基。作為鏈狀或環狀的烷基,可以舉出甲基、乙基、異丙基、第三丁基、環己基等。作為在鏈中具有氧原子之鏈狀的烷基,具體而言,可以舉出烷基氧基烷基,更具體而言,可以舉出甲氧基甲(MOM)基、乙氧基乙(EE)基等。作為在鏈中具有氧原子之環狀的烷基,可以舉出環氧基、縮水甘油基、氧環丁烷基、四氫呋喃基、四氫吡喃(THP)基等。Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.
作為構成L之2價的連接基,並無特別規定,但是烴基為較佳,脂肪族烴基為更佳。烴基可以具有取代基,並且亦可以在烴鏈中具有除了碳原子以外的種類的原子。更具體而言,可以在鏈中具有氧原子的2價的烴連接基為較佳,可以在鏈中具有氧原子的2價的脂肪族烴基、2價的芳香族烴基或與可以在鏈中具有氧原子的2價的脂肪族烴基和2價的芳香族烴基的組合有關之基團為更佳,可以在鏈中具有氧原子的2價的脂肪族烴基為進一步較佳。該等基團不具有氧原子為較佳。 2價的烴連接基為碳數1~24者為較佳,2~12為更佳,2~6為進一步較佳。2價的脂肪族烴基為碳數1~12者為較佳,2~6為更佳,2~4為進一步較佳。2價的芳香族烴基為碳數6~22者為較佳,6~18為更佳,6~10為進一步較佳。與2價的脂肪族烴基和2價的芳香族烴基的組合有關之基團(例如,伸芳基烷基)為碳數7~22者為較佳,7~18為更佳,7~10為進一步較佳。 The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.
作為連接基L,具體而言,直鏈或支鏈的鏈狀伸烷基、環狀伸烷基、與鏈狀伸烷基和環狀伸烷基的組合有關之基團、在鏈中具有氧原子之伸烷基、直鏈或支鏈的鏈狀的伸烯基、環狀的伸烯基、伸芳基、伸芳基伸烷基為較佳。 直鏈或支鏈的鏈狀伸烷基為碳數1~12者為較佳,2~6為更佳,2~4為進一步較佳。 環狀伸烷基為碳數3~12者為較佳,3~6為更佳。 與鏈狀伸烷基和環狀伸烷基的組合有關之基團為碳數4~24者為較佳,4~12為更佳,4~6為進一步較佳。 在鏈中具有氧原子之伸烷基可以為鏈狀,亦可以為環狀,並且可以為直鏈,亦可以為支鏈。在鏈中具有氧原子之伸烷基為碳數1~12者為較佳,1~6為更佳,1~3為進一步較佳。 As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.
直鏈或支鏈的鏈狀的伸烯基為碳數2~12者為較佳,2~6為更佳,2~3為進一步較佳。直鏈或支鏈的鏈狀的伸烯基的C=C鍵的數量為1~10者為較佳,1~6為更佳,1~3為進一步較佳。 環狀的伸烯基為碳數3~12者為較佳,3~6為更佳。環狀的伸烯基的C=C鍵的數量為1~6為較佳,1~4為更佳,1~2為進一步較佳。 伸芳基為碳數6~22者為較佳,6~18為更佳,6~10為進一步較佳。 伸芳基伸烷基為碳數7~23者為較佳,7~19為更佳,7~11為進一步較佳。 其中,鏈狀伸烷基、環狀伸烷基、在鏈中具有氧原子之伸烷基、鏈狀的伸烯基、伸芳基、伸芳基、伸烷基為較佳,1,2-伸乙基、丙烷二基(尤其1,3-丙烷二基)、環己烷二基(尤其1,2-環己烷二基)、伸乙烯基(尤其順式伸乙烯基)、伸苯基(1,2-伸苯基)、伸苯基亞甲基(尤其1,2-伸苯基亞甲基)、氧伸乙基(尤其1,2-乙烯氧基-1,2-伸乙基)為更佳。 The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.
作為鹼產生劑,可以舉出下述例,但是本發明並不僅由此做限定性解釋。As the base generator, the following examples can be given, but the present invention is not limited to these.
【化學式47】 [Chemical formula 47]
非離子型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 alkali generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
作為離子型鹼產生劑的具體的較佳化合物,例如亦可以舉出國際公開第2018/038002號的0148~0163段中所記載的化合物。Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
作為銨鹽的具體例,可以舉出以下化合物,但是本發明並不限定於該等。 【化學式48】 Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 48]
作為亞胺鹽的具體例,可以舉出以下化合物,但是本發明並不限定於該等。 【化學式49】 Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 49]
在感光性組成物包含鹼產生劑之情況下,鹼產生劑的含量相對於感光性組成物中的樹脂100質量份為0.1~50質量份為較佳。下限為0.3質量份以上為更佳,0.5質量份以上為進一步較佳。上限為30質量份以下為更佳,20質量份以下為進一步較佳,10質量份以下為更進一步較佳,可以為5質量份以下,亦可以為4質量份以下。 鹼產生劑能夠使用1種或2種以上。在使用2種以上之情況下,合計量在上述範圍內為較佳。 When the photosensitive composition contains an alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the photosensitive composition. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.
<溶劑> 感光性組成物包含溶劑為較佳。 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,可以舉出酯類、醚類、酮類、環狀烴類、亞碸類、醯胺類、脲類、醇類等化合物。 <Solvent> It is preferable that the photosensitive composition contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.
作為酯類,例如可以舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸己酯、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、己酸乙酯、庚酸乙酯、丙二酸二甲酯、丙二酸二乙酯等作為較佳者。Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. , butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, Ethoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), alkyl 3-alkoxypropanoates (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxypropionate alkyl esters (for example, 2-alkane Methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methyl propionate and 2-alkane Ethyl oxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate , dimethyl malonate, diethyl malonate, etc. are preferred.
作為醚類,例如可以舉出乙二醇二甲醚、二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲基醚、二乙二醇丁基甲基醚、三乙二醇二甲醚、四乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、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***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇二甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、乙二醇單丁醚、乙二醇單丁醚乙酸酯、二乙二醇乙基甲基醚、丙二醇單丙醚乙酸酯、二丙二醇二甲醚等作為較佳者。Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.
作為酮類,例如可以舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、3-甲基環己酮、左旋葡聚糖酮、二氫葡聚糖酮等作為較佳者。Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextran ketone, and dihydrodextran Sugar ketones and the like are preferred.
作為環狀烴類,例如可以舉出甲苯、二甲苯、苯甲醚等芳香族烴類、檸檬烯等環式萜烯類作為較佳者。As cyclic hydrocarbons, aromatic hydrocarbons, such as toluene, xylene, and anisole, and cyclic terpenes, such as limonene, are mentioned as preferable ones, for example.
作為亞碸類,例如可以舉出二甲基亞碸作為較佳者。As the sulfites, for example, dimethyl sulfite can be mentioned as a preferable one.
作為醯胺類,可以舉出N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-環己酯-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基異丁醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N-甲醯基嗎啉、N-乙醯基嗎啉等作為較佳者。Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.
作為脲類,可以舉出N,N,N’,N’-四甲基脲、1,3-二甲基-2-咪唑啶酮等作為較佳者。Preferable examples of the urea include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
作為醇類,可以舉出甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、1-戊醇、1-己醇、苯甲醇、乙二醇單甲基醚、1-甲氧基-2-丙醇、2-乙氧基乙醇、二乙二醇單***、二乙二醇單二乙二醇單己醚、三乙二醇單甲基醚、丙二醇單丙二醇單***、丙二醇單甲醚、聚乙二醇單甲基醚、聚丙二醇、四乙二醇、乙二醇單丁醚、乙二醇單乙二醇單芐醚、乙二醇單乙二醇單苯基醚、甲基苯基甲醇、正戊醇、甲基戊醇及雙丙酮醇等。Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl alcohol Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monodiethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, Propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol and diacetone alcohol, etc.
關於溶劑,從塗佈面性狀的改善等觀點考慮,混合2種以上之形態亦較佳。Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., it is also preferable to mix two or more types.
在本發明中,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、左旋葡聚糖酮、二氫葡聚糖酮中之1種溶劑或由2種以上構成之混合溶劑為較佳。同時使用二甲基亞碸和γ-丁內酯或同時使用N-甲基-2-吡咯啶酮和乳酸乙酯為特佳。In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone, one kind of solvent or two or more kinds of solvents The mixed solvent is preferred. It is particularly preferred to use dimethylsulfoxide and γ-butyrolactone together or N-methyl-2-pyrrolidone and ethyl lactate together.
從塗佈性的觀點考慮,將溶劑的含量設為感光性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20~70質量%為更進一步較佳。關於溶劑含量,只要依據塗膜的所期望厚度和塗佈方法進行調節即可。From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the photosensitive composition, It is more preferable to set it as 10-70 mass %, and it is more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
感光性組成物可以僅含有1種溶劑,亦可以含有2種以上。在含有2種以上的溶劑之情況下,其合計在上述範圍內為較佳。The photosensitive composition may contain only one type of solvent, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned range.
<金屬接著性改良劑> 感光性組成物包含用於提高與電極或配線等中所使用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,可以舉出具有烷氧基甲矽烷基之矽烷偶合劑、鋁系接著助劑、鈦系接著助劑、具有磺醯胺結構之化合物及具有硫脲之化合物、磷酸衍生物化合物、β酮酸酯化合物、胺基化合物等。 <Metal Adhesion Improver> It is preferable that the photosensitive composition contains a metal adhesion improver for improving adhesion with a metal material used for electrodes, wiring, and the like. Examples of the metal adhesion improver include alkoxysilyl-containing silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having sulfonamide structures, compounds having thiourea, and phosphoric acid derivatives. Compounds, β-ketoester compounds, amine compounds, etc.
〔矽烷偶合劑〕 作為矽烷偶合劑,例如可以舉出國際公開第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、日本特開2018-173573的0067~0078段中所記載的化合物,並將該等內容編入本說明書中。又,如日本特開2011-128358號公報的0050~0058段中所記載,使用不同的2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,Me表示甲基,Et表示乙基。 [Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP-A No. 2018-173573 are incorporated herein by reference. Moreover, 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 compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.
【化學式50】 【Chemical formula 50】
作為其他矽烷偶合劑,例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-(三甲氧基甲矽烷基丙基)異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基琥珀酸酐。該等能夠單獨使用1種或組合使用2種以上。Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.
〔鋁系接著助劑〕 作為鋁系接著助劑,例如可以舉出鋁三(乙醯乙酸乙酯)鋁、三(乙醯丙酮)鋁、乙醯乙酸乙酯二異丙醇鋁等。 [Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include aluminum tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, aluminum ethylacetate diisopropoxide, and the like.
又,作為其他金屬接著性改良劑,亦能夠使用日本特開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,並將該等內容編入本說明書中。In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the vulcanized compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, and these contents are incorporated into this specification.
金屬接著性改良劑的含量相對於樹脂A100質量份,較佳為0.1~30質量份,更佳為在0.01~10質量份的範圍內,進一步較佳為在0.5~5質量份的範圍內。藉由設為上述下限值以上,圖案與金屬層的接著性變得良好,藉由設為上述上限值以下,圖案的耐熱性、機械特性變得良好。金屬接著性改良劑可以為僅1種,亦可以為2種以上。在使用2種以上之情況下,其合計在上述範圍內為較佳。The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.01 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the resin A. By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.
<遷移抑制劑> 感光性組成物進一步包含遷移抑制劑為較佳。藉由包含遷移抑制劑,能夠有效地抑制源自金屬層(金屬配線)的金屬離子轉移至膜內。 <Migration inhibitor> It is preferable that the photosensitive composition further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.
作為遷移抑制劑,並無特別限制,可以舉出具有雜環(吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡唑環、異噁唑環、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、嗎啉環、2H-吡喃環及6H-吡喃環、三𠯤環)之化合物、具有硫脲類及氫硫基之化合物、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-***、苯并***、3-胺基-1,2,4-***、3,5-二胺基-1,2,4-***等***系化合物、1H-四唑、5-苯基四唑、5-胺基―1H-四唑等四唑系化合物。The migration inhibitor is not particularly limited, and examples include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetra azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, with sulfur Urea and hydrogen thio compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.
或者,亦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 captures 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,並將該等內容編入本說明書中。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 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 compounds, etc., and these contents are incorporated into this specification.
作為遷移抑制劑的具體例,可以舉出下述化合物。Specific examples of the migration inhibitor include the following compounds.
【化學式51】 【Chemical formula 51】
在感光性組成物具有遷移抑制劑之情況下,遷移抑制劑的含量相對於感光性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 photosensitive composition has a migration inhibitor, the content of the migration inhibitor 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 relative to the total solid content of the photosensitive composition. The mass % is more preferable.
遷移抑制劑可以為僅1種,亦可以為2種以上。在遷移抑制劑為2種以上之情況下,其合計在上述範圍內為較佳。Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned range.
<聚合抑制劑> 感光性組成物包含聚合抑制劑為較佳。作為聚合抑制劑,可以舉出酚系化合物、醌系化合物、胺基系化合物、N-氧自由基化合物系化合物、硝基系化合物、亞硝基系化合物、雜芳香環系化合物、金屬化合物等。 <Polymerization inhibitor> It is preferable that the photosensitive composition contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, and the like .
作為聚合抑制劑的具體的化合物,例如較佳地使用對氫醌、鄰氫醌、甲氧基氫醌、鄰甲氧基酚、對甲氧基酚、二-第三丁基-對甲酚、五倍子酚、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-第三丁基酚)、2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、N-亞硝基苯基羥基胺第一鈰鹽、N-亞硝基-N-苯基羥基胺鋁鹽、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)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、1,3,5-三(4-第三丁基-3-羥基)-2,6-二甲基芐基)-1,3,5-三𠯤-2,4,6-(1H,3H,5H)-三酮、4-羥基-2,2,6,6-四甲基哌啶1-氧自由基、2,2,6,6-四甲基哌啶1-氧自由基、吩噻𠯤、啡噁𠯤、1,1-二苯基-2-吡咯肼、二丁基二硫代碳酸銅(II)、硝基苯、N-亞硝基-N-苯基羥胺鋁鹽、N-亞硝基-N-苯基羥基胺銨鹽、Tabon(1,4,4-三甲基-2,3-二氮雜雙環[3.2.2]-壬-2-烯-N,N-二羰基)等。又,亦能夠使用日本特開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,並將該內容編入本說明書中。As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol are preferably used , gallic phenol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butyl) phenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-benzene Hydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2 ,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 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-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris𠯤 -2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetrakis Methylpiperidine 1-oxyl radical, phenothiazine, phenothiazine, 1,1-diphenyl-2-pyrrole hydrazine, dibutyldithiocopper(II), nitrobenzene, N-idene Nitro-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, Tabon (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2 ]-non-2-ene-N,N-dicarbonyl) and so on. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, and the contents are incorporated into the present specification. .
在感光性組成物包含聚合抑制劑之情況下,聚合抑制劑的含量相對於感光性組成物的總固體成分為0.01~20質量%為較佳0.02~15質量%為更佳,0.05~10質量%為進一步較佳。When the photosensitive composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, preferably 0.02 to 15 mass %, more preferably 0.05 to 10 mass % with respect to the total solid content of the photosensitive composition. % is further preferred.
聚合抑制劑可以為僅1種,亦可以為2種以上。在聚合抑制劑為2種以上之情況下,其合計在上述範圍內為較佳。Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.
<酸捕捉劑> 為了減少因從曝光至加熱為止的經時而引起之性能變化,感光性組成物含有酸捕捉劑為較佳。其中,酸捕捉劑是指藉由存在於系統中而能夠捕捉產生酸之化合物,酸度低且pKa高的化合物為較佳。作為酸捕捉劑,具有胺基之化合物為較佳,一級胺、二級胺、三級胺、銨鹽、三級醯胺等為較佳,一級胺、二級胺、三級胺、銨鹽為較佳,二級胺、三級胺、銨鹽為更佳。 作為酸捕捉劑,可以較佳地舉出具有咪唑結構、二氮雜雙環結構、鎓結構、三烷基胺結構、苯胺結構或吡啶結構之化合物、具有羥基和/或醚鍵之烷基胺衍生物、具有羥基和/或醚鍵之苯胺衍生物等。在具有鎓結構之情況下,酸捕捉劑為具有選自銨、重氮、錪、鋶、鏻、吡啶鎓等中之陽離子和酸度比由酸產生劑所產生之酸更低的酸的陰離子之鹽為較佳。 <Acid scavenger> It is preferable that the photosensitive composition contains an acid scavenger in order to reduce the performance change with time from exposure to heating. Among them, the acid scavenger refers to a compound that can capture and generate an acid by being present in the system, and a compound having a low acidity and a high pKa is preferable. As the acid scavenger, compounds with amine groups are preferred, primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred, primary amines, secondary amines, tertiary amines, ammonium salts More preferably, secondary amine, tertiary amine and ammonium salt are more preferable. As the acid scavenger, compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, and alkylamine derivatives having a hydroxyl group and/or an ether bond can be preferably used. compounds, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid scavenger is an anion having a cation selected from the group consisting of ammonium, diazo, iodonium, perium, phosphonium, pyridinium and the like and an acid having a lower acidity than that generated by the acid generator. Salt is preferred.
作為具有咪唑結構之酸捕捉劑,可以舉出咪唑、2,4,5-三苯基咪唑、苯并咪唑、2-苯基苯并咪唑等。作為具有二氮雜雙環結構之酸捕捉劑,可以舉出1,4-二氮雜雙環[2,2,2]辛烷、1,5-二氮雜雙環[4,3,0]壬-5-烯、1,8-二氮雜雙環[5,4,0]十一碳-7-烯等。作為具有鎓結構之酸捕捉劑,可以舉出氫氧化四丁基銨、氫氧化三芳基鋶、氫氧化苯甲醯甲基鋶、具有2-氧代烷基之鋶氫氧化物、具體而言氫氧化三苯基鋶、氫氧化三(第三丁基苯基)鋶、氫氧化雙(第三丁基苯基)錪、氫氧化苯甲醯甲基噻吩鎓、氫氧化2-氧代丙基噻吩鎓等。作為具有三烷基胺結構之酸捕捉劑,可以舉出三(正丁基)胺、三(正辛基)胺等。作為具有苯胺結構之酸捕捉劑,可以舉出2,6-二異丙基苯胺、N,N-二甲基苯胺、N,N-二丁基苯胺、N,N-二己基苯胺等。作為具有吡啶結構之酸捕捉劑,可以舉出吡啶、4-甲基吡啶等。作為具有羥基和/或醚鍵之烷基胺衍生物,可以舉出乙醇胺、二乙醇胺、三乙醇胺、N-苯基二乙醇胺、三(甲氧基乙氧基乙基)胺等。作為具有羥基和/或醚鍵之苯胺衍生物,可以舉出N,N-雙(羥乙基)苯胺等。As an acid scavenger having an imidazole structure, imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole, etc. are mentioned. As an acid scavenger having a diazabicyclic structure, 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]nonane- 5-ene, 1,8-diazabicyclo[5,4,0]undec-7-ene, etc. Examples of the acid scavenger having an onium structure include tetrabutylammonium hydroxide, triaryl perionium hydroxide, benzylmethyl perionium hydroxide, perium hydroxide having a 2-oxoalkyl group, and specifically Triphenyl perium hydroxide, tris(tert-butylphenyl) perium hydroxide, bis(tert-butylphenyl) iodonium hydroxide, benzalkonium methylthiophenium hydroxide, 2-oxopropane hydroxide base thiophenium, etc. Tri(n-butyl)amine, tri(n-octyl)amine, etc. are mentioned as an acid scavenger which has a trialkylamine structure. As an acid scavenger having an aniline structure, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, N,N-dihexylaniline, etc. are mentioned. As an acid scavenger having a pyridine structure, pyridine, 4-picoline, etc. are mentioned. Examples of alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, tris(methoxyethoxyethyl)amine, and the like. N,N-bis(hydroxyethyl)aniline etc. are mentioned as an aniline derivative which has a hydroxyl group and/or an ether bond.
作為較佳的酸捕捉劑的具體例,可以舉出乙醇胺、二乙醇胺、三乙醇胺、乙胺、二乙胺、三乙胺、己胺、十二胺、環己胺、環己基甲基胺、環己基二甲基胺、苯胺、N-甲基苯胺、N,N-二甲基苯胺、二苯基胺、吡啶、丁胺、異丁胺、二丁胺、三丁胺、二環己胺、DBU(二氮雜雙環十一碳)、DABCO(1,4-二氮雜雙環[2.2.2]辛烷)、N,N-二異丙基乙胺、氫氧化四甲銨、乙二胺、1,5-二胺基戊烷、N-甲基己胺、N-甲基二環己胺、三辛基胺、N-乙基乙二胺、N,N―二乙基乙二胺、N,N,N’,N’-四丁基-1,6-己烷二胺、精三胺、二胺基環己烷、雙(2-甲氧基乙基)胺、哌啶、甲基哌啶、哌𠯤、托烷、N-苯基苄胺、1,2-二苯胺基乙烷(dianilinoethane)、2-胺基乙醇、甲苯胺、胺基酚、己基苯胺、伸苯基二胺、苯基乙基胺、二苄胺、吡咯、N-甲基吡咯、胍、胺基吡咯啶、吡唑、吡唑啉、胺基嗎啉、胺基烷基口末啉等。Specific examples of preferable acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, Cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine , DBU (diazabicyclo undecyl), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylene glycol Amine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine Amine, N,N,N',N'-Tetrabutyl-1,6-hexanediamine, Spermine, Diaminocyclohexane, Bis(2-methoxyethyl)amine, Piperidine , methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylaminoethane (dianilinoethane), 2-aminoethanol, toluidine, aminophenol, hexylaniline, benzene diamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrroleidine, pyrazole, pyrazoline, aminomorpholine, aminoalkylamine, etc.
該等酸捕捉劑可以單獨使用1種,可以組合使用2種以上。 本發明之組成物可以含有酸捕捉劑,亦可以不含有酸捕捉劑,但是在含有之情況下,酸捕捉劑的含量以組成物的總固體成分為基準,通常為0.001~10質量%,較佳為0.01~5質量%。 These acid scavengers may be used alone or in combination of two or more. The composition of the present invention may contain an acid scavenger or may not contain an acid scavenger, but when it does contain an acid scavenger, the content of the acid scavenger is usually 0.001 to 10% by mass based on the total solid content of the composition. Preferably it is 0.01-5 mass %.
酸產生劑與酸捕捉劑的使用比例為酸產生劑/酸捕捉劑(莫耳比)=2.5~300為較佳。亦即,從靈敏度、解析度的觀點考慮,莫耳比為2.5以上為較佳,從抑制由浮雕圖案隨著曝光後至加熱處理為止的經時變厚而引起之解析度的降低的觀點考慮,300以下為較佳。酸產生劑/酸捕捉劑(莫耳比)更佳為5.0~200,進一步較佳為7.0~150。The usage ratio of the acid generator and the acid scavenger is preferably acid generator/acid scavenger (molar ratio)=2.5 to 300. That is, from the viewpoints of sensitivity and resolution, the molar ratio is preferably 2.5 or more, and from the viewpoint of suppressing the reduction of the resolution caused by the increase in thickness of the relief pattern with time from exposure to heat treatment. , 300 or less is better. The acid generator/acid scavenger (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.
<其他添加劑> 感光性組成物在可以獲得本發明的效果之範圍內依據需要能夠配合各種的添加物、例如界面活性劑、高級脂肪酸衍生物、熱聚合起始劑、無機粒子、紫外線吸收劑、有機鈦化合物、抗氧化劑、抗凝聚劑、酚系化合物、其他高分子化合物、可塑劑及其他助劑類(例如,消泡劑、阻燃劑等)等。藉由適當含有該等成分,能夠調整膜物理性質等性質。關於該等成分,例如能夠參閱日本特開2012-003225號公報的0183段以後(所對應之美國專利申請公開第2013/0034812號說明書的0237段)的記載及日本特開2008-250074號公報的0101~0104段、0107~0109段等的記載,並將該等內容編入本說明書中。在配合該等添加劑之情況下,將其合計配合量設為感光性組成物的固體成分的3質量%以下為較佳。 <Other additives> Various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, Antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliary agents (eg, defoamer, flame retardant, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 paragraphs 0101 to 0104, paragraphs 0107 to 0109, etc., and these contents are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 mass % or less of the solid content of the photosensitive composition.
〔界面活性劑〕 作為界面活性劑,能夠使用氟系界面活性劑、矽酮系界面活性劑、烴系界面活性劑等各種界面活性劑。界面活性劑可以為非離子型界面活性劑,亦可以為陽離子型界面活性劑,亦可以為陰離子型界面活性劑。 [Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
藉由在感光性組成物中含有界面活性劑,進一步提高作為塗佈液進行製備時的液體特性(尤其,流動性),從而能夠進一步改善塗佈厚的均勻性或省液性。亦即,在使用適用了含有界面活性劑之組成物之塗佈液而形成膜之情況下,被塗佈面與塗佈液的界面張力降低而改善對被塗佈面的潤濕性,從而提高對被塗佈面的塗佈性。因此,能夠更佳地進行厚度不均勻小的均勻厚度的膜形成。By including a surfactant in the photosensitive composition, the liquid properties (especially, fluidity) at the time of preparation as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, it is possible to more preferably form a film with a uniform thickness with little thickness unevenness.
作為氟系界面活性劑,例如可以舉出MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554、MEGAFACE F780、RS-72-K(以上為DIC CORPORATION製)、Fluorad FC430、Fluorad FC431、Fluorad FC171、Novell FC4430、Novell FC4432(以上為3M Japan Limited製)、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、Surflon SC-381、Surflon SC-383、Surflon S-393、Surflon KH-40(以上為ASAHI GLASS CO.,LTD.製)、PF636、PF656、PF6320、PF6520、PF7002(OMNOVA Solutions Inc.製)等。氟系界面活性劑亦能夠使用日本特開2015-117327號公報的0015~0158段中所記載的化合物、日本特開2011-132503號公報的0117~0132段中所記載的化合物,並將該等內容編入本說明書中。亦能夠使用嵌段聚合物作為氟系界面活性劑,作為具體例,例如可以舉出日本特開2011-89090號公報中所記載之化合物,並將該等內容編入本說明書中。 氟系界面活性劑亦能夠較佳地使用含氟高分子化合物,該含氟高分子化合物包含來自具有氟原子之(甲基)丙烯酸酯化合物之重複單元和來自具有2個以上(較佳為5個以上)的伸烷氧基(較佳為乙烯氧基、丙烯氧基)之(甲基)丙烯酸酯化合物之重複單元,亦可以例示下述化合物作為本發明中所使用之氟系界面活性劑。 【化學式52】 Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used, and these The contents are incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, which are incorporated into the present specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a compound having 2 or more (preferably 5 The repeating unit of the (meth)acrylate compound of an alkaneoxy group (preferably vinyloxy group, propyleneoxy group) of more than one), the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention . 【Chemical formula 52】
上述化合物的重量平均分子量較佳為3,000~50,000,5,000~30,000為更佳。 氟系界面活性劑亦能夠將在側鏈上具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例,可以舉出日本特開2010-164965號公報的0050~0090段及0289~0295段中所記載之化合物,並將該內容編入本說明書中。又,作為市售品,例如可以舉出DIC CORPORATION製的MEGAFACE RS-101、RS-102、RS-718K等。 The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, which are incorporated into the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.
氟系界面活性劑中的氟含有率為3~40質量%為較佳,更佳為5~30質量%,特佳為7~25質量%。在塗佈膜的厚度的均勻性或省液性的方面而言,氟含有率在該範圍內的氟系界面活性劑係有效的,在組成物中之溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving properties, and the solubility in the composition is also good.
作為矽酮系界面活性劑,例如可以舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(以上為Dow Corning Toray Co.,Ltd.製)、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上為Momentive performance Materials Inc.製)、KP341、KF6001、KF6002(以上為Shin-Etsu Chemical Co., Ltd.製)、BYK307、BYK323、BYK330(以上為BYK Chemie GmbH製)等。Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co. ., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), etc.
作為烴系界面活性劑,例如可以舉出PIONIN A-76、Newkalgen FS-3PG、PIONIN B-709、PIONIN B-811-N、PIONIN D-1004、PIONIN D-3104、PIONIN D-3605、PIONIN D-6112、PIONIN D-2104-D、PIONIN D-212、PIONIN D-931、PIONIN D-941、PIONIN D-951、PIONIN E-5310、PIONIN P-1050-B、PIONIN P-1028-P、PIONIN P-4050-T等(以上為TAKEMOTO OIL&FAT CO.,LTD.製)等。Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D -6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (the above are manufactured by TAKEMOTO OIL & FAT CO., LTD.), etc.
作為非離子型界面活性劑,可以例示甘油、三羥甲基丙烷、三羥甲基乙烷以及該等乙氧基化物及丙氧基化物(例如,甘油丙氧基化物、甘油乙氧基化物等)、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨糖醇酐脂肪酸酯等。作為市售品,可以舉出Pluronic(註冊商標)L10、L31、L61、L62、10R5、17R2、25R2(BASF公司製)、Tetronic 304、701、704、901、904、150R1(BASF公司製)、Solsperse 20000(Lubrizol Japan Ltd.製)、NCW-101、NCW-1001、NCW-1002(FUJIFILM Wako Pure Chemical Corporation製)、PIONIN D-6112、D-6112-W、D-6315(TAKEMOTO OIL&FAT CO.,LTD製)、OLFIN E1010、Surfynol 104、400、440(Nissin Chemical co.,ltd.製)等。As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (TAKEMOTO OIL&FAT CO., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.
作為陽離子系界面活性劑,具體而言,可以舉出有機矽氧烷聚合物KP341(Shin-Etsu Chemical Co., Ltd.製)、(甲基)丙烯酸系(共)聚合物Polyflow No.75、No.77、No.90、No.95(KYOEISHA CHEMICAL Co.,LTD.製)、W001(Yusho Co.,Ltd.製)等。Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), W001 (manufactured by Yusho Co., Ltd.), and the like.
作為陰離子系界面活性劑,具體而言,可以舉出W004、W005、W017(Yusho Co.,Ltd.製)、SANDET BL(SANYO KASEI Co.Ltd.製)等。Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), SANDET BL (manufactured by SANYO KASEI Co., Ltd.), and the like.
界面活性劑可以僅使用1種,亦可以組合使用2種以上。 界面活性劑的含量相對於組成物的總固體成分為0.001~2.0質量%為較佳,0.005~1.0質量%為更佳。 Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.
〔高級脂肪酸衍生物〕 為了防止因氧引起的聚合阻礙,可以在感光性組成物中添加如二十二酸或二十二酸醯胺的高級脂肪酸衍生物,從而使其在塗佈後的乾燥過程中不均勻地存在於感光性組成物的表面上。 [Higher fatty acid derivatives] In order to prevent the inhibition of polymerization by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the photosensitive composition, so that it is not uniformly present in the drying process after coating on the surface of the photosensitive composition.
又,高級脂肪酸衍生物亦能夠使用國際公開第2015/199219號的0155段中所記載的化合物,並將該內容編入本說明書中。In addition, the compound described in the paragraph 0155 of International Publication No. WO 2015/199219 can also be used as the higher fatty acid derivative, and the content is incorporated in the present specification.
在感光性組成物具有高級脂肪酸衍生物之情況下,高級脂肪酸衍生物的含量相對於感光性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1種,亦可以為2種以上。在高級脂肪酸衍生物為2種以上之情況下,其合計在上述範圍內為較佳。When the photosensitive composition 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 photosensitive composition. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.
〔熱聚合起始劑〕 感光性組成物可以包含熱聚合起始劑,尤其可以包含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開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,亦能夠進行樹脂及聚合性化合物的聚合反應,因此能夠進一步提高耐溶劑性。又,有時上述光聚合起始劑亦具有藉由熱而開始聚合之功能,有時能夠作為熱聚合起始劑而添加。 [Thermal polymerization initiator] The photosensitive composition may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that the solvent resistance can be further improved. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
作為熱自由基聚合起始劑,具體而言,可以舉出日本特開2008-063554號公報的0074~0118段中所記載之化合物,並將該內容編入本說明書中。Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, which are incorporated herein by reference.
在包含熱聚合起始劑之情況下,其含量相對於感光性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%。熱聚合起始劑可以僅含有1種,亦可以含有2種以上。在含有2種以上的熱聚合起始劑之情況下,合計量在上述範圍內為較佳。When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass relative to the total solid content of the photosensitive composition %. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
〔無機粒子〕 感光性組成物可以包含無機微粒。作為無機粒子,具體而言,能夠包含碳酸鈣、磷酸鈣、二氧化矽、高嶺土、滑石、二氧化鈦、氧化鋁、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、玻璃等。 [Inorganic particles] The photosensitive composition may contain inorganic fine particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.
作為上述無機粒子的平均粒徑,0.01~2.0μm為較佳,0.02~1.5μm為更佳,0.03~1.0μm為進一步較佳,0.04~0.5μm為特佳。 微粒的上述平均粒徑為一次粒徑,並且為體積平均粒徑。關於體積平均粒徑,能夠藉由基於Nanotrac WAVE II EX-150(Nikkiso Co., Ltd.製)之動態光散射法進行測定。 在難以進行上述測定之情況下,亦能夠藉由離心沉降透光法、X射線透射法、雷射繞射/散射法進行測定。 The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above-mentioned average particle diameter of the fine particles is a primary particle diameter and a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the laser diffraction/scattering method.
〔紫外線吸收劑〕 感光性組成物可以包含紫外線吸收劑。作為紫外線吸收劑,能夠使用水楊酸酯系、二苯甲酮系、苯并***系、取代丙烯腈系、三𠯤系等紫外線吸收劑。 作為水楊酸酯系紫外線吸收劑的例子,可以舉出水楊酸苯酯、水楊酸對辛基苯酯、水楊酸對第三丁基苯酯等,作為二苯甲酮系紫外線吸收劑的例子,可以舉出2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-辛氧基二苯甲酮等。又,作為苯并***系紫外線吸收劑的例子,可以舉出2-(2’-羥基-3’,5’-二-第三丁基苯基)-5-氯苯并***、2-(2’-羥基-3’-第三丁基-5’-甲基苯基)-5-氯苯并***、2-(2’-羥基-3’-第三戊基-5’-異丁基苯基)-5-氯苯并***、2-(2’-羥基-3’-異丁基-5’-甲基苯基)-5-氯苯并***、2-(2’-羥基-3’-異丁基-5’-丙基苯基)-5-氯苯并***、2-(2’-羥基-3’,5’-二-第三丁基苯基)苯并***、2-(2’-羥基-5’-甲基苯基)苯并***、2-[2’-羥基-5’-(1,1,3,3-四甲基)苯基]苯并***等。 [Ultraviolet absorber] The photosensitive composition may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Examples of benzophenone-based ultraviolet absorbers include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2- -(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.
作為取代丙烯腈系紫外線吸收劑的例子,可以舉出2-氰基-3,3-二苯基丙烯酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯等。進而,作為三𠯤系紫外線吸收劑的例子,可以舉出2-[4-[(2-羥基-3-十二烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-[4-[(2-羥基-3-十三烷氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三𠯤等單(羥基苯基)三𠯤化合物;2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三𠯤、2,4-雙(2-羥基-3-甲基-4-丙氧基苯基)-6-(4-甲基苯基)-1,3,5-三𠯤、2,4-雙(2-羥基-3-甲基-4-己氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三𠯤等雙(羥基苯基)三𠯤化合物;2,4-雙(2-羥基-4-丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三𠯤、2,4,6-三(2-羥基-4-辛氧基苯基)-1,3,5-三𠯤、2,4,6-三[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三𠯤等三(羥基苯基)三𠯤化合物等。Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.
在本發明中,上述各種紫外線吸收劑可以單獨使用1種,亦可以組合使用2種以上。 感光性組成物可以包含紫外線吸收劑,亦可以不包含紫外線吸收劑,但是在包含之情況下,紫外線吸收劑的含量相對於感光性組成物的總固體成分質量為0.001質量%以上且1質量%以下為較佳,0.01質量%以上且0.1質量%以下為更佳。 In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The photosensitive composition may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001 mass % or more and 1 mass % relative to the total solid content mass of the photosensitive composition The following is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.
〔有機鈦化合物〕 本實施形態的感光性組成物可以含有有機鈦化合物。由於感光性組成物含有有機鈦化合物,因此即使在低溫下進行硬化之情況下亦能夠形成耐藥品性優異之樹脂層。 [Organo-titanium compound] The photosensitive composition of the present embodiment may contain an organic titanium compound. Since the photosensitive composition contains an organotitanium compound, a resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.
作為能夠使用的有機鈦化合物,可以舉出有機基經由共價鍵或離子鍵與鈦原子鍵結者。 將有機鈦化合物的具體例示於以下I)~VII)中: I)鈦螯合化合物:其中,感光性組成物的保存穩定性優異,並且可以獲得良好的硬化圖案,從而具有2個以上的烷氧基之鈦螯合化合物為更佳。具體的例子為二異丙醇雙(三乙醇胺)鈦、二(正丁醇)雙(2,4-戊二酮)鈦、二異丙醇雙(2,4-戊二酮)鈦、二異丙醇雙(四甲基庚二酮)鈦、二異丙醇雙(乙醯乙酸乙酯)鈦等。 II)四烷氧基鈦化合物:例如為四(正丁醇)鈦、四乙醇鈦、四(2-乙基己醇)鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、四甲氧基丙醇鈦、四甲基苯氧化鈦、四(正壬醇)鈦、四(正丙醇)鈦、四硬脂醇鈦、四[雙{2,2-(烯丙氧基甲基)丁醇}]鈦等。 III)二茂鈦化合物:例如為五甲基環戊二烯基三甲醇鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟苯基)鈦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦等。 IV)單烷氧基鈦化合物:例如為三(二辛基磷酸酯)異丙醇鈦、三(十二烷苯基磺酸酯)異丙醇鈦等。 V)氧化鈦化合物:例如為氧化鈦雙(戊二酮)、氧化鈦雙(四甲基庚二酮)、酞菁氧化鈦等。 VI)四乙醯丙酮鈦化合物:例如為四乙醯丙酮鈦等。 VII)鈦酸酯偶合劑:例如為異丙基三十二烷基苯磺醯鈦酸鹽等。 As the organotitanium compound that can be used, an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the photosensitive composition has excellent storage stability and can obtain a good hardened pattern, and thus a titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.
其中,作為有機鈦化合物,從發揮更良好的耐藥品性之觀點考慮,選自包括上述I)鈦螯合化合物、II)四烷氧基鈦化合物及III)二茂鈦化合物之群組中的至少1種化合物為較佳。尤其,二異丙醇雙(乙醯乙酸乙酯)鈦、四(正丁醇)鈦及雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦為較佳。Among them, as the organotitanium compound, from the viewpoint of exhibiting better chemical resistance, those selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds and III) titanocene compounds At least one compound is preferred. In particular, bis(ethylacetate)titanium diisopropoxide, tetrakis(n-butoxide)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.
在配合有機鈦化合物之情況下,其配合量相對於樹脂A100質量份為0.05~10質量份為較佳,更較佳為0.1~2質量份。在配合量為0.05質量份以上之情況下,所獲得之硬化圖案更有效地顯現出良好的耐熱性及耐藥品性,另一方面,在配合量為10質量份以下之情況下,組成物的保存穩定性更優異。When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the resin A. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.
〔抗氧化劑〕 感光性組成物可以包含抗氧化劑。藉由含有抗氧化劑作為添加劑,能夠提高硬化後的膜的伸長特性和與金屬材料的密接性。作為抗氧化劑,可以舉出酚化合物、亞磷酸酯化合物及硫醚化合物等。作為酚化合物,能夠使用作為酚系抗氧化劑已知之任意的酚化合物。作為較佳的酚化合物,可以舉出受阻酚化合物。在與酚性羥基相鄰之部位(鄰位)上具有取代基之化合物為較佳。作為上述取代基,碳數1~22的經取代或未經取代的烷基為較佳。又,抗氧化劑為在相同分子內具有酚基及亞磷酸酯基之化合物亦較佳。又,抗氧化劑亦能夠較佳地使用磷系抗氧化劑。作為磷系抗氧化劑,可以舉出三[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-6-基]氧基]乙基]胺、三[2-[(4,6,9,11-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基)氧基]乙基]胺及亞磷酸乙基雙(2,4-二-第三丁基-6-甲基苯基)等。作為抗氧化劑的市售品,例如可以舉出Adekastab AO-20、Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-50F、Adekastab AO-60、Adekastab AO-60G、Adekastab AO-80及Adekastab AO-330(以上為ADEKA CORPORATION製)等。又,抗氧化劑亦能夠使用日本專利第6268967號公報的0023~0048段中所記載之化合物,並將該內容編入本說明書中。又,感光性組成物依據需要可以含有潛在的抗氧化劑。作為潛在的抗氧化劑,可以舉出發揮抗氧化劑功能之部位被保護基保護之化合物,且為藉由在100~250℃下進行加熱或在酸/鹼觸媒存在下在80~200℃下進行加熱以使保護基脫離而發揮抗氧化劑功能之化合物。作為潛在的抗氧化劑,可以舉出國際公開第2014/021023號、國際公開第2017/030005號及日本特開2017-008219號公報中所記載之化合物,並將該內容編入本說明書中。作為潛在的抗氧化劑的市售品,可以舉出ADEKA ARKLS GPA-5001(ADEKA CORPORATION製)等。 作為較佳的抗氧化劑的例子,可以舉出2,2-硫代雙(4-甲基-6-第三丁基酚)、2,6-二-第三丁基酚及式(3)所表示之化合物。 〔Antioxidants〕 The photosensitive composition may contain an antioxidant. By containing an antioxidant as an additive, the elongation property of the film after hardening and the adhesiveness with a metal material can be improved. As an antioxidant, a phenol compound, a phosphite compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. A hindered phenol compound is mentioned as a preferable phenol compound. A compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. In addition, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f] [1,3,2]Dioxaphosphin-2-yl)oxy]ethyl]amine and phosphite ethylbis(2,4-di-tert-butyl-6-methyl) phenyl) etc. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO- 80 and Adekastab AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and the contents are incorporated in the present specification. Moreover, the photosensitive composition may contain a latent antioxidant as needed. As potential antioxidants, compounds in which a site that functions as an antioxidant is protected by a protective group can be mentioned, and are prepared by heating at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst. A compound that functions as an antioxidant when heated to remove the protecting group. Examples of potential antioxidants include compounds described in International Publication No. WO 2014/021023, International Publication No. 2017/030005, and JP 2017-008219 A, the contents of which are incorporated into the present specification. As a commercial item of a potential antioxidant, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Examples of preferable antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and formula (3) the indicated compound.
【化學式53】 【Chemical formula 53】
通式(3)中,R 5表示氫原子或碳數2以上(較佳為碳數2~10)的烷基,R 6表示碳數2以上(較佳為碳數2~10)的伸烷基。R 7表示碳數2以上(較佳為碳數2~10)的伸烷基、包含氧原子及氮原子中的至少任一個之1~4價的有機基。k表示1~4的整數。 In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R 6 represents an extension of carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R 7 represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.
式(3)所表示之化合物抑制樹脂所具有之脂肪族基和酚性羥基的氧化劣化。又,能夠藉由對金屬材料的防鏽作用來抑制金屬氧化。The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group contained in the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.
能夠同時作用於樹脂和金屬材料,因此k為2~4的整數為更佳。作為R 7,可以舉出烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、-O-、-NH-、-NHNH-、組合了該等者等,還可以具有取代基。其中,從在顯影液中的溶解性和金屬密接性的觀點考慮,具有烷基醚基、-NH-為較佳,從與樹脂的相互作用和金屬錯合物形成時之金屬密接性的觀點考慮,-NH-為更佳。 Since it can act on a resin and a metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R 7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.
關於通式(3)所表示之化合物,作為例子,可以舉出以下者,但是並不限於下述結構。The compounds represented by the general formula (3) include the following as examples, but are not limited to the following structures.
【化學式54】 [Chemical formula 54]
【化學式55】 【Chemical formula 55】
【化學式56】 【Chemical formula 56】
【化學式57】 [Chemical formula 57]
抗氧化劑的添加量相對於樹脂為0.1~10質量份為較佳,0.5~5質量份為更佳。藉由將添加量設為0.1質量份以上,即使在高溫高濕環境下,亦容易獲得提高伸長特性或對金屬材料之密接性的效果,並且藉由將添加量設為10質量份以下,例如藉由與光敏劑的相互作用來提高感光性組成物的靈敏度。抗氧化劑可以僅使用1種,亦可以使用2種以上。在使用2種以上之情況下,該等合計量在上述範圍內為較佳。The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, with respect to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the photosensitive composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.
〔抗凝聚劑〕 本實施形態的感光性組成物依據需要可以含有抗凝聚劑。作為抗凝聚劑,可以舉出聚丙烯酸鈉等。 [Anti-agglomeration agent] The photosensitive composition of this embodiment may contain an anti-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.
在本發明中,抗凝聚劑可以單獨使用1種,亦可以組合使用2種以上。 感光性組成物可以包含抗凝聚劑,亦可以不包含抗凝聚劑,但是在包含之情況下,抗凝聚劑的含量相對於感光性組成物的總固體成分質量為0.01質量%以上且10質量%以下為較佳,0.02質量%以上且5質量%以下為更佳。 In this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The photosensitive composition may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01 mass % or more and 10 mass % relative to the total solid mass of the photosensitive composition The following is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.
〔酚系化合物〕 本實施形態的感光性組成物依據需要可以含有酚系化合物。作為酚系化合物,可以舉出Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、亞甲基三-FR-CR、BisRS-26X(以上為產品名稱,Honshu Chemical Industry Co.,Ltd.製)、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F(以上為產品名稱,ASAHI YUKIZAI CORPORATION製)等。 [Phenolic compounds] The photosensitive composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above is the product name, manufactured by ASAHI YUKIZAI CORPORATION), etc.
在本發明中,酚系化合物可以單獨使用1種,亦可以組合使用2種以上。 感光性組成物可以包含酚系化合物,亦可以不包含酚系化合物,但是在包含之情況下,酚系化合物的含量相對於感光性組成物的總固體成分質量為0.01質量%以上且30質量%以下為較佳,0.02質量%以上且20質量%以下為更佳。 In the present invention, the phenolic compound may be used alone or in combination of two or more. The photosensitive composition may or may not contain the phenolic compound, but when included, the content of the phenolic compound is 0.01 mass % or more and 30 mass % relative to the total solid mass of the photosensitive composition The following is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.
〔其他高分子化合物〕 作為其他高分子化合物,可以舉出矽氧烷樹脂、將(甲基)丙烯酸進行共聚而獲得之(甲基)丙烯酸聚合物、酚醛清漆樹脂、甲酚樹脂、聚羥基苯乙烯樹脂及該等共聚物等。其他高分子化合物可以為導入有羥甲基、烷氧基甲基、環氧基等交聯基之改質體。 [Other polymer compounds] Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.
在本發明中,其他高分子化合物可以單獨使用1種,亦可以組合使用2種以上。 感光性組成物可以包含其他高分子化合物,亦可以不包含其他高分子化合物,但是在包含之情況下,其他高分子化合物的含量相對於感光性組成物的總固體成分質量為0.01質量%以上且30質量%以下為較佳,0.02質量%以上且20質量%以下為更佳。 In the present invention, other polymer compounds may be used alone or in combination of two or more. The photosensitive composition may or may not contain other polymer compounds, but when included, the content of the other polymer compounds is 0.01 mass % or more relative to the total solid mass of the photosensitive composition. 30 mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.
<感光性組成物的特性> 關於感光性組成物的黏度,能夠藉由感光性組成物的固體成分濃度來調整。從塗佈膜厚的觀點考慮,1,000mm 2/s~12,000mm 2/s為較佳,2,000mm 2/s~10,000mm 2/s為更佳,2,500mm 2/s~8,000mm 2/s為進一步較佳。只要在上述範圍內,則容易獲得均勻性高的塗佈膜。若為1,000mm 2/s以上,則例如容易以作為再配線層用層間絕緣膜所需要之膜厚進行塗佈,若為12,000mm 2/s以下,則可以獲得塗佈表面形態優異之塗膜。 <Characteristics of the photosensitive composition> The viscosity of the photosensitive composition can be adjusted by the solid content concentration of the photosensitive composition. From the viewpoint of the coating film thickness, 1,000 mm 2 /s to 12,000 mm 2 /s is preferable, 2,000 mm 2 /s to 10,000 mm 2 /s is more preferable, and 2,500 mm 2 /s to 8,000 mm 2 /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. If it is 1,000 mm 2 /s or more, for example, it is easy to coat with a film thickness required as an interlayer insulating film for rewiring layers, and if it is 12,000 mm 2 /s or less, a coating film with excellent coating surface morphology can be obtained. .
<關於感光性組成物的含有物質的限制> 感光性組成物的含水率小於2.0質量%為較佳,小於1.5質量%為更佳,小於1.0質量%為進一步較佳。只要小於2.0%,則提高感光性組成物的保存穩定性。 作為維持水分的含量之方法,可以舉出調整保管條件中之濕度及降低保管時的收容容器的孔隙率等。 <Regulations on Substances Contained in Photosensitive Compositions> The water content of the photosensitive composition is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. As long as it is less than 2.0%, the storage stability of the photosensitive composition will be improved. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like are exemplified.
從絕緣性的觀點考慮,感光性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,可以舉出鈉、鉀、鎂、鈣、鐵、銅、鉻、鎳等,但是作為有機化合物與金屬的錯合物而包含之金屬除外。在包含複數個金屬之情況下,該等金屬的合計在上述範圍內為較佳。From the viewpoint of insulating properties, the metal content of the photosensitive composition is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.
又,作為減少意外包含於感光性組成物中之金屬雜質之方法,可以舉出如下方法:選擇金屬含量少的原料作為構成感光性組成物之原料;對構成感光性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 for reducing the metal impurities accidentally contained in the photosensitive composition, a method of selecting a raw material with a small metal content as a raw material constituting the photosensitive composition; filtering the raw material constituting the photosensitive composition can be mentioned. Filtration; lining the apparatus with Teflon, etc., to carry out distillation under conditions that suppress contamination as much as possible.
若考慮感光性組成物作為半導體材料的用途,則從配線腐蝕性的觀點考慮,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,可以舉出氯原子及溴原子。氯原子及溴原子或氯離子及溴離子的合計分別在上述範圍內為較佳。 作為調節鹵素原子的含量之方法,可以較佳地舉出離子交換處理等。 Considering the use of the photosensitive composition as a semiconductor material, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm. Among them, it is preferable that it is less than 5 mass ppm in the state of halide ions, it is more preferable that it is less than 1 mass ppm, and it is more preferable that it is less than 0.5 mass ppm. As a halogen atom, a chlorine atom and a bromine atom are mentioned. The total of chlorine atoms and bromine atoms or chlorine ions and bromine ions is preferably within the above ranges, respectively. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like can be preferably used.
作為感光性組成物的收容容器,能夠使用先前公知的收容容器。又,作為收容容器,為了抑制雜質混入原材料或感光性組成物中,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。作為該種容器,例如可以舉出日本特開2015-123351號公報中所記載的容器。As the storage container of the photosensitive composition, a conventionally known storage container can be used. In addition, as the container, in order to suppress the contamination of impurities into the raw material or the photosensitive composition, it is also preferable to use a multi-layer 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. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.
<感光性組成物的製備> 感光性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,能夠藉由先前公知的方法來進行。 混合能夠採用基於攪拌葉片之混合、基於球磨機之混合、使罐自身旋轉之混合等。 混合中的溫度為10~30℃為較佳,15~25℃為更佳。 <Preparation of photosensitive composition> The photosensitive composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be performed by a conventionally known method. For the mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating a tank itself, and the like can be employed. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.
又,為了去除感光性組成物中的灰塵或微粒等異物,進行使用過濾器之過濾為較佳。關於過濾器孔徑,例如可以舉出5μm以下之態樣,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。在過濾器的材質為聚乙烯之情況下,HDPE(高密度聚乙烯)為更佳。過濾器可以使用用有機溶劑預先清洗者。在過濾器的過濾步驟中,亦可以串聯或並聯連接複數種過濾器而使用。在使用複數種過濾器之情況下,可以組合使用孔徑或材質不同之過濾器。作為連接態樣,例如可以舉出將孔徑1μm的HDPE過濾器作為第1級且將孔徑0.2μm的HDPE過濾器作為第2級進行串聯連接之態樣。又,可以將各種材料過濾複數次。在過濾複數次之情況下,可以為循環過濾。又,亦可以在加壓之後進行過濾。在加壓並進行過濾之情況下,進行加壓之壓力例如可以舉出0.01MPa以上且1.0MPa以下之態樣,0.03MPa以上且0.9MPa以下為較佳,0.05MPa以上且0.7MPa以下為更佳,0.05MPa以上且0.5MPa以下為進一步較佳。 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,可以舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。 進而,在使用過濾器之過濾之後,還可以實施在減壓狀態下放置填充於瓶中之感光性組成物並進行脫氣之步驟。 [實施例] In addition, in order to remove foreign matter such as dust and particles in the photosensitive composition, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, 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. When the material of the filter is polyethylene, HDPE (High Density Polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm as the first stage and an HDPE filter having a pore diameter of 0.2 μm as the second stage are connected in series. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. Preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine 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 mentioned. Furthermore, after the filtration using a filter, the step of leaving the photosensitive composition filled in the bottle in a reduced pressure state and deaerating may be performed. [Example]
以下,舉出實施例對本發明進行更具體的說明。以下實施例所示之材料、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,本發明的範圍並不限定於以下所示之具體例。除非另有說明,則“份”、“%”為質量基準。Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.
<合成例:聚合物P-1的合成> 在乾燥氮氣流下,使4,4’-氧二鄰苯二甲酸二酐(ODPA、下述化合物)13.96g(0.045莫耳)溶解於NMP(N-甲基-2-吡咯啶酮)100g中。向其中加入MAP(下述化合物)1.09g(0.010莫耳)和NMP20g。進而,加入HFHA(下述化合物)19.95g(0.033莫耳)、Jeffamine(註冊商標)ED600 6.00g(0.010莫耳)、SiDA(下述化合物)0.62g(0.003莫耳)和NMP20g,並在60℃下反應1小時,接著在180℃下攪拌了4小時。攪拌結束之後,將溶液投入到水2L中,從而獲得了白色沉澱物。藉由濾過收集該沉澱並用水清洗3次之後,使用50℃的真空乾燥機乾燥72小時,從而獲得了聚合物P-1的粉末。 【化學式58】 <Synthesis example: Synthesis of polymer P-1> 13.96 g (0.045 mol) of 4,4'-oxydiphthalic dianhydride (ODPA, the following compound) was dissolved in NMP (NMP) under a stream of dry nitrogen. -methyl-2-pyrrolidone) in 100 g. Thereto were added 1.09 g (0.010 mol) of MAP (the compound described below) and 20 g of NMP. Further, 19.95 g (0.033 mol) of HFHA (the following compound), 6.00 g (0.010 mol) of Jeffamine (registered trademark) ED600, 0.62 g (0.003 mol) of SiDA (the following compound), and 20 g of NMP were added, and the mixture was heated to 60 The reaction was carried out for 1 hour at 180°C, followed by stirring at 180°C for 4 hours. After the stirring was completed, the solution was poured into 2 L of water to obtain a white precipitate. After the precipitate was collected by filtration and washed with water three times, it was dried using a vacuum dryer at 50° C. for 72 hours, thereby obtaining a powder of polymer P-1. 【Chemical formula 58】
<合成例:聚合物P-2的合成> 向具備攪拌機、溫度計之燒瓶中加入N-甲基吡咯啶酮60g,並添加2,2’-雙(3-胺基-4-羥基苯基)六氟丙烷13.92g(38mmol)進行攪拌以使其溶解。接著,一邊將溫度保持在0~5℃一邊經10分鐘滴加十二烷二醯氯(Dodecanedioyl dichloride)7.48g(28mmol)及4,4’-二苯基醚二甲醯氯3.56g(12mmol)之後,返回至室溫(25℃)並繼續攪拌3小時。將溶液投入到3升的水中並回收析出物,將其用純水清洗3次之後進行減壓,從而獲得了聚羥基醯胺(以下,稱為P-2)。P-2的重量平均分子量為41,800,分散度為2.0。 聚合物P-2為下述結構的樹脂。在下述記載中,x:y表示各重複單元的含有比(莫耳比)。 【化學式59】 <Synthesis example: Synthesis of polymer P-2> To a flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was added, and 2,2'-bis(3-amino-4-hydroxyphenyl) was added 13.92 g (38 mmol) of hexafluoropropane were stirred and dissolved. Next, 7.48 g (28 mmol) of dodecanedioyl dichloride and 3.56 g (12 mmol) of 4,4'-diphenyl ether dimethyl chloride were added dropwise over 10 minutes while maintaining the temperature at 0 to 5°C. ), return to room temperature (25°C) and continue stirring for 3 hours. The solution was poured into 3 liters of water, and the precipitate was recovered, washed with pure water three times, and then reduced in pressure to obtain polyhydroxyamide (hereinafter, referred to as P-2). The weight average molecular weight of P-2 was 41,800, and the degree of dispersion was 2.0. The polymer P-2 is a resin of the following structure. In the following description, x:y represents the content ratio (molar ratio) of each repeating unit. 【Chemical formula 59】
<合成例:聚合物P-3的合成> 向將4,4’-氧二鄰苯二甲酸二酐(ODPA)23.5g溶解於3-甲氧基-N,N-二甲基丙醯胺190g中而獲得之溶液中滴加將2,2’-二甲基聯苯-4,4’-二胺(DMAP)13g溶解於3-甲氧基-N,N-二甲基丙醯胺75g中而獲得之溶液,並在30℃下攪拌2小時,從而獲得了聚醯胺酸。 在40℃以下向其中加入37g的三氟乙酸酐,在45℃下攪拌3小時之後,加入甲基丙烯酸2-羥基乙酯(HEMA)25.5g,並在40℃下攪拌了10小時。重複3次將該反應液滴加到蒸餾水中,過濾收集沉澱物並進行減壓乾燥之步驟,從而獲得了聚醯亞胺前驅物。 使用凝膠滲透層析(GPC)法,並藉由標準聚苯乙烯換算在以下條件下求出重量平均分子量、數量平均分子量及分散度。聚合物P-3的重量平均分子量為20,000,分散度為1.74。 聚合物P-3為下述結構的樹脂。 【化學式60】 <Synthesis example: Synthesis of polymer P-3> 23.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) was dissolved in 3-methoxy-N,N-dimethylpropionamide 13 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dissolved in 3-methoxy-N,N-dimethylpropionamide by dropwise addition to the solution obtained in 190 g 75 g of the obtained solution was stirred at 30° C. for 2 hours to obtain a polyamic acid. To this was added 37 g of trifluoroacetic anhydride at 40° C. or lower, and after stirring at 45° C. for 3 hours, 25.5 g of 2-hydroxyethyl methacrylate (HEMA) was added, and the mixture was stirred at 40° C. for 10 hours. The reaction was added dropwise to distilled water three times, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide precursor. Using gel permeation chromatography (GPC), the weight average molecular weight, the number average molecular weight, and the degree of dispersion were determined by standard polystyrene conversion under the following conditions. The weight average molecular weight of polymer P-3 was 20,000, and the degree of dispersion was 1.74. The polymer P-3 is a resin of the following structure. 【Chemical formula 60】
<合成例:聚合物P-4的合成> 混合20.0g(64.5毫莫耳)的4,4’-氧二鄰苯二甲酸酐(在140℃下乾燥12小時)、16.8g(129毫莫耳)的甲基丙烯酸2-羥乙酯、0.05g的氫醌、20.4g(258毫莫耳)的吡啶及100g的二甘醇二甲醚。之後,在60℃的溫度下攪拌18小時,從而製造了4,4’-氧代二鄰苯二甲酸和甲基丙烯酸2-羥乙酯的二酯。接著,將反應混合物冷卻至-5℃,一邊將溫度保持在-5±2℃一邊經2小時加入了16.12g(135.5毫莫耳)的SOCl 2。接著,將使11.32g(60.0毫莫耳)的4,4’-二胺基二苯醚溶解於100mL的N-甲基吡咯啶酮中而獲得之溶液調整在-5~0℃的溫度範圍內的同時,經2小時滴加到反應混合物中。在使反應混合物在0℃下反應1小時之後,加入70g的乙醇,並在室溫下攪拌1小時。 接著,使聚醯亞胺前驅物在5升的水中沉澱,並將水-聚醯亞胺前驅物混合物以5,000rpm的速度攪拌了15分鐘。過濾去除聚醯亞胺前驅物,在4升的水中再次攪拌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在45℃下乾燥2天,從而獲得了聚合物P-4。該聚合物P-4(聚醯亞胺前驅物)的重量平均分子量為18,000。 聚合物P-4為下述結構的樹脂。 【化學式61】 <Synthesis example: Synthesis of polymer P-4> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) were mixed ear) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 100 g of diglyme. Then, it stirred at the temperature of 60 degreeC for 18 hours, and produced the diester of 4,4'- oxodiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -5°C, and 16.12 g (135.5 mmol) of SOCl 2 was added over 2 hours while maintaining the temperature at -5±2°C. Next, a solution obtained by dissolving 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C was added dropwise to the reaction mixture over a period of 2 hours. After the reaction mixture was allowed to react at 0°C for 1 hour, 70 g of ethanol was added and stirred at room temperature for 1 hour. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45° C. for 2 days under reduced pressure to obtain polymer P-4. The weight average molecular weight of the polymer P-4 (polyimide precursor) was 18,000. The polymer P-4 is a resin of the following structure. [Chemical formula 61]
<合成例:聚合物P-5的合成> 將4,4’-氧二鄰苯二甲酸二酐(ODPA)7.76g(25毫莫耳)及3,3’,4,4’-聯苯四羧酸二酐6.23g(25毫莫耳)加入反應容器中,並加入了甲基丙烯酸2-羥乙酯(HEMA)13.4g及γ―丁內酯100ml。在室溫下一邊攪拌一邊加入吡啶7.91g,從而獲得了反應混合物。基於反應之發熱結束之後,冷卻至室溫,並進一步靜置了16小時。 接著,在冰冷卻下,將二環己基碳二醯亞胺(DCC)20.6g(99.9毫莫耳)溶解於γ-丁內酯30ml中而獲得之溶液一邊攪拌一邊經40分鐘加入到反應混合物中。接著,一邊攪拌一邊經60分鐘加入了將4,4’-二胺基二苯醚(DADPE)9.3g(46毫莫耳)懸浮於γ-丁內酯350ml中之懸浮液。 進而,在室溫下攪拌2小時之後,加入乙醇3ml並攪拌了1小時。之後,加入了γ-丁內酯100ml。藉由過濾而去除在反應混合物中所產生之沉澱物,從而獲得了反應液。 將所獲得之反應液加入3升的乙醇中,從而生成由粗聚合物形成之沉澱物。濾取所生成之粗聚合物並將其溶解於四氫呋喃200ml中,從而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加到3升的水中以使聚合物沉澱,並濾取所獲得之沉澱物之後進行真空乾燥,從而獲得了粉末狀的聚合物P-5。 測定該聚合物的重量平均分子量(Mw),其結果,為23,000。 聚合物P-5為下述結構的樹脂。括號的下標表示各重複單元的莫耳比。 【化學式62】 <Synthesis example: Synthesis of polymer P-5> 7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3',4,4'-biphenyl 6.23 g (25 mmol) of tetracarboxylic dianhydride was added to the reaction vessel, and 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone were added. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the heat generation by the reaction was completed, it was cooled to room temperature, and was further left to stand for 16 hours. Next, under ice-cooling, a solution obtained by dissolving 20.6 g (99.9 mmol) of dicyclohexylcarbodiimide (DCC) in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. middle. Next, a suspension of 9.3 g (46 mmol) of 4,4′-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. Furthermore, after stirring at room temperature for 2 hours, 3 ml of ethanol was added and the mixture was stirred for 1 hour. After that, 100 ml of γ-butyrolactone was added. A reaction liquid was obtained by removing the precipitate generated in the reaction mixture by filtration. The obtained reaction solution was added to 3 liters of ethanol, whereby a precipitate formed of a crude polymer was generated. The resulting crude polymer was collected by filtration and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 3 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain a powdery polymer P-5. The weight average molecular weight (Mw) of this polymer was measured, and as a result, it was 23,000. The polymer P-5 is a resin of the following structure. Subscripts in parentheses indicate the molar ratio of each repeating unit. 【Chemical formula 62】
<實施例及比較例> 混合下述表中所記載的成分,從而獲得了組成物1~9。 表中所記載的數值為由“質量份”表示各成分的含量者。 將所獲得之組成物通過過濾器孔徑為0.8μm的聚四氟乙烯製過濾器來進行了加壓過濾。 又,在表中,“-”的記載表示不含有對應之成分。 <Examples and Comparative Examples> Compositions 1 to 9 were obtained by mixing the components described in the following tables. The numerical values described in the tables are those expressed by "parts by mass" as the content of each component. The obtained composition was subjected to pressure filtration through a filter made of polytetrafluoroethylene having a filter pore diameter of 0.8 μm. In addition, in the table|surface, the description of "-" means that the corresponding component is not contained.
【表1】
表中所記載之各成分的詳細內容如下。The details of each component described in the table are as follows.
〔樹脂〕 ·P-1~P-5:如上述合成之P-1~P-5 [resin] ·P-1~P-5: P-1~P-5 synthesized as above
〔聚合性化合物〕 ·B-1:SR-209(Sartomer公司製) ·B-2:NIKALAC MX-270(Sanwa Chemical Co.,Ltd.製) ·B-3:TML-BPA(Honshu Chemical Industry Co.,Ltd.製) ·B-4:三乙二醇二甲基丙烯酸酯 ·B-5:Shin-Nakamura Chemical Co.,Ltd.製、A-TMMT [Polymerizable compound] · B-1: SR-209 (manufactured by Sartomer) · B-2: NIKALAC MX-270 (manufactured by Sanwa Chemical Co., Ltd.) ·B-3: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.) ·B-4: Triethylene glycol dimethacrylate ·B-5: A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
〔光敏劑〕 ·C-1:Irgacure OXE-01(BASF公司製) ·C-2:Irgacure 784(BASF公司製) ·C-3:下述結構的化合物。2:1表示各結構的莫耳比。 【化學式63】 [Photosensitizer] - C-1: Irgacure OXE-01 (manufactured by BASF Corporation) - C-2: Irgacure 784 (manufactured by BASF Corporation) - C-3: A compound of the following structure. 2:1 represents the molar ratio of each structure. [Chemical formula 63]
〔金屬接著性改良劑〕 ·D-1:γ脲基丙基三乙基矽烷 ·D-2:N-[3-(三乙氧基甲矽烷基)丙基]順丁烯二醯胺酸(CAS.33525-68-7) [Metal Adhesion Improver] D-1: gamma ureidopropyl triethylsilane D-2: N-[3-(triethoxysilyl)propyl]maleic acid (CAS.33525-68-7)
〔遷移抑制劑〕 ·E-1:(5-胺基四唑) ·E-2:四唑 [Migration inhibitor] ·E-1: (5-aminotetrazole) · E-2: Tetrazole
〔聚合抑制劑〕 ·F-1:2MeHQ(甲氧基氫醌) ·F-2:Tabon(1,4,4-三甲基-2,3-二氮雜雙環[3.2.2]-壬-2-烯-N,N-二羰基) ·F-3:PBQ(對苯醌) ·F-4:MEHQ(4-甲氧基酚) [Polymerization inhibitor] · F-1: 2MeHQ (methoxyhydroquinone) F-2: Tabon (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dicarbonyl) · F-3: PBQ (p-benzoquinone) · F-4: MEHQ (4-methoxyphenol)
〔鹼產生劑〕 ·G-1:(1-[4-(2-羥乙基)-1-哌啶基(Piperidinyl)]-3-(2-羥基苯基)-1-丙酮) ·G-2:(下述結構的化合物) 【化學式64】 [Base generator] G-1: (1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone) G -2: (Compound of the following structure) [Chemical formula 64]
〔添加劑〕 ·H-1:下述結構的化合物 ·H-2:下述結構的化合物 ·H-3:7-二乙胺基-4-甲基香豆素 【化學式65】 [Additive] · H-1: Compound of the following structure · H-2: Compound of the following structure · H-3: 7-diethylamino-4-methylcoumarin [Chemical formula 65]
〔溶劑〕 ·I-1:GBL(γ-丁內酯) ·I-2:DMSO(二甲基亞碸) ·I-3:MDM(二乙二醇二甲醚) ·I-4:IPA(異丙醇) ·I-5:EL(乳酸乙酯) ·I-6:NMP(N-甲基-2-吡咯啶酮) [Solvent] I-1: GBL (gamma-butyrolactone) · I-2: DMSO (dimethyl sulfoxide) ·I-3: MDM (diethylene glycol dimethyl ether) I-4: IPA (isopropyl alcohol) ·I-5: EL (ethyl lactate) I-6: NMP (N-methyl-2-pyrrolidone)
〔評價〕 <硬化物的製作方法> 藉由旋塗法將下述表的“組成物”一欄中所記載的各感光性組成物適用於矽晶圓上,從而形成了感光性層。在加熱板上將形成有上述感光性層之矽晶圓在100℃下乾燥5分鐘,從而在矽晶圓上形成了表的“膜厚(μm)”一欄中所記載的厚度均勻的感光性層。 在使用除了組成物2以外的組成物作為組成物之例子中,在矽晶圓上的感光性層上載置條狀樣品(3mm×30mm)評價用光罩,並照射了400mJ/cm 2的紫外線(寬頻光)。在使用除了組成物5以外的組成物作為組成物之例子中,使用環戊酮對曝光後的感光性層進行60秒鐘的顯影,並用PGMEA進行了沖洗。在使用組成物5作為組成物之例子中,使用2.38質量%TMAH(氫氧化四甲銨)水溶液對曝光後的感光性層進行顯影,並用純水進行了沖洗。之後,使用表的“加熱裝置(波長)”一欄中所記載的加熱裝置,將“升溫溫度”一欄中所記載的加熱溫度維持“加熱時間”一欄中所記載的時間以使其硬化,從而獲得了硬化後的樹脂層。在表中的“環境”一欄中記載為“N 2”之例子中,上述加熱在氮氣環境下進行,在記載為“N 2+O 2(500ppm)”之例子中,上述加熱在包含500ppm的氧氣之氮氣環境下進行。 在“加熱裝置(波長)”一欄中記載為IR之例子中,使用ADVANCE RIKO, Inc.製的紅外線燈加熱裝置RTP-6進行加熱。 在“加熱裝置(波長)”一欄中記載為Box烘箱之例子中,使用Koyo Thermo Systems Co., Ltd.製的潔淨烘箱CLH-21進行加熱。 將上述硬化後的樹脂層浸漬於3質量%氫氟酸溶液中,並從矽晶圓剝離樹脂層,從而獲得了硬化物。 在使用組成物2作為組成物之例子中,不進行曝光及顯影,除此以外,藉由相同的方法進行加熱來製備硬化物,並使用切割器將所剝離之硬化物切割成3mmx30mm的條狀樣品。 [Evaluation] <Preparation method of cured product> The photosensitive layer was formed by applying each photosensitive composition described in the column of "composition" in the following table to a silicon wafer by spin coating. The silicon wafer on which the photosensitive layer was formed was dried at 100° C. for 5 minutes on a hot plate to form a photosensitive film with a uniform thickness described in the column of “film thickness (μm)” in the table on the silicon wafer. sexual layer. In the example of using compositions other than composition 2 as compositions, a strip-shaped sample (3 mm × 30 mm) evaluation mask was placed on the photosensitive layer on the silicon wafer, and 400 mJ/cm 2 of ultraviolet rays were irradiated (broadband light). In the example in which a composition other than Composition 5 was used as the composition, the exposed photosensitive layer was developed for 60 seconds using cyclopentanone, and rinsed with PGMEA. In the example using the composition 5 as a composition, the photosensitive layer after exposure was developed using a 2.38 mass % TMAH (tetramethylammonium hydroxide) aqueous solution, and rinsed with pure water. Then, using the heating device described in the column of "heating device (wavelength)" in the table, the heating temperature described in the column of "heating temperature" is maintained for the time described in the column of "heating time" to cure , thereby obtaining a hardened resin layer. In the example described as "N 2 " in the column of "environment" in the table, the heating was performed in a nitrogen atmosphere, and in the example described as "N 2 +O 2 (500 ppm)", the heating was performed at 500 ppm including 500 ppm carried out in an oxygen-nitrogen atmosphere. In the example described as IR in the column of "heating device (wavelength)", heating was performed using an infrared lamp heating device RTP-6 manufactured by ADVANCE RIKO, Inc. In the example described as a Box oven in the column of "heating device (wavelength)", the heating was performed using a clean oven CLH-21 manufactured by Koyo Thermo Systems Co., Ltd. The cured resin layer was immersed in a 3 mass % hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a cured product. In the example in which the composition 2 was used as the composition, the exposure and development were not carried out, except that the cured product was heated by the same method to prepare a cured product, and the peeled cured product was cut into strips of 3 mm x 30 mm using a cutter sample.
<斷裂伸長率的評價方法> 使用Instron公司製的5960雙柱台式試驗機對所獲得之硬化物(條狀樣品)的斷裂伸長率進行測定。 按照下述評價基準進行評價,評價結果記載於表的“斷裂伸長率”一欄中。 -評價基準- A:超過了60%。 B:超過55%且為60%以下。 C:超過50%且為55%以下。 D:為50%以下。 <Evaluation method of elongation at break> The elongation at break of the obtained hardened|cured material (stripe sample) was measured using the 5960 double-column bench-top tester manufactured by Instron. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "elongation at break" in the table. -Evaluation criteria- A: More than 60%. B: More than 55% and 60% or less. C: More than 50% and 55% or less. D: 50% or less.
<玻璃轉移溫度的測定方法> 使用UBM公司製的Rheogel E4000對所獲得之硬化物的玻璃轉移溫度(Tg)進行測定。 按照下述評價基準進行評價,評價結果記載於表的“Tg”一欄中。 -評價基準- A:Tg超過了250℃。 B:Tg超過200℃且為250℃以下。 C:Tg為200℃以下。 <Measuring method of glass transition temperature> The glass transition temperature (Tg) of the obtained hardened|cured material was measured using the Rheogel E4000 by UBM company. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "Tg" in the table. -Evaluation criteria- A: Tg exceeds 250°C. B: Tg exceeds 200°C and is 250°C or lower. C: Tg is 200°C or lower.
<耐藥品性的評價方法> 將所獲得之硬化物在加熱至75℃的抗蝕劑剝離液(MS6310)中浸漬15分鐘,用流水清洗1分鐘並進行了風乾。之後,依據浸漬於上述抗蝕劑剝離液中之前或之後的膜厚的變化率(%)對耐藥品性進行了評價。 上述變化率(%)為由下述式表示之值。 變化率(%)=浸漬於抗蝕劑剝離液中之後的硬化物的膜厚(μm)/浸漬於抗蝕劑剝離液中之前的硬化物的膜厚(μm)×100 按照下述評價基準進行評價,評價結果記載於表的“耐藥品性”一欄中。 -評價基準- A:超過了85%。 B:超過75%且為85%以下。 C:超過65%且為75%以下。 D:為65%以下。 <Method for evaluating chemical resistance> The obtained cured product was immersed in a resist stripping solution (MS6310) heated to 75° C. for 15 minutes, washed with running water for 1 minute, and air-dried. Then, the chemical resistance was evaluated based on the change rate (%) of the film thickness before and after the immersion in the above-mentioned resist stripping solution. The above-mentioned change rate (%) is a value represented by the following formula. Change rate (%)=film thickness of cured product after immersion in resist stripping solution (μm)/film thickness of cured product before immersion in resist stripping solution (μm)×100 The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "chemical resistance" in the table. -Evaluation criteria- A: More than 85%. B: More than 75% and 85% or less. C: More than 65% and 75% or less. D: It is 65% or less.
【表2】
從以上結果可知,依據本發明的硬化物的製造方法,可以獲得耐藥品性優異之硬化物。 在比較例1中,不包含電磁波照射步驟,而是藉由箱式烘箱進行加熱。 在比較例2中,組成物不是感光性組成物。 在該等比較例中,可知耐藥品性差。 From the above results, according to the method for producing a cured product of the present invention, a cured product excellent in chemical resistance can be obtained. In Comparative Example 1, the electromagnetic wave irradiation step was not included, but heating was performed by a box oven. In Comparative Example 2, the composition was not a photosensitive composition. In these comparative examples, it turns out that chemical resistance is inferior.
<實施例101> 藉由旋塗法將上述組成物1以層狀適用於表面上形成有銅薄層之樹脂基材的銅薄層的表面上,並在100℃下乾燥了300秒鐘。膜厚設為所獲得之硬化物的膜厚成為5μm之膜厚。之後,使用步進機(Nikon Co.,Ltd.製、NSR1505 i6)進行了曝光。關於曝光,經由遮罩(圖案為1:1線與空間、線寬為10μm的二元遮罩)在波長365nm下進行。曝光後,在120℃下加熱了300秒鐘。上述加熱後,使用環戊酮進行顯影,並用PGMEA進行沖洗,從而獲得了層的圖案。 接著,使用IR烘箱(ADVANCE RIKO, Inc.製RTP-6),以5℃/秒鐘的升溫速度進行升溫,在達到240℃之後,維持30分鐘以將層進行硬化,從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元件,其結果,確認到正常動作。 <Example 101> The above-mentioned composition 1 was applied to the surface of the copper thin layer of the resin substrate having the copper thin layer formed thereon in a layer form by spin coating, and was dried at 100° C. for 300 seconds. The film thickness was set so that the film thickness of the obtained cured product was 5 μm. Then, exposure was performed using a stepper (Nikon Co., Ltd. make, NSR1505 i6). For exposure, via a mask (binary mask with 1:1 line and space pattern, line width 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 120°C for 300 seconds. After the above heating, development was performed using cyclopentanone, followed by rinsing with PGMEA to obtain a layer pattern. Next, using an IR oven (RTP-6 manufactured by ADVANCE RIKO, Inc.), the temperature was increased at a temperature increase rate of 5°C/sec, and after reaching 240°C, the layer was maintained for 30 minutes to harden, thereby forming a rewiring layer. Use an interlayer insulating film. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.
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