TW202323370A - Photosensitive composition, dry film, cured product, and electronic component - Google Patents
Photosensitive composition, dry film, cured product, and electronic component Download PDFInfo
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- TW202323370A TW202323370A TW111132703A TW111132703A TW202323370A TW 202323370 A TW202323370 A TW 202323370A TW 111132703 A TW111132703 A TW 111132703A TW 111132703 A TW111132703 A TW 111132703A TW 202323370 A TW202323370 A TW 202323370A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- 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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
Description
本發明為關於包含聚苯醚之感光性組成物、乾膜、硬化物及電子零件。The present invention relates to a photosensitive composition containing polyphenylene ether, a dry film, a cured product and an electronic part.
半導體裝置等電子零件中,形成絕緣層、保護膜、導體層之圖案時,多使用光微影法。In electronic components such as semiconductor devices, photolithography is often used to form patterns of insulating layers, protective films, and conductive layers.
光微影法係於矽晶圓、覆銅層合板等基材上形成由感光性組成物所構成的層,光照射(曝光)規定之圖案後,以顯影液溶解去除未曝光部或曝光部之任一者以形成圖案之方法。 這種光微影法,具有:使曝光部溶解於顯影液的方式,即正型;與(曝光部不溶於顯影液,)使未曝光部溶解於顯影液的方式,即負型。 The photolithography method is to form a layer composed of a photosensitive composition on a substrate such as a silicon wafer or a copper-clad laminate. After the light is irradiated (exposed) to a prescribed pattern, the unexposed part or the exposed part is dissolved and removed with a developing solution. Either of them is a method of forming a pattern. This photolithography method has: the method of dissolving the exposed part in the developer, that is, the positive type; and the method of dissolving the unexposed part in the developer (the exposed part is insoluble in the developer), that is, the negative type.
考量該顯影步驟之差異,例如,為了以負型形成解析度高的圖案,要求所使用的感光性組成物兼具曝光部對於顯影液之耐溶解性與未曝光部對於顯影液的優異之溶解性,換言之,要求曝光部與未曝光部之顯影速度差(顯影對比)大。Considering the difference in the development steps, for example, in order to form a high-resolution pattern in the negative type, the photosensitive composition used is required to have both the resistance to dissolution of the exposed part in the developing solution and the excellent dissolution of the unexposed part in the developing solution In other words, it is required that the development speed difference (development contrast) between the exposed part and the unexposed part is large.
另一方面,電子零件的絕緣材中,就抑制對於高頻帶訊號之傳輸損耗的觀點而言,而檢討降低相對介電率(Dk)、介電正切(Df)等介電特性。例如專利文獻1及2中已揭示作為印刷配線板之永久保護膜之阻焊劑等為有用之降低介電正切的負型感光性樹脂組成物。 [先前技術文獻] [專利文獻] On the other hand, in insulating materials for electronic parts, from the viewpoint of suppressing transmission loss for high frequency band signals, it is considered to reduce dielectric properties such as relative permittivity (Dk) and dielectric tangent (Df). For example, Patent Documents 1 and 2 have disclosed that solder resist as a permanent protective film of a printed wiring board is a useful negative photosensitive resin composition for lowering the dielectric tangent. [Prior Art Literature] [Patent Document]
專利文獻1:日本特開2017-15890號公報 專利文獻2:日本特開2017-68242號公報 Patent Document 1: Japanese Patent Laid-Open No. 2017-15890 Patent Document 2: Japanese Patent Laid-Open No. 2017-68242
[發明所欲解決之課題][Problem to be Solved by the Invention]
然而,專利文獻1及2之感光性樹脂組成物中,作為組成物成分,即使藉由用於賦予顯影性之羧基等親水性基、或用於賦予光聚合性之(甲基)丙烯酸酯基來降低介電特性,但仍有極限。However, in the photosensitive resin compositions of Patent Documents 1 and 2, as composition components, even if a hydrophilic group such as a carboxyl group for imparting developability or a (meth)acrylate group for imparting photopolymerization To reduce the dielectric properties, but there is still a limit.
本發明之目的在於將提供介電特性低與顯影對比優異之感光性組成物作為課題。 [用以解決課題之手段] The object of the present invention is to provide a photosensitive composition having low dielectric properties and excellent development contrast. [Means to solve the problem]
本發明人等著眼於可溶於有機溶劑的具有分支構造之聚苯醚、將該有機溶劑作為顯影液的光微影法並努力進行研究。其結果,本發明人等發現藉由組合摻合有由特定之原料苯酚類所得的2種聚苯醚、與導入於該聚苯醚中之與不飽和碳鍵進行自由基聚合的化合物之感光性組成物,可有利於解決上述課題,從而完成本發明。亦即,本發明為如以下者。The inventors of the present invention focused on polyphenylene ether having a branched structure soluble in an organic solvent, and conducted intensive studies using photolithography using the organic solvent as a developing solution. As a result, the inventors of the present invention found that by combining two kinds of polyphenylene ethers obtained from specific raw material phenols and a compound introduced into the polyphenylene ethers to radically polymerize unsaturated carbon bonds, the photosensitive The property composition can be advantageous in solving the above-mentioned problems, thereby completing the present invention. That is, the present invention is as follows.
本發明為一種感光性組成物,其包含:聚苯醚A、聚苯醚B、具有可與不飽和碳鍵進行自由基聚合之官能基的化合物、與光自由基產生劑, 前述聚苯醚A與前述聚苯醚B分別係由包含至少滿足下述條件1的苯酚類與至少滿足下述條件2的苯酚類的原料苯酚類所得, 前述聚苯醚A係重量平均分子量為超過40,000且200,000以下,並且,滿足條件2的苯酚類相對於合成時之原料苯酚類全體的含量未滿20mol%, 前述聚苯醚B係滿足條件2的苯酚類相對於合成時之原料苯酚類全體的含量為20mol%以上。 (條件1) 於鄰位及對位具有氫原子 (條件2) 於對位具有氫原子,且具有包含不飽和碳鍵之官能基 The present invention is a photosensitive composition, which includes: polyphenylene ether A, polyphenylene ether B, a compound having a functional group capable of radical polymerization with an unsaturated carbon bond, and a photoradical generator, The polyphenylene ether A and the polyphenylene ether B are obtained from raw material phenols including phenols satisfying at least the following condition 1 and phenols satisfying at least the following condition 2, respectively, The polyphenylene ether A-based weight average molecular weight is more than 40,000 and not more than 200,000, and the content of phenols satisfying condition 2 is less than 20 mol% with respect to the entire raw material phenols at the time of synthesis, The content of the polyphenylene ether B-based phenols satisfying Condition 2 is 20 mol% or more relative to the entire raw material phenols at the time of synthesis. (Condition 1) Has hydrogen atoms in the ortho and para positions (Condition 2) Has a hydrogen atom at the para position and has a functional group containing an unsaturated carbon bond
前述聚苯醚B係重量平均分子量較佳為5,000以上40,000以下。 前述聚苯醚A與前述聚苯醚B之含有比例(聚苯醚A:聚苯醚B)係以質量比計,較佳為25:75~75:25。 前述可與不飽和碳鍵進行自由基聚合之官能基較佳為硫醇基及/或烯丙基。 The polyphenylene ether B-based weight average molecular weight is preferably not less than 5,000 and not more than 40,000. The content ratio of the aforementioned polyphenylene ether A to the aforementioned polyphenylene ether B (polyphenylene ether A: polyphenylene ether B) is based on a mass ratio, preferably 25:75-75:25. The aforementioned functional groups capable of radical polymerization with unsaturated carbon bonds are preferably thiol groups and/or allyl groups.
本發明可為具有由前述感光性組成物所構成之樹脂層之乾膜。The present invention may be a dry film having a resin layer composed of the aforementioned photosensitive composition.
本發明可為前述感光性組成物或前述樹脂層之硬化物。The present invention may be a cured product of the aforementioned photosensitive composition or the aforementioned resin layer.
本發明可為具有前述硬化物之電子零件。 [發明的效果] The present invention may be an electronic component having the aforementioned cured product. [Effect of the invention]
根據本發明而可能提供介電特性低與顯影對比優異之感光性組成物。According to the present invention, it is possible to provide a photosensitive composition with low dielectric properties and excellent development contrast.
本實施形態之硬化性組成物為光微影法所使用之感光性組成物。The curable composition of this embodiment is a photosensitive composition used in photolithography.
以下,感光性組成物可僅標示為「硬化性組成物」。又,本說明書中,可將「樹脂組成物」作為「硬化性組成物」的意義來使用。Hereinafter, the photosensitive composition may only be referred to as "curable composition". In addition, in this specification, "resin composition" can be used in the meaning of "curable composition".
所說明之化合物存在異構物的情況下,只要未特別排除,則本發明可能使用可存在之全部異構物。When there are isomers in the illustrated compounds, all the isomers that may exist may be used in the present invention unless specifically excluded.
本發明中,「不飽和碳鍵」只要未特別排除,則表示乙烯性或乙炔性之碳-碳多重鍵(雙鍵或三鍵)。In the present invention, "unsaturated carbon bond" means an ethylenic or acetylene carbon-carbon multiple bond (double bond or triple bond) unless specifically excluded.
本發明中,作為具有不飽和碳鍵之官能基,並未特別限定,例舉有烯基(例如,乙烯基、烯丙基)、炔基(例如,乙炔基)、或(甲基)丙烯醯基,就硬化性優異的觀點而言,可選擇乙烯基、烯丙基、(甲基)丙烯醯基,其中就低介電特性優異的觀點而言,較佳為烯丙基。另外,該等具有不飽和碳鍵之官能基,可將碳數設為例如15以下,10以下,8以下,5以下,3以下等。In the present invention, the functional group having an unsaturated carbon bond is not particularly limited, and examples include alkenyl (for example, vinyl, allyl), alkynyl (for example, ethynyl), or (meth)acrylic As the acyl group, vinyl, allyl, and (meth)acryl can be selected from the viewpoint of excellent curability, and among them, allyl is preferable from the viewpoint of excellent low dielectric properties. In addition, these functional groups having an unsaturated carbon bond can have a carbon number of, for example, 15 or less, 10 or less, 8 or less, 5 or less, 3 or less, and the like.
本發明中,作為聚苯醚(PPE)之原料而使用,總稱可成為聚苯醚之構成單元的苯酚類為「原料苯酚類」。In the present invention, phenols that can be used as raw materials for polyphenylene ether (PPE) are collectively referred to as "raw material phenols" that can serve as constituent units of polyphenylene ether.
本發明中,對原料苯酚類進行說明時,標示為「鄰位」、「對位」等的情況下,只要未特別排除,將苯酚性羥基的位置作為基準(本位)。In the present invention, when describing raw material phenols, when "ortho position", "para position" and the like are indicated, unless otherwise specifically excluded, the position of the phenolic hydroxyl group is taken as the reference (standard position).
本發明中,僅標示為「鄰位」等的情況下,表示為「鄰位之至少一方」等。因此,只要不特別產生矛盾,僅設為「鄰位」的情況下,可解釋為表示鄰位之任一方,亦可解釋為表示鄰位之兩方。In the present invention, when only "ortho position" and the like are indicated, "at least one of the ortho position" and the like are indicated. Therefore, as long as there is no particular contradiction, when only "neighbor" is used, it can be interpreted as indicating either one of the neighbors, or both of the neighbors.
本發明中,聚苯醚之數平均分子量(Mn)與重量平均分子量(Mw)係藉由凝膠浸透層析法(GPC)而求得。GPC中,將Shodex K-805L作為管柱使用,將管柱溫度設為40℃,流量設為1mL/min,溶析液設為氯仿,標準物質設為聚苯乙烯。In the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) of polyphenylene ether are obtained by gel permeation chromatography (GPC). In GPC, Shodex K-805L was used as a column, the column temperature was set to 40°C, the flow rate was set to 1mL/min, the eluent was set to chloroform, and the standard substance was set to polystyrene.
本說明書中,作為原料苯酚類主要揭示1價苯酚類,但在不阻礙本發明之效果的範圍內,可使用多價苯酚類作為原料苯酚類。In this specification, monovalent phenols are mainly shown as raw material phenols, but polyvalent phenols can be used as raw material phenols in the range which does not inhibit the effect of this invention.
本說明書中,於分別記載數值範圍之上限值與下限值的情況下,在不產生矛盾的範圍內,認定為實質上已記載各下限值與各上限值之全部組合。In this specification, when an upper limit and a lower limit of a numerical range are described separately, it is assumed that substantially all combinations of each lower limit and each upper limit are described within the range where no contradiction arises.
<<<<<硬化性組成物之成分>>>>> 硬化性組成物包含:聚苯醚A、聚苯醚B、具有可與不飽和碳鍵進行自由基聚合之官能基的化合物及光自由基產生劑。又,硬化性組成物亦可視需要含有其他成分。以下,針對各個成分進行說明。 <<<<Components of hardening composition>>>>> The curable composition includes: polyphenylene ether A, polyphenylene ether B, a compound having a functional group capable of radical polymerization with an unsaturated carbon bond, and a photoradical generator. In addition, the curable composition may contain other components as needed. Hereinafter, each component is demonstrated.
<<<<聚苯醚A、B>>>> 本發明之硬化性組成物所含有之聚苯醚A及B分別由包含至少滿足下述條件1的苯酚類與至少滿足下述條件2的苯酚類之原料苯酚類所得。具體而言,作為至少滿足下述條件1的苯酚類,例舉有滿足條件1且不滿足條件2的苯酚類或滿足條件1及條件2的苯酚類;作為至少滿足下述條件2的苯酚類,例舉有滿足條件2且不滿足條件1的苯酚類或滿足條件1及條件2的苯酚類。 (條件1) 於鄰位及對位具有氫原子 (條件2) 於對位具有氫原子,且具有包含不飽和碳鍵之官能基 <<<<Polyphenylene ether A, B>>>> The polyphenylene ethers A and B contained in the curable composition of the present invention are respectively obtained from raw material phenols including phenols satisfying at least the following condition 1 and phenols satisfying at least the following condition 2. Specifically, as the phenols satisfying at least the following condition 1, phenols satisfying the condition 1 but not satisfying the condition 2 or satisfying the conditions 1 and 2 are exemplified; as the phenols satisfying at least the following condition 2 , exemplified are phenols satisfying condition 2 but not satisfying condition 1, or phenols satisfying condition 1 and condition 2. (Condition 1) Has hydrogen atoms in the ortho and para positions (Condition 2) Has a hydrogen atom at the para position and has a functional group containing an unsaturated carbon bond
<<<原料苯酚(類)>>> <<滿足條件1的苯酚類>> 滿足條件1的苯酚類於鄰位具有氫原子,因此在與苯酚類氧化聚合時,不僅本位及對位,亦可於鄰位形成醚鍵,故將該苯酚類作為原料苯酚類使用而得的聚苯醚可能形成支鏈狀的構造。 <<<Raw material phenol (type)>>> <<Phenols that satisfy condition 1>> Phenols satisfying condition 1 have a hydrogen atom at the ortho-position, so when oxidatively polymerized with phenols, ether bonds can be formed not only at the home and para-positions, but also at the ortho-position, so this phenol is used as a raw material phenol Polyphenylene ether may form a branched structure.
具體而言,由滿足條件1的苯酚類所得的聚苯醚,其構造之一部分,至少在本位、鄰位、對位3處藉由經醚鍵結的苯環而成為分支狀。Specifically, a polyphenylene ether obtained from a phenol satisfying condition 1 has a part of its structure branched at least at three positions of the ortho-position and the para-position through the benzene ring bonded via ether.
如上述,將於其骨架內具有分支構造之聚苯醚稱為分支聚苯醚。藉由該分支聚苯醚,而可獲得對於有機溶劑之優異溶解性。As mentioned above, polyphenylene ether having a branched structure in its skeleton is called branched polyphenylene ether. With the branched polyphenylene ether, excellent solubility in organic solvents can be obtained.
作為滿足條件1的苯酚類,可舉出苯酚、鄰甲酚、間甲酚、鄰乙基苯酚、間乙基苯酚、2,3-二甲酚、2,5-二甲酚、3,5-二甲酚、鄰-tert-丁基苯酚、間-tert-丁基苯酚、鄰苯基苯酚、間苯基苯酚、2-十二烷基苯酚等,可僅使用1種,亦可使用2種以上。Phenols satisfying condition 1 include phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, -Xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, 2-dodecylphenol, etc., may use only one type, or may use two more than one species.
<<滿足條件2的苯酚類>> 滿足條件2的苯酚類具有包含不飽和碳鍵之官能基,因此將該苯酚類作為原料苯酚使用而得的聚苯醚具有包含乙烯性或乙炔性之碳-碳多重鍵之官能基。 <<Phenols that satisfy condition 2>> Phenols satisfying condition 2 have functional groups containing unsaturated carbon bonds, and therefore polyphenylene ethers obtained by using such phenols as raw material phenols have functional groups containing ethylenic or acetylenic carbon-carbon multiple bonds.
具體而言,由滿足條件2的苯酚類所得的聚苯醚,其構造之一部分,至少在苯環之間位或鄰位2處之任一者具有包含不飽和碳鍵之官能基。Specifically, a polyphenylene ether obtained from a phenol satisfying condition 2 has a functional group including an unsaturated carbon bond at least in either the inter-position or the two ortho-positions of the benzene ring as part of its structure.
如上述,於其骨架內具有包含不飽和碳鍵之官能基之聚苯醚稱為感光性聚苯醚。藉由該感光性聚苯醚,而可獲得自由基等活性種所致之自由基聚合性。As mentioned above, a polyphenylene ether having a functional group including an unsaturated carbon bond in its skeleton is called a photosensitive polyphenylene ether. By the photosensitive polyphenylene ether, radical polymerizability due to active species such as radicals can be obtained.
滿足條件2的苯酚類,可舉出2-烯丙基-6-甲基苯酚、2-烯丙基-6-乙基苯酚、2-烯丙基-6-苯基苯酚、2-烯丙基-6-苯乙烯基苯酚、2,6-二乙烯基苯酚、2,6-二烯丙基苯酚、2,6-二異丙烯基苯酚、2,6-二丁烯基苯酚、2,6-二異丁烯基苯酚、2,6-二異戊烯基苯酚、2-甲基-6-苯乙烯基苯酚、2-乙烯基-6-甲基苯酚、2-乙烯基-6-乙基苯酚等,可僅使用1種,亦可使用2種以上。Phenols satisfying condition 2 include 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl Base-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2, 6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethyl Phenol etc. may use only 1 type, and may use 2 or more types.
<<滿足條件1及條件2的苯酚類>> 滿足條件1及條件2的苯酚類為於鄰位及對位具有氫原子,並且為具有包含不飽和碳鍵之官能基之苯酚類。將該苯酚類作為原料苯酚使用而得的聚苯醚,其構造之一部分,至少在本位、鄰位、對位3處藉由經醚鍵結的苯環而分支,並且具有包含至少一個不飽和碳鍵之烴基作為官能基。 <<Phenols satisfying conditions 1 and 2>> The phenols satisfying the condition 1 and the condition 2 have hydrogen atoms at the ortho-position and the para-position, and are phenols having a functional group including an unsaturated carbon bond. A polyphenylene ether obtained by using the phenol as a raw material phenol has a part of its structure branched by benzene rings bonded via ether at least at three positions of the ortho-position, the ortho-position, and the para-position, and has at least one unsaturated A carbon-bonded hydrocarbon group is used as a functional group.
作為滿足條件1及條件2的苯酚類,可舉出鄰乙烯基苯酚、間乙烯基苯酚、鄰烯丙基苯酚、間烯丙基苯酚、3-乙烯基-6-甲基苯酚、3-乙烯基-6-乙基苯酚、3-乙烯基-5-甲基苯酚、3-乙烯基-5-乙基苯酚、3-烯丙基-6-甲基苯酚、3-烯丙基-6-乙基苯酚、3-烯丙基-5-甲基苯酚、3-烯丙基-5-乙基苯酚等,可僅使用1種,亦可使用2種以上。Examples of phenols satisfying conditions 1 and 2 include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinylphenol, Base-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6- Ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, etc. may use only 1 type, and may use 2 or more types.
<<不滿足條件1及條件2之任一者的苯酚類>> 本發明之聚苯醚之合成所使用之原料苯酚類,就調整分支構造所致之溶解性、自由基聚合性的觀點而言,可包含不滿足條件1及條件2之任一者的苯酚類。 <<Phenols that do not satisfy either of the conditions 1 and 2>> The raw material phenols used in the synthesis of the polyphenylene ether of the present invention may contain phenols that do not satisfy either of the conditions 1 and 2 from the viewpoint of adjusting the solubility and radical polymerizability due to the branched structure. .
作為這種原料苯酚類,例如,作為於對位具有氫原子、於鄰位不具有氫原子且不具有包含不飽和碳鍵之官能基之苯酚類,例舉有2,6-二甲基苯酚、2,3,6-三甲基苯酚、2-甲基-6-乙基苯酚、2-乙基-6-正丙基苯酚、2-甲基-6-正丁基苯酚、2-甲基-6-苯基苯酚、2,6-二苯基苯酚、2,6-二甲苯基苯酚等,藉由該苯酚類於苯環之本位及對位形成醚鍵並直鏈狀地聚合,故分支構造減少且溶解性降低。又,不具有包含不飽和碳鍵之官能基,因此自由基聚合性降低。Such raw material phenols include, for example, 2,6-dimethylphenol as phenols having a hydrogen atom at the para-position, no hydrogen atom at the ortho-position, and no functional group including an unsaturated carbon bond. , 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl Base-6-phenylphenol, 2,6-diphenylphenol, 2,6-xylylphenol, etc., by forming ether bonds at the normal and para-positions of the benzene ring and polymerizing them linearly, Therefore, the branching structure is reduced and the solubility is reduced. Moreover, since it does not have a functional group containing an unsaturated carbon bond, radical polymerizability falls.
又,作為不滿足條件1及條件2之任一者的苯酚類,亦例舉有於對位與鄰位不具有氫原子,且不具有包含不飽和碳鍵之官能基之苯酚類。該苯酚類可抑制聚苯醚之聚合反應。 這種不滿足條件1及條件2之任一者的苯酚類,可僅使用1種,亦可使用2種以上。 Moreover, as phenols which do not satisfy any one of the condition 1 and the condition 2, the phenol which does not have a hydrogen atom in a para position and an ortho position, and does not have a functional group containing an unsaturated carbon bond is also mentioned. The phenols can inhibit the polymerization reaction of polyphenylene ether. Such phenols that do not satisfy either of Condition 1 and Condition 2 may be used alone or in combination of two or more.
<<<聚苯醚A>>> 本發明中之聚苯醚A由包含至少滿足條件1的苯酚類與至少滿足條件2的苯酚類的原料苯酚類所得,且為滿足條件2的苯酚類相對於合成時之原料苯酚類全體的含量未滿20mol%,重量平均分子量為超過40,000且200,000以下之聚苯醚。 <<<Polyphenylene ether A>>> The polyphenylene ether A in the present invention is obtained from raw material phenols including at least phenols satisfying condition 1 and phenols satisfying condition 2, and is the content of phenols satisfying condition 2 relative to the entire raw material phenols at the time of synthesis Polyphenylene ether having a weight average molecular weight of more than 40,000 and less than 200,000 is less than 20 mol%.
聚苯醚A為具有分支構造與包含不飽和碳鍵之官能基之聚苯醚,滿足條件2的苯酚類相對於合成時之原料苯酚類全體之含有比率與聚苯醚B相較下更低,故包含不飽和碳鍵之官能基所致之介電特性惡化被抑制,且合成中之聚合反應容易進行,重量平均分子量相對較大,藉此而耐顯影性優異。Polyphenylene ether A is a polyphenylene ether having a branched structure and functional groups containing unsaturated carbon bonds, and the ratio of the content of phenols satisfying condition 2 to the entire raw material phenols at the time of synthesis is lower than that of polyphenylene ether B , so the deterioration of dielectric properties caused by functional groups containing unsaturated carbon bonds is suppressed, and the polymerization reaction during synthesis is easy to proceed, and the weight average molecular weight is relatively large, thereby excellent development resistance.
聚苯醚A就未曝光部之顯影性與曝光部之耐顯影性之平衡的觀點而言,重量平均分子量較佳為超過40,000且200,000以下,更佳為60,000以上200,000以下,又,數平均分子量較佳為10,000以上30,000以下,更佳為15,000以上20,000以下。Polyphenylene ether A has a weight average molecular weight of preferably more than 40,000 and 200,000 or less, more preferably 60,000 or more and 200,000 or less from the viewpoint of the balance between the developability of the unexposed part and the development resistance of the exposed part, and the number average molecular weight It is preferably from 10,000 to 30,000, more preferably from 15,000 to 20,000.
使用於聚苯醚A之合成之至少滿足條件1的苯酚類的含量,相對於合成時之原料苯酚類全體,可設為1mol%以上99mol%以下,較佳為5mol%以上30mol%以下,更佳為5mol%以上15mol%以下,進而佳為10mol%。The content of phenols used in the synthesis of polyphenylene ether A that satisfies at least condition 1 may be 1 mol% or more and 99 mol% or less, preferably 5 mol% or more and 30 mol% or less, relative to the total raw material phenols during synthesis. Preferably, it is 5 mol% or more and 15 mol% or less, More preferably, it is 10 mol%.
使用於聚苯醚A之合成之至少滿足條件2的苯酚類的含量,相對於合成時之原料苯酚類全體,可設為未滿20mol%,較佳為1mol%以上且未滿20mol%,更佳為5mol%以上15mol%以下,進而佳為10mol%。The content of phenols used in the synthesis of polyphenylene ether A that satisfies at least condition 2 may be less than 20 mol%, preferably 1 mol% or more and less than 20 mol%, relative to the total phenols used as raw materials for synthesis. Preferably, it is 5 mol% or more and 15 mol% or less, More preferably, it is 10 mol%.
聚苯醚A之合成中,在不損及本發明之效果的範圍內可使用不滿足條件1及條件2之任一者的苯酚類。In the synthesis of polyphenylene ether A, phenols that do not satisfy either of Condition 1 or Condition 2 can be used within the range that does not impair the effect of the present invention.
<<<聚苯醚B>>> 本發明中之聚苯醚B由含有包含至少滿足條件1的苯酚類與至少滿足條件2的苯酚類之原料苯酚類之原料苯酚類所得,且為滿足條件2的苯酚類相對於合成時之原料苯酚類全體的含量為20mol%以上之聚苯醚。 <<<Polyphenylene ether B>>> The polyphenylene ether B in the present invention is obtained from raw material phenols containing phenols satisfying at least condition 1 and phenols satisfying condition 2, and the ratio of the phenols satisfying condition 2 to the raw material at the time of synthesis is Polyphenylene ether with an overall phenol content of 20 mol % or more.
聚苯醚B為具有分支構造與包含不飽和碳鍵之官能基之聚苯醚,滿足條件2的苯酚類相對於合成時之原料苯酚類全體的含有比率與聚苯醚A相較下更高,具有較多包含不飽和碳鍵之官能基,故自由基聚合性優異。另一方面,藉由滿足條件2的苯酚類難以進行聚合反應,重量平均分子量相對較小,因此顯示優異的顯影性。Polyphenylene ether B is a polyphenylene ether having a branched structure and functional groups containing unsaturated carbon bonds, and the content ratio of phenols satisfying condition 2 relative to the total phenols used in synthesis is higher than that of polyphenylene ether A , has more functional groups containing unsaturated carbon bonds, so it has excellent free radical polymerizability. On the other hand, since the phenols satisfying the condition 2 are difficult to undergo polymerization reaction and have a relatively small weight average molecular weight, they exhibit excellent developability.
聚苯醚B之重量平均分子量較佳為5,000以上40,000以下,由於更提升自由基聚合性、顯影性,故更佳為10,000以上20,000以下。又,數平均分子量較佳為5,000以上20,000以下,更佳為5,000以上12,000以下。The weight-average molecular weight of polyphenylene ether B is preferably from 5,000 to 40,000, and more preferably from 10,000 to 20,000 because radical polymerizability and developability are further improved. In addition, the number average molecular weight is preferably from 5,000 to 20,000, more preferably from 5,000 to 12,000.
使用於聚苯醚B之合成之至少滿足條件1的苯酚類的含量,相對於合成時之原料苯酚類全體,可設為1mol%以上90mol%以下,較佳為2mol%以上50mol%以下,更佳為5mol%以上20mol%以下。The content of phenols used in the synthesis of polyphenylene ether B that satisfies at least condition 1 may be 1 mol% to 90 mol%, preferably 2 mol% to 50 mol%, with respect to the total raw material phenols at the time of synthesis. Preferably, it is not less than 5 mol% and not more than 20 mol%.
使用於聚苯醚B之合成之至少滿足條件2的苯酚類的含量,相對於合成時之原料苯酚類全體,可設為20mol%以上,較佳為20mol%以上90mol%以下,更佳為50mol%以上90mol%以下。The content of phenols used in the synthesis of polyphenylene ether B that satisfies at least condition 2 may be 20 mol% or more, preferably 20 mol% or more and 90 mol% or less, more preferably 50 mol% with respect to the total phenols used as raw materials for synthesis. % above 90mol% below.
聚苯醚B之合成中,在不損及本發明之效果的範圍內可使用不滿足條件1及條件2之任一者的苯酚類。In the synthesis of polyphenylene ether B, phenols that do not satisfy either of Condition 1 or Condition 2 can be used within the range that does not impair the effect of the present invention.
<<<聚苯醚的含量>>> 本發明之硬化性組成物中聚苯醚(聚苯醚A及聚苯醚B)的含量,以去除硬化性組成物中之揮發成分與無機充填劑之總量基準計,較佳為50~90質量%,更佳為60~80質量%。又,硬化性組成物中聚苯醚A與聚苯醚B之含有比例(聚苯醚A:聚苯醚B),以質量比計,較佳為10:90~90:10,更佳為25:75~75:25,在提升曝光部之耐顯影性的情況下,可設為50:50~75:25,在提升光自由基聚合性(感光性)、未曝光部之顯影性的情況下,可設為25:75~50:50。 <<<Polyphenylene ether content>>> The content of polyphenylene ether (polyphenylene ether A and polyphenylene ether B) in the curable composition of the present invention is preferably 50~ 90% by mass, more preferably 60-80% by mass. In addition, the content ratio of polyphenylene ether A to polyphenylene ether B in the curable composition (polyphenylene ether A:polyphenylene ether B) is preferably 10:90~90:10 in terms of mass ratio, more preferably 25:75~75:25, in the case of improving the development resistance of the exposed part, it can be set to 50:50~75:25, in order to improve the photoradical polymerization (photosensitivity) and the developability of the unexposed part Under normal circumstances, it can be set to 25:75~50:50.
<<<聚苯醚A、B之製造方法>>> 本發明之聚苯醚A及聚苯醚B,除了變更使用之原料苯酚類以外,能夠以習知的聚苯醚合成方法來製造。例如,能夠以國際公開第2020/017570號所揭示的合成方法來製造。 <<<Manufacturing method of polyphenylene ether A and B>>> The polyphenylene ether A and polyphenylene ether B of the present invention can be produced by a conventional polyphenylene ether synthesis method except that the raw material phenols used are changed. For example, it can be produced by the synthesis method disclosed in International Publication No. 2020/017570.
聚苯醚之分子量,雖取決於使用之原料苯酚類之種類,但藉由變更合成聚苯醚時之反應溫度、反應時間等亦可能調整。Although the molecular weight of polyphenylene ether depends on the type of raw material phenols used, it can also be adjusted by changing the reaction temperature and reaction time when synthesizing polyphenylene ether.
<<<<具有可與不飽和碳鍵進行自由基聚合之官能基的化合物>>>> 本發明之硬化性組成物所含有之具有可與不飽和碳鍵進行自由基聚合之官能基的化合物(以下,亦稱為自由基聚合化合物),為具有2個以上能夠與上述聚苯醚構造中的不飽和碳鍵進行自由基聚合的官能基之化合物。可能進行前述自由基聚合的官能基,可使用習知慣用之官能基,例如,例舉有硫醇基、烯丙基等。 <<<<Compounds with functional groups that can undergo radical polymerization with unsaturated carbon bonds>>>> The compound having a functional group capable of radically polymerizing with an unsaturated carbon bond contained in the curable composition of the present invention (hereinafter also referred to as a radically polymerizable compound) has two or more structures that can be combined with the above-mentioned polyphenylene ether. Compounds with functional groups whose unsaturated carbon bonds undergo free radical polymerization. As the functional group that may undergo radical polymerization, known and commonly used functional groups can be used, for example, thiol group, allyl group and the like are exemplified.
自由基聚合化合物,例如,作為具有硫醇基之化合物,例舉有三羥甲基丙烷參(3-巰基丙酸酯)、參-[(3-巰基丙醯氧基)-乙基]-異三聚氰酸酯、季戊四醇肆(3-巰基丙酸酯)、四乙二醇雙(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)等。作為具有烯丙基之化合物,例舉有三烯丙基異三聚氰酸酯、鄰苯二甲酸二烯丙酯、間苯二甲酸二烯丙酯、1,4-環己烷二羧酸二烯丙酯等。Radical polymerizable compounds, for example, as compounds having a thiol group, trimethylolpropane ginseng (3-mercaptopropionate), ginseng-[(3-mercaptopropionyloxy)-ethyl]-iso Cyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), etc. Examples of compounds having an allyl group include triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, 1,4-cyclohexanedicarboxylic acid di- Allyl ester etc.
<<<具有可與不飽和碳鍵進行自由基聚合之官能基的化合物的含量>>> 硬化性組成物中自由基聚合化合物的含量,相對於硬化性組成物中之聚苯醚,較佳為1~99質量%,較佳為10~20質量%。 <<<Content of compounds having functional groups that can undergo radical polymerization with unsaturated carbon bonds>>> The content of the radical polymerizable compound in the curable composition is preferably 1 to 99% by mass, more preferably 10 to 20% by mass relative to the polyphenylene ether in the curable composition.
<<<<光自由基產生劑>>>> 本發明之硬化性組成物所含有之光自由基產生劑為藉由光照射(曝光)而產生自由基的化合物,藉由所產生的自由基而使上述聚苯醚、自由基聚合化合物進行自由基聚合,賦予曝光部耐顯影性。 <<<<Photofree Radical Generator>>>> The photoradical generator contained in the curable composition of the present invention is a compound that generates free radicals by light irradiation (exposure), and causes the above-mentioned polyphenylene ether and radical polymerization compound to undergo free radicals by the generated free radicals. Polymerizes the exposed part and imparts development resistance to the exposed part.
作為光自由基產生劑,可使用習知慣用之光自由基產生劑。例如,例舉有安息香醚系、苯乙酮系、α-酮醇系、芳香族磺醯氯系、光活性肟系、安息香系、二苯乙二酮系、二苯基酮系、縮酮系、噻噸酮系、醯基氧化膦系等。As the photoradical generator, a conventional photoradical generator can be used. For example, benzoin ether series, acetophenone series, α-ketol series, aromatic sulfonyl chloride series, photoactive oxime series, benzoin series, diphenyl ketone series, diphenyl ketone series, ketal series, etc. series, thioxanthone series, acyl phosphine oxide series, etc.
作為安息香醚系光自由基產生劑,例如,例舉有安息香甲基醚、安息香乙基醚、安息香丙基醚、安息香異丙基醚、安息香異丁基醚、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、茴香偶因等。Examples of benzoin ether-based photoradical generators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy -1,2-diphenylethan-1-one, anise, etc.
作為苯乙酮系光自由基產生劑,例如,例舉有1-羥基環己基苯基酮、4-苯氧基二氯苯乙酮、4-t-丁基-二氯苯乙酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、甲氧基苯乙酮等。As an acetophenone-based photoradical generator, for example, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1 -[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane- 1-ketone, methoxyacetophenone, etc.
作為α-酮醇系光自由基產生劑,例如,例舉有2-甲基-2-羥基苯丙酮、1-[4-(2-羥基乙基)-苯基]-2-羥基-2-甲基丙烷-1-酮等。Examples of α-ketol-based photoradical generators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2 -Methylpropan-1-one and the like.
作為芳香族磺醯氯系光自由基產生劑,例如例舉有2-萘磺醯氯等。作為光活性肟系光聚合起始劑,例如,例舉有1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)-肟等。As an aromatic sulfonyl chloride type photoradical generator, 2-naphthalenesulfonyl chloride etc. are mentioned, for example. As a photoactive oxime type photoinitiator, 1-phenyl-1, 2-propanedione-2-(O-ethoxycarbonyl)-oxime etc. are mentioned, for example.
作為安息香系光自由基產生劑,例如,例舉有安息香等。Examples of the benzoin-based photoradical generating agent include benzoin and the like.
作為二苯乙二酮系光自由基產生劑,例如,例舉有二苯乙二酮等。As the benzphenone-based photoradical generator, for example, benzphenone and the like are exemplified.
作為二苯基酮光自由基產生劑,例如,例舉有二苯基酮、苯甲醯基安息香酸、3,3´-二甲基-4-甲氧基二苯基酮、聚乙烯二苯基酮、α-羥基環己基苯基酮等。As the benzophenone photoradical generator, for example, benzophenone, benzoylbenzoic acid, 3,3´-dimethyl-4-methoxydiphenyl ketone, polyethylene diphenyl Phenyl ketone, α-hydroxycyclohexyl phenyl ketone, etc.
作為縮酮系光自由基產生劑,例如,例舉有苄基二甲基縮酮等。As a ketal type photoradical generator, benzyl dimethyl ketal etc. are mentioned, for example.
作為噻噸酮系光自由基產生劑,例如,例舉有噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、異丙基噻噸酮、2,4-二異丙基噻噸酮、十二烷基噻噸酮等。Examples of thioxanthone-based photoradical generators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and Xanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone wait.
作為醯基氧化膦系光自由基產生劑,例如,例舉有雙(2,6-二甲氧基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)(2,4,4-三甲基戊基)氧化膦、雙(2,6-二甲氧基苯甲醯基)正丁基氧化膦、雙(2,6-二甲氧基苯甲醯基)-(2-甲基丙烷-1-基)氧化膦、雙(2,6-二甲氧基苯甲醯基)-(1-甲基丙烷-1-基)氧化膦、雙(2,6-二甲氧基苯甲醯基)-t-丁基氧化膦、雙(2,6-二甲氧基苯甲醯基)環己基氧化膦、雙(2,6-二甲氧基苯甲醯基)辛基氧化膦、雙(2-甲氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2-甲氧基苯甲醯基)(1-甲基丙烷-1-基)氧化膦、雙(2,6-二乙氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2,6-二乙氧基苯甲醯基)(1-甲基丙烷-1-基)氧化膦、雙(2,6-二丁氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2,4-二甲氧基苯甲醯基)(2-甲基丙烷-1-基)氧化膦、雙(2,4,6-三甲基苯甲醯基)(2,4-二戊氧基苯基)氧化膦、雙(2,6-二甲氧基苯甲醯基)苄基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基丙基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基乙基氧化膦、雙(2,6-二甲氧基苯甲醯基)苄基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基丙基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2-苯基乙基氧化膦、2,6-二甲氧基苯甲醯基苄基丁基氧化膦、2,6-二甲氧基苯甲醯基苄基辛基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,5-二異丙基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2-甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-4-甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,5-二乙基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,3,5,6-四甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,4-二正丁氧基苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,4,6-三甲基苯甲醯基)異丁基氧化膦、2,6-二甲氧基苯甲醯基-2,4,6-三甲基苯甲醯基正丁基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-2,4-二丁氧基苯基氧化膦、1,10-雙[雙(2,4,6-三甲基苯甲醯基)氧化膦]癸烷、三(2-甲基苯甲醯基)氧化膦等。As an acylphosphine oxide-based photoradical generator, for example, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) base)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)n-butylphosphine oxide, bis(2,6-dimethoxybenzene Formyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethyl Oxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl) (1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-bis Ethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide , bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4 -dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-benzene propylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide , Bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide , 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethyl Benzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, Bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- 2,4-Di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 ,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2, 4,6-Trimethylbenzoyl n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzene Formyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2- methylbenzoyl) phosphine oxide, etc.
該等光自由基產生劑,可僅使用1種,亦可使用2種以上。These photoradical generators may use only 1 type, and may use 2 or more types.
<<<光自由基產生劑的含量>>> 硬化性組成物中光自由基產生劑的含量,相對於硬化性組成物中之聚苯醚,較佳為0.1~10質量%,更佳為1~5質量%。 <<<Content of Photo Radical Generator>>> The content of the photoradical generator in the curable composition is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, relative to the polyphenylene ether in the curable composition.
<<<<溶劑>>>> 本發明之硬化性組成物,配合摻合、塗佈等步驟,可視需要包含溶劑。作為溶劑,較佳為可溶解上述聚苯醚之溶劑,例如,在氯仿、二氯甲烷、甲苯等以往可能使用的溶劑以外,可較佳地使用N-甲基-2-吡咯啶酮(NMP)、四氫呋喃(THF)、環己酮、丙二醇單甲基醚乙酸酯(PMA)、二乙二醇單乙基醚乙酸酯(CA)、甲乙酮、乙酸乙酯等。 該等可僅使用1種,亦可使用2種以上。 <<<<Solvent>>>> The curable composition of the present invention may optionally contain a solvent in conjunction with steps such as blending and coating. As a solvent, it is preferable to be a solvent that can dissolve the above-mentioned polyphenylene ether. For example, in addition to solvents that may be used in the past such as chloroform, methylene chloride, toluene, etc., N-methyl-2-pyrrolidone (NMP ), tetrahydrofuran (THF), cyclohexanone, propylene glycol monomethyl ether acetate (PMA), diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, ethyl acetate, etc. These may use only 1 type, and may use 2 or more types.
<<<<其他成分>>>> 本發明之硬化性組成物,於上述成分以外,在不損及本發明之效果的範圍內,亦可含有其他成分。例如,亦可包含二氧化矽等無機充填材、α,α’-雙(t-丁基過氧基間異丙基)苯等過氧化物、上述聚苯醚以外的聚苯醚、馬來醯亞胺樹脂、苯乙烯系彈性體等樹脂及聚合物成分、增感劑、接著助劑、界面活性劑、調平劑、塑化劑、密著劑、著色劑、纖維、矽烷偶合劑、阻燃性劑、纖維素奈米纖維、分散劑、熱硬化觸媒、增黏劑、消泡劑、抗氧化劑、防鏽劑、密著性賦予劑等。 該等成分可因應用途等而摻合適宜量。作為一例,在欲提升介電特性的情況下,硬化性組成物中之過氧化物的含量,相對於硬化性組成物中之聚苯醚,較佳為0.1~10質量%,更佳為1~5質量%。 該等成分分別可單獨使用1種,亦可組合2種以上使用。 <<<<Other Ingredients>>>> The curable composition of the present invention may contain other components in addition to the above-mentioned components within the range that does not impair the effect of the present invention. For example, inorganic fillers such as silicon dioxide, peroxides such as α,α'-bis(t-butylperoxym-isopropyl)benzene, polyphenylene ethers other than the above-mentioned polyphenylene ethers, maleic acid, etc. Resins and polymer components such as imide resins and styrene-based elastomers, sensitizers, adhesive additives, surfactants, leveling agents, plasticizers, adhesives, colorants, fibers, silane coupling agents, Flame retardant, cellulose nanofiber, dispersant, thermosetting catalyst, thickener, defoamer, antioxidant, rust inhibitor, adhesion imparting agent, etc. These components can be blended in appropriate amounts depending on the application and the like. As an example, when improving the dielectric properties, the content of the peroxide in the curable composition is preferably 0.1 to 10% by mass, more preferably 1% by mass, relative to the polyphenylene ether in the curable composition. ~5% by mass. These components may be used individually by 1 type, respectively, and may use it in combination of 2 or more types.
<<<<<乾膜>>>>> 乾膜於膜材料上具有由本發明之硬化性組成物所構成之樹脂層。乾膜係將樹脂層以與基材接觸的方式層合並使用。 <<<<Dry Film>>>>> The dry film has a resin layer made of the curable composition of the present invention on the film material. The dry film is used by laminating a resin layer in contact with a substrate.
乾膜係於載體膜(支持膜)上藉由刮刀塗佈器、唇模塗佈器、缺角輪塗佈器、膜塗佈器等適當方法均一地塗佈硬化性組成物,並使其乾燥,形成前述樹脂層,較佳可藉由於其上層合罩膜(保護膜)而製造。罩膜與載體膜可使用相同之膜材料,亦可使用相異之膜。The dry film is uniformly coated with a curable composition on the carrier film (support film) by an appropriate method such as a knife coater, a lip die coater, a chip coater, a film coater, etc., and make it It is dried to form the aforementioned resin layer, preferably manufactured by laminating a cover film (protective film) thereon. The cover film and the carrier film can use the same film material or different films.
載體膜及罩膜之膜材料,可使用任一種使用於乾膜的習知者。The film material of the carrier film and the cover film can be any conventional one used for dry film.
作為載體膜,例如,可使用厚度2~150μm之聚對苯二甲酸乙二酯等聚酯膜等熱塑性膜。As the carrier film, thermoplastic films such as polyester films such as polyethylene terephthalate having a thickness of 2 to 150 μm can be used, for example.
作為罩膜可使用聚乙烯膜、聚丙烯膜等,但理想為與樹脂層之接著力比載體膜小者。A polyethylene film, a polypropylene film, etc. can be used as a cover film, but it is preferable that the adhesive force with a resin layer is smaller than a carrier film.
乾膜上之樹脂層之膜厚,較佳為100μm以下,更佳為5~50μm之範圍。The film thickness of the resin layer on the dry film is preferably less than 100 μm, more preferably in the range of 5-50 μm.
<<<<<硬化物>>>>> 可使用硬化性組成物、或具有由硬化性組成物所構成之樹脂層之乾膜來製造硬化物。 <<<<hardened product>>>>> The cured product can be produced using a curable composition or a dry film having a resin layer made of the curable composition.
本實施形態之硬化性組成物通常適用於負型的光微影法。以下,將本實施形態之硬化性組成物適用於負型的光微影法,說明製造作為本實施形態之硬化性組成物的硬化物之圖案膜的方法。The curable composition of this embodiment is generally suitable for negative photolithography. Hereinafter, a method of manufacturing a patterned film that is a cured product of the curable composition of the present embodiment will be described by applying the curable composition of the present embodiment to negative photolithography.
首先,作為步驟1,於基材上塗佈硬化性組成物並乾燥形成樹脂層、或於基材上層合乾膜轉印由硬化性組成物所構成之樹脂層。作為將硬化性組成物塗佈於基材上的方法,可使用以往使用於硬化性組成物的塗佈的方法,例如,利用旋轉塗佈器、棒式塗佈器、刮刀塗佈器、簾幕塗佈器、絲網印刷機等進行塗佈的方法、利用噴霧塗佈器進行噴霧塗佈的方法、進而可使用噴墨法等。First, as step 1, a curable composition is applied on a substrate and dried to form a resin layer, or a dry film is laminated on a substrate to transfer a resin layer composed of a curable composition. As a method of coating the curable composition on the base material, a method conventionally used for coating a curable composition can be used, for example, using a spin coater, a rod coater, a knife coater, a curtain coater, etc. A method of coating with a curtain coater, a screen printer, or the like, a method of spray coating with a spray coater, and an inkjet method, etc. can also be used.
作為塗膜之乾燥方法,可使用風乾、利用烘箱或加熱板的加熱乾燥、真空乾燥等方法。又,塗膜之乾燥條件,並未特別限定,能夠以60~130℃下1~30分鐘的條件進行自然乾燥、送風乾燥或加熱乾燥。As a drying method of the coating film, methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying can be used. Moreover, the drying conditions of a coating film are not specifically limited, Natural drying, ventilation drying, or heat drying can be performed at 60-130 degreeC for 1-30 minutes.
關於基材,並無特別限制,可廣泛適用矽晶圓等半導體基材、配線基板、由各種樹脂、金屬等所構成的基材。The substrate is not particularly limited, and substrates made of semiconductor substrates such as silicon wafers, wiring boards, various resins, metals, and the like can be widely used.
接著,作為步驟2,將形成於基材上的樹脂層介隔具有圖案的光罩、或直接圖案狀地進行光照射(曝光)。另外,層合乾膜的方法中,剝離膜材料並曝光,或者在膜材料具有透光性的情況下,在樹脂層上殘留有膜材料的狀態下進行曝光,之後再剝離膜材料。曝光中,使用可使光自由基聚合起始劑活性化的波長之光。具體而言,較佳為最大波長在350~410nm之範圍內。作為曝光裝置,可使用接觸對準機、鏡面投影機、步進機、雷射直接曝光裝置等。Next, as step 2, the resin layer formed on the base material is irradiated with light (exposure) through a photomask having a pattern or directly in a pattern form. In addition, in the method of laminating a dry film, the film material is peeled off and exposed, or when the film material is light-transmitting, the film material is exposed with the film material remaining on the resin layer, and then the film material is peeled off. For exposure, light of a wavelength capable of activating the photoradical polymerization initiator is used. Specifically, it is preferable that the maximum wavelength is within the range of 350 to 410 nm. As the exposure apparatus, a contact aligner, a mirror projector, a stepper, a laser direct exposure apparatus, etc. can be used.
接著,作為步驟3,以顯影液處理樹脂層。藉此,可去除樹脂層之未曝光部分形成圖案膜。顯影後可視需要藉由沖洗液洗淨樹脂層。Next, as Step 3, the resin layer is treated with a developing solution. Thereby, the unexposed part of the resin layer can be removed to form a pattern film. After developing, the resin layer may be washed with a rinse solution if necessary.
作為顯影所使用之方法,可由以往已知的光阻顯影方法,例如旋轉噴霧法、覆液(paddle)法、伴隨超音波處理的浸漬法等中選擇任意方法。As the method used for development, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, a dipping method with ultrasonic treatment, and the like.
顯影液可使用溶解作為硬化性組成物之主成分的聚苯醚之溶劑,為了防止電路等的腐蝕,較佳設為有機溶劑。例如,在氯仿、二氯甲烷、甲苯等溶劑以外,可使用N-甲基-2-吡咯啶酮(NMP)、四氫呋喃(THF)、環己酮、丙二醇單甲基醚乙酸酯(PMA)、二乙二醇單乙基醚乙酸酯(CA)、甲乙酮、乙酸乙酯等溶劑,可僅使用1種,亦可混合2種以上而使用。 又,顯影液中,就調整顯影速度的觀點而言,可組合上述有機溶劑以外之溶劑,可視需要含有適當量的界面活性劑等。 As the developer, a solvent that dissolves polyphenylene ether as a main component of the curable composition can be used, and an organic solvent is preferably used in order to prevent corrosion of circuits and the like. For example, in addition to solvents such as chloroform, methylene chloride, and toluene, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, and propylene glycol monomethyl ether acetate (PMA) can be used Solvents such as , diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, and ethyl acetate may be used alone or in combination of two or more. In addition, in the developing solution, from the viewpoint of adjusting the development speed, solvents other than the above-mentioned organic solvents may be combined, and an appropriate amount of a surfactant or the like may be contained as necessary.
作為沖洗液,例舉有蒸餾水、甲醇、乙醇、異丙醇等。As the rinsing liquid, distilled water, methanol, ethanol, isopropanol and the like are exemplified.
又,作為步驟5,可視需要加熱圖案膜。加熱溫度並未特別限定,例如於100~220℃下加熱30~120分鐘左右等。作為此時的環境(氣體),可使用空氣,亦可使用氮、氬等惰性氣體。In addition, as step 5, the patterned film may be heated if necessary. The heating temperature is not particularly limited, for example, heating at 100 to 220° C. for about 30 to 120 minutes or the like. As the atmosphere (gas) at this time, air may be used, and inert gases such as nitrogen and argon may be used.
<<<<<電子零件>>>>> 電子零件為具有前述本實施形態之硬化物者,由於本實施形態之硬化物具有優異之介電特性、耐熱性,因此可能作為構成電子零件的材料使用於各種用途。 <<<<<Electronic Parts>>>>> The electronic component has the hardened product of the above-mentioned embodiment. Since the cured product of the present embodiment has excellent dielectric properties and heat resistance, it can be used in various applications as a material constituting the electronic component.
其用途並未特別限定,較佳例舉有以第5代通訊系統(5G)為代表之大容量高速通訊、汽車之ADAS(先進駕駛輔助系統)用之毫米波雷達等電子零件中之絕緣材料。 [實施例] Its use is not particularly limited, but preferred examples include high-capacity high-speed communications represented by the fifth generation communication system (5G), and insulation materials in electronic components such as millimeter-wave radars for automotive ADAS (advanced driver assistance systems) . [Example]
<<<聚苯醚A之合成>>> <<PPEA-1之合成>> 於3L之二口茄型燒瓶中,加入二-μ-羥基-雙[(N,N,N’, N’-四甲基伸乙二胺)銅(II)]氯化物(Cu/TMEDA)2.6g、與四甲基伸乙二胺(TMEDA)3.18mL並使其充分溶解,以100ml/min的條件供給氧。使作為原料苯酚類之2,6-二甲基苯酚89.1g(90mol%)與2-烯丙基苯酚10.9g(10mol%)溶解於甲苯1.5L而調製原料溶液。將該原料溶液滴入燒瓶,一面以600rpm之旋轉速度進行攪拌一面於40℃下使其反應10小時。反應結束後,以甲醇20L:濃鹽酸22mL之混合液進行再沉澱並過濾取出,於80℃下使其乾燥24小時,得到PPEA-1。PPEA-1之數平均分子量為17,500,重量平均分子量為192,000。 <<<Synthesis of Polyphenylene Ether A>>> <<Synthesis of PPEA-1>> In a 3L two-necked eggplant-shaped flask, add di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)]chloride (Cu/TMEDA) 2.6 g, and 3.18 mL of tetramethylethylenediamine (TMEDA) were fully dissolved, and oxygen was supplied at a rate of 100 ml/min. A raw material solution was prepared by dissolving 89.1 g (90 mol %) of 2,6-dimethylphenol as raw material phenols and 10.9 g (10 mol %) of 2-allylphenol in 1.5 L of toluene. This raw material solution was dripped into the flask, and it was made to react at 40 degreeC for 10 hours, stirring at the rotation speed of 600 rpm. After the reaction, reprecipitate with a mixture of 20 L of methanol: 22 mL of concentrated hydrochloric acid, take it out by filtration, and dry it at 80° C. for 24 hours to obtain PPEA-1. The number average molecular weight of PPEA-1 was 17,500, and the weight average molecular weight was 192,000.
<<PPEA-2之合成>> 上述PPEA-1之合成方法中,除了將反應時間設為8小時以外,利用相同方法得到PPEA-2。PPEA-2之數平均分子量為19,000,重量平均分子量為84,600。 <<Synthesis of PPEA-2>> In the above synthesis method of PPEA-1, PPEA-2 was obtained by the same method except that the reaction time was set to 8 hours. The number average molecular weight of PPEA-2 was 19,000, and the weight average molecular weight was 84,600.
<<PPEA-3之合成>> 上述PPEA-1之合成方法中,除了將反應時間設為6小時以外,利用相同方法得到PPEA-3。PPEA-3之數平均分子量為14,500,重量平均分子量為50,000。 <<Synthesis of PPEA-3>> In the above synthesis method of PPEA-1, except that the reaction time was set to 6 hours, PPEA-3 was obtained by the same method. The number average molecular weight of PPEA-3 was 14,500, and the weight average molecular weight was 50,000.
<<PPEA-4之合成>> 上述PPEA-1之合成方法中,除了將反應時間設為5小時以外,利用相同方法得到PPEA-4。PPEA-4之數平均分子量為12,000,重量平均分子量為36,000。 <<Synthesis of PPEA-4>> In the above synthesis method of PPEA-1, PPEA-4 was obtained by the same method except that the reaction time was set to 5 hours. The number average molecular weight of PPEA-4 was 12,000, and the weight average molecular weight was 36,000.
<<<聚苯醚B之合成>>> <<PPEB-1之合成>> 於3L之二口茄型燒瓶中,加入二-μ-羥基-雙[(N,N,N’, N’-四甲基伸乙二胺)銅(II)]氯化物(Cu/TMEDA)0.050g與四甲基伸乙二胺(TMEDA)0.0047g並使其充分溶解,以50ml/min的條件供給氧。使作為原料苯酚類之2,6-二甲基苯酚8.8g(80mol%)與2-烯丙基-6-甲基苯酚0.67g(10mol%)2-烯丙基苯酚1.2g(10mol%)溶解於甲苯60mL而調製原料溶液。將該原料溶液滴入燒瓶,一面以600rpm之旋轉速度進行攪拌一面於40℃下使其反應18小時。反應結束後,以甲醇1.2L:濃鹽酸4mL之混合液進行再沉澱並過濾取出,於80℃下使其乾燥24小時,得到PPEB-1。PPEB-1之數平均分子量為5,600,重量平均分子量為11,500。 <<<Synthesis of polyphenylene ether B>>> <<Synthesis of PPEB-1>> In a 3L two-necked eggplant-shaped flask, add di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)]chloride (Cu/TMEDA) 0.050 g and 0.0047 g of tetramethylethylenediamine (TMEDA) were fully dissolved, and oxygen was supplied at a rate of 50 ml/min. 8.8g (80mol%) of 2,6-dimethylphenol as raw material phenols and 0.67g (10mol%) of 2-allyl-6-methylphenol and 1.2g (10mol%) of 2-allylphenol It was dissolved in 60 mL of toluene to prepare a raw material solution. This raw material solution was dripped into the flask, and it was made to react at 40 degreeC for 18 hours, stirring at the rotation speed of 600 rpm. After the reaction, reprecipitate with a mixture of methanol 1.2L:concentrated hydrochloric acid 4mL, filter it out, and dry it at 80°C for 24 hours to obtain PPEB-1. The number average molecular weight of PPEB-1 was 5,600, and the weight average molecular weight was 11,500.
<<PPEB-2之合成>> 上述PPEB-1之合成方法中,除了將作為原料苯酚類之2,6-二甲基苯酚變更為5.5g(50mol%)與將2-烯丙基-6-甲基苯酚變更為5.3g(40mol%)以外,利用相同方法得到PPEB-2。PPEB-2之數平均分子量為5,400,重量平均分子量為11,200。 <<Synthesis of PPEB-2>> In the synthesis method of the above-mentioned PPEB-1, in addition to changing 2,6-dimethylphenol as raw material phenols to 5.5g (50mol%) and changing 2-allyl-6-methylphenol to 5.3g ( 40mol%), the same method was used to obtain PPEB-2. The number average molecular weight of PPEB-2 was 5,400, and the weight average molecular weight was 11,200.
<<PPEB-3之合成>> 上述PPEB-1之合成方法中,除了將作為原料苯酚類之2,6-二甲基苯酚變更為1.1g(10mol%)與將2-烯丙基-6-甲基苯酚變更為10.7g(80mol%)以外,利用相同方法得到PPEB-3。PPEB-2之數平均分子量為5,600,重量平均分子量為14,000。 <<Synthesis of PPEB-3>> In the synthesis method of PPEB-1 mentioned above, in addition to changing 2,6-dimethylphenol as raw material phenols to 1.1g (10mol%) and changing 2-allyl-6-methylphenol to 10.7g ( 80mol%), the same method was used to obtain PPEB-3. The number average molecular weight of PPEB-2 was 5,600, and the weight average molecular weight was 14,000.
<<<硬化性組成物之調製>>> <<實施例1>> 摻合PPEA-1:75質量份、PPEB-3:25質量份、作為光自由基產生劑之苯基雙(2,4,6-三甲基苯甲醯基)氧化膦(IGM Resins公司製:商品名「Omnirad 819」):3質量份、及作為含硫醇基化合物之三羥甲基丙烷參(3-巰基丙酸酯)(SC有機化學股份有限公司製:商品名「TMMP」):20質量份,加入環己酮:400質量份,於40℃混合30分鐘並加以攪拌使其完全溶解。接著,摻合作為過氧化物之α,α’-雙(t-丁基過氧基間異丙基)苯(日本油脂股份有限公司製:商品名「PERBUTYL P」):2質量份,以電磁攪拌器進行攪拌,得到實施例1之樹硬化性組成物之塗料。 <<<Preparation of curable composition>>> <<Example 1>> PPEA-1: 75 parts by mass, PPEB-3: 25 parts by mass, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins Co. : trade name "Omnirad 819"): 3 parts by mass, and trimethylolpropane ginseng (3-mercaptopropionate) as a thiol group-containing compound (manufactured by SC Organic Chemicals Co., Ltd.: trade name "TMMP") : 20 parts by mass, add cyclohexanone: 400 parts by mass, mix and stir at 40°C for 30 minutes to completely dissolve. Next, α,α'-bis(t-butylperoxym-isopropyl)benzene (manufactured by NOF Co., Ltd.: trade name "PERBUTYL P") as a peroxide: 2 parts by mass was blended with Stir with an electromagnetic stirrer to obtain the coating of the tree hardening composition of Example 1.
<<實施例2~10、比較例1~6>> 除了將各成分與含量設為示於表1的成分及數值以外,與實施例1相同地調製硬化性組成物,得到實施例2-13、比較例1-3之硬化性組成物之塗料。 <<Example 2~10, Comparative Example 1~6>> Except that each component and content were the components and values shown in Table 1, curable compositions were prepared in the same manner as in Example 1, and coating materials of curable compositions in Examples 2-13 and Comparative Examples 1-3 were obtained.
<<<評價>>> 對於各硬化性組成物及硬化各硬化性組成物而得的硬化膜,進行以下評價。將評價結果示於表1。 <<<Evaluation>>> The following evaluations were performed on each curable composition and the cured film obtained by curing each curable composition. Table 1 shows the evaluation results.
<<感光性及顯影性評價>> 以使乾燥後的膜厚成為約3μm的方式,將各硬化性組成物之塗料使用旋轉塗佈器而塗佈於矽晶圓上,利用加熱板於80℃乾燥1分鐘,形成由各硬化性組成物所構成之樹脂層。之後,將形成有樹脂層的矽晶圓裁切成2.5×15cm之形狀,作為感光性及顯影性之試驗用樣品。對於各試驗樣品之樹脂層,照射以累積光量計0(未曝光)、400、800、1200、1600、2000mJ/cm 2的波長365nm之光,接著,於環己酮浸漬10秒浸漬進行顯影。使顯影後之試驗樣品乾燥後,以觸針式表面形狀測定器測定各曝光量下殘存的樹脂層之厚度。基於未曝光部之殘存膜厚與各曝光部之殘存膜厚之差(顯影對比),利用以下基準評價可否進行光微影。 (評價基準) ◎◎:以800mJ/cm 2以上之曝光得到充分的顯影對比。 ◎:以1200mJ/cm 2以上之曝光得到充分的顯影對比。 ○:以2000mJ/cm 2之曝光得到充分的顯影對比。 △:以2000mJ/cm 2之曝光得到些微的顯影對比。 ×:曝光部未得到耐顯影性、或未曝光部未顯影,無法得到顯影對比。 <<Photosensitivity and Developability Evaluation>> The paint of each curable composition was applied on a silicon wafer using a spin coater so that the film thickness after drying was about 3 μm, and the coating was heated at 80 Dry at ℃ for 1 minute to form a resin layer composed of each curable composition. Afterwards, the silicon wafer formed with the resin layer was cut into a shape of 2.5×15 cm, which was used as a test sample for photosensitivity and developability. The resin layer of each test sample was irradiated with light with a wavelength of 365nm of 0 (unexposed), 400, 800, 1200, 1600, and 2000 mJ/ cm2 in terms of cumulative light intensity, and then dipped in cyclohexanone for 10 seconds for development. After drying the test sample after development, the thickness of the remaining resin layer at each exposure amount was measured with a stylus surface shape measuring device. Based on the difference between the remaining film thickness of the unexposed part and the remaining film thickness of each exposed part (developing contrast), the possibility of photolithography was evaluated by the following criteria. (Evaluation Criteria) ◎◎: Sufficient development contrast was obtained at an exposure of 800 mJ/cm 2 or more. ◎: Sufficient development contrast was obtained with an exposure of 1200 mJ/cm 2 or more. ◯: Sufficient development contrast was obtained at an exposure of 2000 mJ/cm 2 . Δ: Slight development contrast was obtained with an exposure of 2000 mJ/cm 2 . x: The exposure part did not acquire development resistance, or the non-exposed part was not developed, and the image development contrast was not obtained.
<<介電特性>> 以使乾燥後之膜厚成為30μm的方式,以塗敷器將各硬化性組成物塗佈於厚度18μm銅箔之光澤面,利用熱風式循環式乾燥爐於90℃乾燥30分鐘。接著,於無氧化烘箱以200℃硬化1h後,藉由蝕刻銅箔得到由各組成物所構成之硬化物(硬化膜)。 <<Dielectric properties>> Each curable composition was applied to the glossy surface of copper foil with a thickness of 18 μm by an applicator so that the film thickness after drying would be 30 μm, and dried at 90° C. for 30 minutes in a hot-air circulation drying oven. Next, after curing in a non-oxidizing oven at 200° C. for 1 hour, a cured product (cured film) composed of each composition was obtained by etching the copper foil.
將所製作之硬化膜裁切成長度80mm、寬度45mm並將其作為試驗片,藉由SPDR(Split Post Dielectric Resonator)共振器法測定相對介電率Dk及介電正切Df。測定器中,使用Keysight Technologies有限責任公司製向量型網絡分析儀E5071C、SPDR共振器、計算程式使用QWED公司製。條件設為頻率數10GHz、測定溫度25℃。The produced cured film was cut into length 80mm, width 45mm and used as a test piece, and relative permittivity Dk and dielectric tangent Df were measured by SPDR (Split Post Dielectric Resonator) resonator method. As a measuring device, a vector network analyzer E5071C manufactured by Keysight Technologies Co., Ltd., an SPDR resonator, and a calculation program manufactured by QWED Corporation were used. The conditions were set to a frequency of 10 GHz and a measurement temperature of 25°C.
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