TW201602188A - Resin insulation layer formation method, resin insulation layer and printed circuit board - Google Patents
Resin insulation layer formation method, resin insulation layer and printed circuit board Download PDFInfo
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- TW201602188A TW201602188A TW104106816A TW104106816A TW201602188A TW 201602188 A TW201602188 A TW 201602188A TW 104106816 A TW104106816 A TW 104106816A TW 104106816 A TW104106816 A TW 104106816A TW 201602188 A TW201602188 A TW 201602188A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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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
- G03F7/16—Coating processes; Apparatus therefor
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
Abstract
Description
本發明係關於樹脂絕緣層之形成方法、樹脂絕緣層以及印刷配線板。 The present invention relates to a method of forming a resin insulating layer, a resin insulating layer, and a printed wiring board.
印刷配線板一般係利用蝕刻去除貼合於積層板上之銅箔的不必要部分而形成電路配線者，且以焊接將電子零件配置於特定部位。該種印刷配線板係使用塗布於基材上並硬化形成之阻焊劑作為焊接電子零件時之電路之保護膜(例如，專利文獻1、2)。 The printed wiring board is generally formed by etching to remove unnecessary portions of the copper foil bonded to the laminated board to form a circuit wiring, and the electronic component is placed at a specific portion by soldering. In such a printed wiring board, a solder resist which is applied to a substrate and hardened is used as a protective film for a circuit when soldering an electronic component (for example, Patent Documents 1 and 2).
該阻焊劑係在焊接時，防止焊料附著於不必要部分，同時防止電路導體直接暴露於空氣中因氧或濕氣造成之劣化。另外，阻焊劑亦揮發作為電路基板之永久保護膜之功能。因此，其除了要求密著性、電絕緣性、焊料耐熱性、耐溶劑性等諸特性外，亦要求耐酸性等耐藥品性。且，針對無電解鍍金部周邊之阻劑不易剝離，或因氧化造成之銅箔變色導致之外觀不良之抑制，亦要求高性能化。 The solder resist prevents solder from adhering to unnecessary portions during soldering while preventing direct deterioration of the circuit conductor to air due to oxygen or moisture. In addition, the solder resist also functions as a permanent protective film for the circuit substrate. Therefore, in addition to properties such as adhesion, electrical insulation, solder heat resistance, and solvent resistance, chemical resistance such as acid resistance is also required. Further, it is required that the resist agent around the electroless gold plating portion is not easily peeled off, or the appearance of the copper foil due to oxidation is suppressed, and the performance is also required to be improved.
專利文獻1：日本特開昭50-6408號公報(申請專利範圍) Patent Document 1: Japanese Laid-Open Patent Publication No. SHO-50-6408 (Application No.)
專利文獻2：日本特開平7-50473號公報(申請專利範圍) Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 7-50473 (Application No.)
因此本發明之目的係提供耐酸性、無電解鍍金耐性及銅箔之變色抑制優異之樹脂絕緣層之形成方法、以該形成方法形成之樹脂絕緣層、及具有該樹脂絕緣層之印刷配線板。 Therefore, an object of the present invention is to provide a method for forming a resin insulating layer which is excellent in acid resistance, electroless gold plating resistance, and discoloration suppression of a copper foil, a resin insulating layer formed by the forming method, and a printed wiring board having the resin insulating layer.
本發明人等積極檢討之結果，發現在熱硬化時藉由使用奈米化過熱乾燥蒸氣形成樹脂絕緣層，可解決上述課題，終於完成本發明。 As a result of a positive review by the inventors of the present invention, it has been found that the above problem can be solved by forming a resin insulating layer by using a nano-heated dry steam at the time of thermosetting, and finally completed the present invention.
亦即，本發明之樹脂絕緣層之形成方法係在基材上形成硬化性樹脂組成物之乾燥塗膜，接著進行熱硬化之樹脂絕緣層之形成方法，其特徵為前述熱硬化具備使用奈米化過熱乾燥蒸氣進行熱硬化之步驟。 That is, the method of forming the resin insulating layer of the present invention is a method of forming a dried coating film of a curable resin composition on a substrate, followed by a method of forming a resin insulating layer which is thermally cured, characterized in that the thermosetting has a use of a nanometer. The step of thermally hardening the superheated dry steam.
本發明之樹脂絕緣層之形成方法較好為前述乾燥塗膜為於基材上塗布前述硬化性樹脂組成物，並使其乾燥所形成者。 In the method for forming a resin insulating layer of the present invention, it is preferred that the dried coating film is formed by applying the curable resin composition to a substrate and drying the composition.
本發明之樹脂絕緣層之形成方法較好為前述乾燥塗膜係使用乾膜所形成，該乾膜為於薄膜上塗布前述硬化性樹脂組成物，並使其乾燥所得。 In the method for forming a resin insulating layer of the present invention, it is preferred that the dry coating film is formed by using a dry film obtained by applying the curable resin composition onto a film and drying the film.
本發明之樹脂絕緣層之形成方法較好為前述乾膜為使用奈米化過熱乾燥蒸氣進行乾燥處理者。 In the method for forming the resin insulating layer of the present invention, it is preferred that the dry film is dried by using a nano-heated dry steam.
本發明之樹脂絕緣層之形成方法較好為前述硬化性樹脂組成物為鹼顯像型之硬化性樹脂組成物。 In the method for forming the resin insulating layer of the present invention, the curable resin composition is preferably a curable resin composition of an alkali developing type.
本發明之樹脂絕緣層之形成方法較好為在形成前述乾燥塗膜之後，進行曝光、顯像。 In the method for forming the resin insulating layer of the present invention, it is preferred to perform exposure and development after forming the dried coating film.
本發明之樹脂絕緣層之形成方法較好為前述乾燥塗膜被形成於前述基材上之銅上。 In the method of forming the resin insulating layer of the present invention, it is preferred that the dried coating film is formed on the copper on the substrate.
本發明之樹脂絕緣層為特徵為以前述樹脂絕緣層之形成方法所製造者。 The resin insulating layer of the present invention is characterized by being produced by the above-described method of forming a resin insulating layer.
本發明之印刷配線板之特徵為具備前述樹脂絕緣層者。 The printed wiring board of the present invention is characterized in that it has the resin insulating layer described above.
依據本發明，可提供耐酸性、無電解鍍金耐性及銅箔之變色抑制優異之樹脂絕緣層之形成方法、以該形成方法形成之樹脂絕緣層、及具有該樹脂絕緣層之印刷配線板。 According to the present invention, it is possible to provide a method for forming a resin insulating layer which is excellent in acid resistance, electroless gold plating resistance, and discoloration suppression of a copper foil, a resin insulating layer formed by the forming method, and a printed wiring board having the resin insulating layer.
本發明之樹脂絕緣層之形成方法係在基材上形成硬化性樹脂組成物之乾燥塗膜，接著進行熱硬化之樹脂絕緣層之形成方法，其特徵為前述熱硬化具備使用奈米化過熱乾燥蒸氣進行熱硬化之步驟。藉由使用奈米化過熱乾燥蒸氣進行熱硬化，可提高硬化獲得之樹脂絕緣層之耐酸性、無電解鍍金耐性及銅箔之變色抑制。藉由提高銅箔之變色抑制，亦可在硬化性樹脂組成物中實質上不調配三聚氰胺等用以防止銅燒蝕之抗氧化劑或用以使銅燒蝕不易看見之紅色著色劑。此外，藉由使用奈米化過熱乾燥蒸氣而熱硬化，可產生乾燥塗膜中所含之有機溶劑之揮發、分解及降低。 The method for forming a resin insulating layer of the present invention is a method for forming a dried coating film of a curable resin composition on a substrate, followed by a method of forming a resin insulating layer which is thermally cured, characterized in that the thermosetting is performed by using a nano-heating drying method. The step of steam hardening. By using a nano-heated dry steam for thermal hardening, the acid resistance of the resin insulating layer obtained by hardening, the electroless gold plating resistance, and the discoloration suppression of the copper foil can be improved. By increasing the discoloration inhibition of the copper foil, it is also possible to substantially prevent the oxidizing resin composition such as melamine or the like from being used to prevent copper ablation or the red coloring agent which is used to make copper ablate difficult to see. Further, by using a nano-heated dry steam to be thermally hardened, volatilization, decomposition, and reduction of the organic solvent contained in the dried coating film can be caused.
本發明之樹脂絕緣層之形成方法中，使用奈米化過熱乾燥蒸氣之熱硬化較好在130℃以上進行。在130℃以上時，更提高硬化性。更好為130~300℃，又更好為170~300℃，最好為180~300℃。 In the method for forming a resin insulating layer of the present invention, thermal hardening using a nano-heated dry steam is preferably carried out at 130 ° C or higher. When it is 130 ° C or more, the hardenability is further improved. It is preferably 130 to 300 ° C, more preferably 170 to 300 ° C, and most preferably 180 to 300 ° C.
又，使用奈米化過熱乾燥蒸氣之熱硬化較好進行1~10分鐘。於1~10分鐘時，更提高硬化性。更好為1~5分鐘。 Further, the thermal hardening using the nano-heated dry steam is preferably carried out for 1 to 10 minutes. At 1 to 10 minutes, the hardenability is further improved. Better for 1~5 minutes.
此外本發明之樹脂絕緣層之形成方法中，根據硬化性樹脂組成物之種類或樹脂絕緣層之形成條件而定，即使在用以使溶劑揮發，形成前述乾燥塗膜之乾燥處理中，仍可使用奈米化過熱乾燥蒸氣。乾燥溫度較好為60~100℃，更好為70~90℃。 Further, in the method for forming the resin insulating layer of the present invention, depending on the type of the curable resin composition or the formation conditions of the resin insulating layer, even in the drying treatment for forming the dried coating film by volatilizing the solvent, Use nano-heated dry steam. The drying temperature is preferably from 60 to 100 ° C, more preferably from 70 to 90 ° C.
本發明之樹脂絕緣層之形成方法中使用之奈 米化過熱乾燥蒸氣係使飽和水蒸氣加熱並乾燥之過熱乾燥蒸氣進一步微細化者。微細化方法並無特別限制，例如可藉由對過熱乾燥蒸氣賦予噴射能、衝撞能及利用超音波或電磁波之激發能等之能量而微細化。 The nephew used in the method for forming a resin insulating layer of the present invention The rice superheated and dried steam is obtained by further heating the superheated dry steam which is heated and dried by the saturated steam. The method of miniaturization is not particularly limited, and can be made fine by, for example, imparting energy to the superheated dry steam, collision energy, and excitation energy by ultrasonic waves or electromagnetic waves.
前述噴射能之賦予方法列舉為例如藉由過熱乾燥蒸氣之生成中產生之蒸氣壓，自噴嘴噴射而團簇化(cluster)之方法等。前述衝撞能之賦予方法列舉為例如使過熱乾燥蒸氣衝撞到經開口之振動板盤面之方法等。激發能之賦予方法列舉為將超音波振動元件安裝於前述振動板上之方法等。利用超音波賦予激發能時，宜將其超音波之頻率設定在50~200kHz之範圍，且，利用電磁波賦予激發能時，其波長宜設定為0.7~2.5μm之範圍，但可依硬化性樹脂組成物之組成或塗布之厚度等適當設定。 The method of imparting the above-described ejection energy is, for example, a method of clustering from a nozzle by a vapor pressure generated in the formation of superheated drying vapor, and the like. The method of imparting the collision energy is exemplified by a method of causing the superheated dry steam to collide with the opening of the vibrating plate surface. The method of imparting excitation energy is exemplified by a method of attaching an ultrasonic vibration element to the above-mentioned vibration plate. When the excitation energy is given by the ultrasonic wave, the frequency of the ultrasonic wave should be set in the range of 50 to 200 kHz, and when the excitation energy is given by the electromagnetic wave, the wavelength should be set in the range of 0.7 to 2.5 μm, but the curable resin can be used. The composition of the composition, the thickness of the coating, and the like are appropriately set.
過熱乾燥蒸氣之微細化方法較好為藉由對過熱乾燥蒸氣賦予噴射能，使過熱乾燥蒸氣微細化而團簇化，且藉由對前述團簇化之過熱乾燥蒸氣賦予衝撞能，使前述經團簇化之過熱乾燥蒸氣之粒子進一步微細化之方法，及進一步藉由對經賦予前述能量之奈米化過熱乾燥蒸氣賦予激發能而使過熱乾燥蒸氣超微細化之方法。 In the method of miniaturizing the superheated dry steam, it is preferred to impart a jet energy to the superheated dry steam to refine the superheated dry steam to be clustered, and to impart collision energy to the superposed dry steam of the clustering. A method of further refining the clustered superheated dry vapor particles, and further superheating the superheated dry steam by imparting excitation energy to the nano-heated superheated dry steam to which the energy is applied.
奈米化過熱乾燥蒸氣對樹脂絕緣層之應用，較好在將奈米化過熱乾燥蒸氣供給至超過飽和狀態而形成之無氧氛圍內進行。 The application of the nano-heated dry steam to the resin insulating layer is preferably carried out in an oxygen-free atmosphere formed by supplying the nano-heated dry steam to a state exceeding the saturated state.
此外，奈米化過熱乾燥蒸氣對樹脂絕緣層之應用可使用KESSEL公司製造之DEON或日本特開2013- 177986號公報中所記載之乾燥裝置等習知慣用之裝置進行。 In addition, the application of nano-heated dry steam to the resin insulation layer can be performed by DESEN or Japan Special Open 2013-made by KESSEL. A conventionally used device such as a drying device described in Japanese Patent Publication No. 177986 is used.
本發明之樹脂絕緣層之形成方法中，硬化性樹脂組成物並無特別限制，可使用例如阻焊層之形成所用之硬化性樹脂組成物。具體例可列舉為包含環氧樹脂之熱硬化性樹脂組成物；含羧基之樹脂或含羧基之感光性樹脂、具有乙烯性不飽和鍵之化合物、包含光聚合起始劑及熱反應性化合物之光硬化性熱硬化性樹脂組成物；及含羧基之樹脂、包含光鹼產生劑及熱反應性化合物之感光性熱硬化性樹脂組成物等，其中亦可含著色劑或體質原料，但並不限於該等。鹼顯像型之硬化性樹脂組成物並無特別限制，可使用前述光硬化性熱硬化性樹脂組成物或前述感光性熱硬化性樹脂組成物等。 In the method of forming the resin insulating layer of the present invention, the curable resin composition is not particularly limited, and for example, a curable resin composition for forming a solder resist layer can be used. Specific examples thereof include a thermosetting resin composition containing an epoxy resin; a carboxyl group-containing resin or a carboxyl group-containing photosensitive resin; a compound having an ethylenically unsaturated bond; and a photopolymerization initiator and a heat-reactive compound. a photocurable thermosetting resin composition; a carboxyl group-containing resin; a photosensitive thermosetting resin composition containing a photobase generator and a heat-reactive compound, and the like, which may contain a coloring agent or a body material, but not Limited to these. The alkali-developing type of the curable resin composition is not particularly limited, and the photocurable thermosetting resin composition or the photosensitive thermosetting resin composition or the like can be used.
本發明之樹脂絕緣層之形成方法中，硬化性樹脂組成物可如上述，藉由提高銅箔之變色抑制、耐酸性及無電解鍍金耐性，而將硬化性樹脂組成物中之三聚氰胺等用以防止銅燒蝕之抗氧化劑之調配量減量或實質上不含於組成物中。本說明書中，所謂實質上不含為未積極地調配作為構成成分，且不排除在不損及本發明效果之範圍內少量含有。例如，可將抗氧化劑之調配量設為在去除有機溶劑之揮發成分後之硬化性樹脂組成物中1質量%以下，更好為0.5質量%以下，又更好為0.1質量%以下。 In the method for forming a resin insulating layer of the present invention, the curable resin composition can be used for melamine in a curable resin composition by improving discoloration suppression, acid resistance, and electroless gold plating resistance of the copper foil as described above. The amount of the antioxidant which prevents copper ablation is reduced or substantially absent from the composition. In the present specification, the term "substantially not contained" is not actively formulated as a constituent component, and is not excluded to be contained in a small amount within a range not impairing the effects of the present invention. For example, the amount of the antioxidant to be added is 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less, of the curable resin composition after removing the volatile component of the organic solvent.
本發明之樹脂絕緣層之形成方法中，硬化性樹脂組成物亦可包含用以調整組成物黏度之有機溶劑。有 機溶劑可使用習知慣用者。列舉為例如甲苯、二甲苯、乙酸乙酯、乙酸丁酯、甲醇、乙醇、異丙醇、異丁醇、1-丁醇、二丙酮醇、乙二醇單丁基醚、丙二醇單乙基醚、丙二醇單甲基醚乙酸酯、松油醇(terpineol)、甲基乙基酮、卡必醇、卡必醇乙酸酯、丁基卡必醇、丁基卡必醇乙酸酯、二乙二醇單乙基醚乙酸酯、二丙二醇單甲基醚、芳香族烴等。溶劑可單獨使用1種，亦可組合2種以上使用。 In the method of forming a resin insulating layer of the present invention, the curable resin composition may further comprise an organic solvent for adjusting the viscosity of the composition. Have The organic solvent can be used by a conventional one. Listed as, for example, toluene, xylene, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, isobutanol, 1-butanol, diacetone alcohol, ethylene glycol monobutyl ether, propylene glycol monoethyl ether , propylene glycol monomethyl ether acetate, terpineol, methyl ethyl ketone, carbitol, carbitol acetate, butyl carbitol, butyl carbitol acetate, two Ethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, aromatic hydrocarbons, and the like. The solvent may be used singly or in combination of two or more.
本發明之樹脂絕緣層之形成方法可較好地使用於印刷配線板之永久保護膜之形成，其中可較好地使用於阻焊層、層間絕緣層、可撓性印刷配線板之保護層之形成。 The method for forming a resin insulating layer of the present invention can be preferably used for forming a permanent protective film of a printed wiring board, and can be preferably used for a solder resist layer, an interlayer insulating layer, and a protective layer of a flexible printed wiring board. form.
本發明之樹脂絕緣層之形成方法中之基材除了預先形成電路之印刷配線板或可撓性印刷配線板以外，可列舉為使用利用紙酚、紙環氧樹脂、玻璃布環氧樹脂、玻璃聚醯亞胺、玻璃布/不織布環氧樹脂、玻璃布/紙環氧樹脂、合成纖維環氧樹脂、氟樹脂、聚乙烯‧聚苯醚‧氰酸酯樹脂等之高頻回路用貼銅積層板等材質者全部等級(FR-4等)之貼銅基層板、其他聚醯亞胺薄膜、PET薄膜、玻璃基板、陶瓷基板、晶圓板等。 The substrate in the method for forming a resin insulating layer of the present invention may be exemplified by using a paper phenol, a paper epoxy resin, a glass cloth epoxy resin, or a glass, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance. Copper-clad laminate for high-frequency circuits such as polyimide, glass cloth/non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin, polyethylene ‧ polyphenylene ether ‧ cyanate resin A copper-based base plate, other polyimide film, PET film, glass substrate, ceramic substrate, wafer plate, etc. of all grades (FR-4, etc.).
本發明之樹脂絕緣層之形成方法中乾燥塗膜之形成方法並無特別限制，例如，只要將硬化性樹脂組成物塗布於基材上，或者，將硬化性樹脂組成物塗布於薄膜上，經乾燥獲得之乾燥薄膜層合於基材上且使形成之塗膜乾燥即可。硬化性樹脂組成物之塗布只要利用缺角輪塗布 器、刮刀塗布器、唇模塗布器、薄膜塗布器、棒塗布器、擠壓(squeeze)塗布器、逆向輥塗布器、轉移輥塗布器、凹版塗布器、噴霧塗布器等適宜之方法進行即可。塗布膜厚並無特別限制，只要以乾燥膜厚計成為10~50μm之方式塗布即可。乾燥方法並無特別限制，可使用熱風循環式乾燥爐、IR(紅外線)爐、加熱板、對流烘箱等之使用具備利用蒸氣之空氣加熱方式之熱源者，使乾燥機內之熱風對流接觸之方法及自噴嘴吹向支撐體之方法。較好以熱風循環式乾燥爐、遠紅外線乾燥爐等進行。此外，乾燥方法亦可使用奈米化過熱乾燥蒸氣，該情況下，可獲得觸黏性(指觸乾燥性)優異之乾燥塗膜。 The method for forming the dried coating film in the method for forming a resin insulating layer of the present invention is not particularly limited. For example, if the curable resin composition is applied onto a substrate, or the curable resin composition is applied onto the film, The dried film obtained by drying is laminated on a substrate and the formed coating film is dried. Coating of the curable resin composition is only required to be coated by a notch wheel Suitable methods, such as a knife applicator, a lip coater, a film applicator, a bar coater, a squeeze coater, a reverse roll coater, a transfer roll coater, a gravure coater, a spray coater, etc. can. The coating film thickness is not particularly limited, and it may be applied so as to have a dry film thickness of 10 to 50 μm. The drying method is not particularly limited, and a hot air circulating drying furnace, an IR (infrared) furnace, a heating plate, a convection oven, or the like, which uses a heat source using a steam heating method, can be used to bring the hot air in the dryer into contact with each other. And a method of blowing from the nozzle to the support. It is preferably carried out in a hot air circulation type drying furnace or a far infrared ray drying furnace. Further, the drying method may also use a nano-heated dry steam, and in this case, a dry coating film excellent in contact resistance (dryness to touch) can be obtained.
乾膜所用之載體膜係使用塑膠膜，較好使用聚對苯二甲酸乙二酯等聚酯膜、聚醯亞胺膜、聚醯胺醯亞胺膜、聚丙烯膜、聚苯乙烯膜等塑膠膜。載體膜之厚度無特別限制，但一般係在10~150μm之範圍內適當選擇。 The carrier film used for the dry film is a plastic film, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like. Plastic film. The thickness of the carrier film is not particularly limited, but is generally suitably selected within the range of 10 to 150 μm.
此外，基於防止灰塵附著於乾膜之硬化性樹脂組成物層表面之目的，較好於硬化性樹脂組成物層之表面積層可剝離之保護膜。可剝離之保護膜可使用例如聚乙烯膜、聚四氟乙烯膜、聚丙烯膜、經表面處理之紙等，只要在剝離保護膜時，硬化性樹脂組成物層與保護膜之接著力比硬化性樹脂組成物層與載體膜之接著力小者即可。 Further, for the purpose of preventing dust from adhering to the surface of the curable resin composition layer of the dry film, a protective film which is peelable from the surface layer of the curable resin composition layer is preferable. As the peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, as long as the adhesion between the curable resin composition layer and the protective film is harder than when the protective film is peeled off. The adhesive force of the resin composition layer and the carrier film may be small.
硬化性樹脂組成物為顯像型之硬化性樹脂組成物時，可在乾燥塗膜形成後，將利用曝光步驟及顯像步驟之過去習知之光微影法進行之圖型化應用於乾燥塗膜 上。曝光步驟並無特別限制，例如可利用接觸式(或非接觸式)，通過形成所需圖型之光罩選擇性以活性能量線曝光，或者亦可利用直接描繪裝置直接使期望之圖型以活性能量線曝光。 When the curable resin composition is a development type curable resin composition, after the formation of the dried coating film, the patterning by the conventional photolithography method using the exposure step and the development step can be applied to the dry coating. membrane on. The exposure step is not particularly limited. For example, contact type (or non-contact type) can be used to selectively expose the active energy line by forming a mask of a desired pattern, or the direct drawing device can be used to directly make the desired pattern Active energy line exposure.
曝光機之光源可使用例如金屬鹵素燈、高壓水銀燈、超高壓水銀燈、水銀短弧燈、LED等。且，以直接描繪裝置曝光時，可使用氣體雷射、固體雷射等之雷射，或高壓水銀燈、超高壓水銀燈等之紫外線燈、LED燈等。此種直接描繪裝置可使用例如日本ORBOTECH公司製造、ORK製作所公司製造、大日本網版製造公司製造等者。活性能量線較好使用最大波長為350~410nm之範圍之雷射光。藉由將最大波長設為該範圍，可自光聚合起始劑有效地生成自由基。且，其曝光量係隨膜厚等而異，但一般可設為5~500mJ/cm2，較好10~300mL/cm2之範圍內。 As the light source of the exposure machine, for example, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a mercury short arc lamp, an LED, or the like can be used. Further, when exposing by a direct drawing device, a laser such as a gas laser or a solid laser or an ultraviolet lamp such as a high pressure mercury lamp or an ultrahigh pressure mercury lamp or an LED lamp can be used. Such a direct drawing device can be, for example, manufactured by ORBOTECH Co., Ltd., manufactured by ORK Manufacturing Co., Ltd., manufactured by Dainippon Screen Manufacturing Co., Ltd., and the like. The active energy ray preferably uses laser light having a maximum wavelength of 350 to 410 nm. By setting the maximum wavelength to this range, radicals can be efficiently generated from the photopolymerization initiator. Further, the amount of exposure varies depending on the film thickness, etc., but it can be generally in the range of 5 to 500 mJ/cm 2 , preferably 10 to 300 mL/cm 2 .
顯像步驟並無特別限制，可使用浸漬法、淋洗法、噴佈法、刷塗法等。此外，顯像液可使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等鹼性水溶液。 The developing step is not particularly limited, and a dipping method, a rinsing method, a spray method, a brush method, or the like can be used. Further, as the developing solution, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine can be used.
本發明之樹脂絕緣層之形成方法中，乾燥塗膜之熱硬化係如上述，使用奈米化過熱乾燥蒸氣。 In the method for forming a resin insulating layer of the present invention, the thermal curing of the dried coating film is as described above, and the dried superheated steam is used.
以下，使用實施例更詳細說明本發明。 Hereinafter, the present invention will be described in more detail by way of examples.
於具備溫度計、氮氣導入裝置兼環氧烷導入裝置及攪拌裝置之高壓釜中饋入酚醛清漆型甲酚樹脂(昭和高分子公司製造，商品名「SHONOL CRG951」、OH當量：119.4)119.4份、氫氧化鉀1.19份及甲苯119.4份，邊攪拌邊將系統內部置換成氮氣，且加熱升溫。接著緩慢滴加環氧丙烷63.8份，在125~132℃以0~4.8kg/cm2反應16小時。隨後，冷卻至室溫，將89%磷酸1.56份添加混合於該反應溶液中以中和氫氧化鉀，獲得不揮發份62.1%、羥基價182.2g/eq.之酚酸清漆型甲酚樹脂之環氧丙烷反應溶液。其係酚性羥基每1當量平均加成1.08莫耳之環氧烷而成者。 119.4 parts of a novolac type cresol resin (product name "SHONOL CRG951", OH equivalent: 119.4) was fed into an autoclave equipped with a thermometer, a nitrogen gas introduction device, an alkylene oxide introduction device, and a stirring device. 1.19 parts of potassium hydroxide and 119.4 parts of toluene were replaced with nitrogen gas while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide was slowly added dropwise, and the mixture was reacted at 0 to 4.8 kg/cm 2 at 125 to 132 ° C for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed in the reaction solution to neutralize potassium hydroxide to obtain a phenolic varnish type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. A propylene oxide reaction solution. It is a phenolic hydroxyl group which is an average of 1.08 moles of alkylene oxide per one equivalent.
將所得酚醛清漆型甲酚樹脂之環氧烷反應溶液293.0份、丙烯酸43.2份、甲烷磺酸11.53份、甲基氫醌0.18份及甲苯252.9份饋入具備攪拌機、溫度計及空氣吹入管之反應器中，以10ml/分鐘之速度吹入空氣，邊攪拌邊在110℃反應12小時。因反應生成之水作為與甲苯之共沸混合物餾出12.6份之水。隨後，冷卻至室溫，所得反應溶液以15%氫氧化鈉水溶液35.35份中和，接著水洗。隨後，以蒸餾器邊以二乙二醇單乙基醚乙酸酯118.1份置換邊餾除甲苯，獲得酚醛清漆型丙烯酸酯樹脂溶液。 293.0 parts of an alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were fed into a reactor equipped with a stirrer, a thermometer, and an air blowing tube. In the air, air was blown at a rate of 10 ml/min, and reacted at 110 ° C for 12 hours while stirring. Water formed by the reaction was distilled off as 12.6 parts of water as an azeotropic mixture with toluene. Subsequently, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, followed by washing with water. Subsequently, toluene was distilled off with a distillation apparatus while replacing 118.1 parts of diethylene glycol monoethyl ether acetate to obtain a novolac type acrylate resin solution.
接著，將所得酚醛清漆型丙烯酸酯樹脂溶液332.5份及三苯基膦1.22份饋入具備攪拌機、溫度計及空 氣吹入管之反應器中，以10ml/分鐘之速度吹入空氣，邊攪拌邊緩慢添加四氫鄰苯二甲酸酐60.8份，在95~101℃下反應6小時，冷卻後取出。如此獲得之含羧基之感光性樹脂之不揮發分為70.6%，固體成分之酸價為87.7mgKOH/g。 Next, 332.5 parts of the obtained novolac type acrylate resin solution and 1.22 parts of triphenylphosphine were fed with a stirrer, a thermometer, and an empty The air was blown into the reactor of the tube, air was blown at a rate of 10 ml/min, and 60.8 parts of tetrahydrophthalic anhydride was slowly added while stirring, and reacted at 95 to 101 ° C for 6 hours, and then taken out after cooling. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 70.6%, and the solid content had an acid value of 87.7 mgKOH/g.
於具備氣體導入管、攪拌裝置、冷卻管、溫度計及鹼金屬氫氧化物水溶液之連續滴加用之滴加漏斗之反應容器中饋入羥基當量80g/當量之1,5-二羥基萘224份與雙酚A型環氧樹脂(三菱化學公司製造，jER828、環氧當量189g/當量)1075份，在氮氣氛圍下，攪拌下於110℃溶解。隨後，添加三苯基膦0.65份，使反應容器內之溫度升溫至105℃，邊使溫度保持在150℃，邊反應約90分鐘，獲得環氧當量452g/當量之環氧化合物(1-a)。接著使燒瓶內之溫度冷卻至40℃，添加表氯醇1920份、甲苯1690份、溴化四甲基銨70份，攪拌下升溫至45℃且保持。隨後，在60分鐘內連續滴加48%氫氧化鈉水溶液364份，接著，再反應6小時。反應結束後，減壓蒸餾且回收過量表氯醇及大半之甲苯，使含副生之鹽與甲苯之反應產物溶解於甲基異丁基酮中並經水洗。分離有機溶劑層與水層後，自有機溶劑層減壓蒸餾餾除甲基異丁基酮，獲得環氧當量277g/當量之多核環氧樹脂(1-b)。所得之多核環氧樹脂(1-b)若由環氧當量計算，環氧化合物(1-a)中之醇性羥基1.98個中約1.59個經環氧化。據此，醇性羥 基之環氧化率約為80%。 The reaction vessel containing a gas introduction tube, a stirring device, a cooling tube, a thermometer, and an aqueous alkali metal hydroxide aqueous solution for dropping the dropping funnel is fed with a hydroxyl equivalent of 80 g/eq. of 1,5-dihydroxynaphthalene 224 parts. 1075 parts of a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent 189 g/eq.) was dissolved in a nitrogen atmosphere at 110 ° C with stirring. Subsequently, 0.65 parts of triphenylphosphine was added, and the temperature in the reaction vessel was raised to 105 ° C, and the temperature was maintained at 150 ° C, and the reaction was carried out for about 90 minutes to obtain an epoxy compound having an epoxy equivalent of 452 g / equivalent (1-a). ). Next, the temperature in the flask was cooled to 40 ° C, and 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the mixture was heated to 45 ° C with stirring and kept. Subsequently, 364 parts of a 48% aqueous sodium hydroxide solution was continuously added dropwise over 60 minutes, followed by further reaction for 6 hours. After completion of the reaction, the mixture was distilled under reduced pressure and excess epichlorohydrin and most of toluene were recovered, and the reaction product containing the by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After separating the organic solvent layer and the aqueous layer, methyl isobutyl ketone was distilled off under reduced pressure from the organic solvent layer to obtain a polynuclear epoxy resin (1-b) having an epoxy equivalent of 277 g/eq. When the obtained multinuclear epoxy resin (1-b) is calculated from the epoxy equivalent, about 1.59 of the 1.98 alcoholic hydroxyl groups in the epoxy compound (1-a) are epoxidized. According to this, alcoholic hydroxyl The epoxidation rate of the base is about 80%.
接著，將多核環氧樹脂(1-b)277份饋入具備攪拌裝置、冷卻管及溫度計之燒瓶中，添加卡必醇乙酸酯290份，加熱溶解，且添加甲基氫醌0.46份與三苯基膦1.38份，加熱至95~105℃，緩慢滴加丙烯酸72份，且反應16小時。將該反應產物冷卻至80~90℃，添加四氫鄰苯二甲酸酐129份，反應8小時。反應係以電位差滴定測定反應液之氧化、全氧化而進行，以所得加成率追蹤，將反應率95%以上設為終點。如此獲得之含羧基之感光性樹脂係不揮發分62%，固體成分之酸價100mgKOH/g。 Next, 277 parts of the multi-core epoxy resin (1-b) was fed into a flask equipped with a stirring device, a cooling tube, and a thermometer, and 290 parts of carbitol acetate was added thereto, and dissolved by heating, and 0.46 parts of methylhydroquinone was added thereto. 1.38 parts of triphenylphosphine, heated to 95-105 ° C, slowly added 72 parts of acrylic acid, and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C, and 129 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted for 8 hours. The reaction system was carried out by measuring the oxidation and total oxidation of the reaction liquid by potentiometric titration, and the obtained addition rate was followed, and the reaction rate was 95% or more as the end point. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 62%, and the solid content had an acid value of 100 mgKOH/g.
依據下述表1所記載之樹脂組成，分別調配各成份，以攪拌機預混合後，以3軸輥混練機混練，調整硬化性樹脂組成物，且藉下述評價方法進行評價。表中之值只要無特別指明即為質量份。又，實施例1所用之硬化性樹脂組成物為熱硬化性樹脂組成物，實施例2、3、5、6所用之硬化性樹脂組成物為光硬化性熱硬化性樹脂組成物。實施例4所用之硬化性樹脂組成物與實施例2之硬化性樹脂組成物相同，但實施例4係藉由乾膜進行各種評價。比較例1~6所用之硬化性樹脂組成物分別與實施例1~6所用之硬化性樹脂組成物相同，差異點為未使用奈米化過熱乾燥蒸氣進行熱硬化。 Each of the components was prepared according to the resin composition described in the following Table 1, and premixed with a stirrer, and then kneaded by a 3-axis roll kneader to adjust the curable resin composition, and evaluated by the following evaluation method. The values in the table are parts by mass unless otherwise specified. Further, the curable resin composition used in Example 1 is a thermosetting resin composition, and the curable resin composition used in Examples 2, 3, 5, and 6 is a photocurable thermosetting resin composition. The curable resin composition used in Example 4 was the same as the curable resin composition of Example 2, but Example 4 was subjected to various evaluations by dry film. The curable resin compositions used in Comparative Examples 1 to 6 were the same as those of the curable resin compositions used in Examples 1 to 6, respectively, and the difference was that the nano-heated dry steam was not used for thermal curing.
感光性樹脂1：上述合成例1所得之含羧基之感光性樹脂 Photosensitive resin 1: the carboxyl group-containing photosensitive resin obtained in the above Synthesis Example 1.
感光性樹脂2：上述合成例2所得之含羧基之感光性樹脂 Photosensitive resin 2: a carboxyl group-containing photosensitive resin obtained in the above Synthesis Example 2.
＊1：EPICLON N-695：原甲酚酚醛清漆型環氧樹脂(DIC公司製造) *1: EPICLON N-695: Original cresol novolak type epoxy resin (manufactured by DIC Corporation)
＊2：LUCIRIN TPO：2,4,6-三甲基苯甲醯基二苯基氧化膦(日本BASF公司製造) *2: LUCIRIN TPO: 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (manufactured by BASF, Japan)
＊3：1B2PZ：1-苯甲醯基-2-苯基咪唑(四國化成工業公司製造) *3:1B2PZ: 1-Benzylmercapto-2-phenylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd.)
＊4：DPHA：二季戊四醇六及五丙烯酸酯混合物(日本化藥公司製造) *4: DPHA: dipentaerythritol hexa- and pentaacrylate mixture (manufactured by Nippon Kayaku Co., Ltd.)
＊5：TMPTA：三羥甲基丙烷三丙烯酸酯(日本化藥公司製造) *5: TMPTA: Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
＊6：RE306：酚醛清漆型環氧樹脂(日本化藥公司製造) *6: RE306: Novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
＊7：EPOTOT YDCN-704P：酚醛清漆型環氧樹脂(東都化成公司製造) *7: EPOTOT YDCN-704P: Novolac type epoxy resin (manufactured by Dongdu Chemical Co., Ltd.)
＊8：B-100：硫酸鋇(堺化學工業公司製造) *8: B-100: Barium sulfate (manufactured by Dai Chemical Industry Co., Ltd.)
＊9：乾燥方法之「-」表示未設置乾燥步驟 *9: "-" of the drying method means that the drying step is not set.
以網版印刷法，使用100網目之聚酯篩網，以成為20~30μm厚之方式將上述獲得之樹脂組成物整面塗布於形 成圖型之印刷配線板上，使用KESSEL公司製造之DEON，在180℃下以奈米化過熱乾燥蒸氣進行加熱硬化5分鐘，製作評價基板。 The above-obtained resin composition was applied to the entire surface by a screen printing method using a 100 mesh mesh screen in a manner of 20 to 30 μm thick. On the patterned printed wiring board, DEON manufactured by KESSEL Co., Ltd. was used, and heat-hardened by nano-heated dry steam at 180 ° C for 5 minutes to prepare an evaluation substrate.
以網版印刷法，使用100網目之聚酯篩網，以成為20~30μm厚之方式將上述獲得之樹脂組成物整面塗布於形成圖型之印刷配線板上，且使用80℃之熱風乾燥器使塗膜乾燥30分鐘。接著，將具有阻劑圖型之負型薄膜密著於塗膜上，使用紫外線曝光裝置(OAK製作所公司製造，型號HMW-680GW)，照射紫外線(曝光量200mJ/cm2)，以1%碳酸鈉水溶液，以2.0kg/cm2之噴射壓顯像60秒並溶解去除未曝光部分。隨後使用KESSEL公司製造之(DEON)，在180℃下以奈米化過熱乾燥蒸氣進行加熱硬化5分鐘，製作評價基板。 The resin composition obtained above was applied to the printed wiring board of the pattern by a screen printing method using a 100 mesh polyester screen in a manner of 20 to 30 μm thick, and dried by hot air at 80 ° C. The film was allowed to dry for 30 minutes. Next, a negative film having a resist pattern was adhered to the coating film, and an ultraviolet ray exposure apparatus (manufactured by OAK Co., Ltd., model HMW-680GW) was irradiated with ultraviolet rays (exposure amount: 200 mJ/cm 2 ) to 1% carbonic acid. The sodium aqueous solution was imaged at a jet pressure of 2.0 kg/cm 2 for 60 seconds and dissolved to remove the unexposed portion. Subsequently, using DEON, manufactured by KESSEL Co., Ltd., heat-hardening was carried out at 180 ° C in a nano-heated dry steam for 5 minutes to prepare an evaluation substrate.
以甲基乙基酮稀釋上述獲得之樹脂組成物，以網版印刷法，塗布於PET薄膜上，在80℃乾燥30分鐘，形成厚20μm之樹脂組成物層。再將保護膜貼合於其上，製作乾膜。接著，剝離保護膜，將薄膜熱層合於形成圖型之印刷配線板上，使樹脂組成物層密著於銅箔基板上。以與上述實施例2、3相同之條件進行紫外線照射及顯像。隨後，使用KESSEL公司製造之(DEON)，在180℃下以奈米 化過熱乾燥蒸氣進行加熱硬化5分鐘，製作評價基板。 The resin composition obtained above was diluted with methyl ethyl ketone, applied to a PET film by a screen printing method, and dried at 80 ° C for 30 minutes to form a resin composition layer having a thickness of 20 μm. Further, a protective film was attached thereto to prepare a dry film. Next, the protective film was peeled off, and the film was thermally laminated on the printed wiring board on which the pattern was formed, and the resin composition layer was adhered to the copper foil substrate. Ultraviolet irradiation and development were carried out under the same conditions as in the above Examples 2 and 3. Subsequently, using DESEN, manufactured by KESSEL, at 180 ° C in nanometer The superheated dry steam was heat-hardened for 5 minutes to prepare an evaluation substrate.
上述實施例1~6之評價基板之製作中，除將熱硬化條件變更為利用熱風乾燥器之150℃、60分鐘以外，餘以相同條件製作之評價基板分別設為比較例1~6之評價基板。 In the production of the evaluation substrates of the above-mentioned Examples 1 to 6, the evaluation substrates prepared under the same conditions were evaluated as Comparative Examples 1 to 6 except that the thermosetting conditions were changed to 150 ° C for 60 minutes using a hot air dryer. Substrate.
針對上述獲得之評價基板，依據JIS C 6481之試驗方法，將試驗基板浸漬於260℃之焊料浴中10秒且進行3次，依據以下基準評價外觀變化。 With respect to the evaluation substrate obtained above, the test substrate was immersed in a solder bath at 260 ° C for 10 seconds in accordance with the test method of JIS C 6481, and the appearance was changed in accordance with the following criteria.
○：外觀沒變化。 ○: The appearance did not change.
△：確認有硬化皮膜變色者。 △: It was confirmed that the hardened film was discolored.
×：硬化皮膜鼓起、剝離、焊料滲入。 ×: The hardened film is bulged, peeled off, and solder infiltrated.
針對上述獲得之評價基板，依據後述步驟進行無電解鍍金，針對其試驗基板之外觀變化及使用透明黏著膠帶進行剝離試驗，依據以下基準評價阻劑皮膜之剝離狀態。 With respect to the evaluation substrate obtained above, electroless gold plating was performed in accordance with the procedure described later, and the peeling test was performed on the test substrate by the appearance change of the test substrate and the peeling test using a transparent adhesive tape, and the peeling state of the resist film was evaluated based on the following criteria.
○：外觀沒變化，阻劑皮膜亦全未剝離 ○: The appearance did not change, and the resist film was not peeled off at all.
△：外觀雖沒變化，但阻劑皮膜稍有剝離 △: Although the appearance did not change, the resist film was slightly peeled off.
×：發現阻劑皮膜鼓起，焊料滲入，剝離試驗時阻劑皮膜之剝離大。 X: It was found that the resist film swelled and the solder penetrated, and the peeling of the resist film was large at the peeling test.
無電解電金步驟： Electroless gold step:
1.脫脂：將試驗基板浸漬於30℃之酸性脫脂溶液(日本MAC DERMID公司製造，MetexL-5B之20Vol%水溶液)3分鐘。 1. Degreasing: The test substrate was immersed in an acidic degreasing solution (manufactured by MAC DERMID, Japan, 20 Vol% aqueous solution of Metex L-5B) at 30 ° C for 3 minutes.
2.水洗：將試驗基板浸漬於水流中3分鐘。 2. Water washing: The test substrate was immersed in a water stream for 3 minutes.
3.軟蝕刻：在室溫下將試驗基板浸漬於14.3wt%之過硫酸銨水溶液中3分鐘。 3. Soft etching: The test substrate was immersed in a 14.3 wt% aqueous solution of ammonium persulfate for 3 minutes at room temperature.
4.水洗：將試驗基板浸漬於水流中3分鐘。 4. Water washing: The test substrate was immersed in a water stream for 3 minutes.
5.酸浸漬：在室溫下將試驗基板浸漬於10Vol%之硫酸水溶液中1分鐘。 5. Acid impregnation: The test substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute.
6.水洗：將試驗基板浸漬於水流中30秒~1分鐘。 6. Water washing: The test substrate was immersed in a water stream for 30 seconds to 1 minute.
7.觸媒賦予：將試驗基板浸漬於30℃之觸媒液(MELTEX公司製造，金屬板活化劑350之10Vol%水溶液)中7分鐘。 7. Catalyst application: The test substrate was immersed in a catalyst liquid (manufactured by MELTEX, Inc., 10 Vol% aqueous solution of metal plate activator 350) at 30 ° C for 7 minutes.
8.水洗：將試驗基板浸漬於水流中3分鐘。 8. Water washing: The test substrate was immersed in a water stream for 3 minutes.
9.無電解鍍鎳：將試驗基板浸漬於85℃、pH=4.6之鎳鍍敷液(MELTEX公司製造之MEL PLATE Ni-865M，20Vol%水溶液)中20分鐘。 9. Electroless nickel plating: The test substrate was immersed in a nickel plating solution (MEL PLATE Ni-865M, 20 Vol% aqueous solution manufactured by MELTEX Co., Ltd.) at 85 ° C and pH = 4.6 for 20 minutes.
10.酸浸漬：在室溫下將試驗基板浸漬於10Vol%之硫酸水溶液中1分鐘。 10. Acid impregnation: The test substrate was immersed in a 10 vol% aqueous sulfuric acid solution at room temperature for 1 minute.
11.水洗：將試驗基板浸漬於水流中30秒~1分鐘。 11. Water washing: The test substrate was immersed in a water stream for 30 seconds to 1 minute.
12.無電解鍍金：將試驗基板浸漬於95℃、pH=6之金鍍敷液(MELTEX公司製造之AUROLECTROLESS UP 15Vol%，氰化金鉀3Vol%之水溶液)中10分鐘。 12. Electroless gold plating: The test substrate was immersed in a gold plating solution (AUROLECTROLESS UP 15 Vol% manufactured by MELTEX, an aqueous solution of 3 Vol% of potassium cyanide) at 95 ° C and pH = 6 for 10 minutes.
13.水洗：將試驗基板浸漬於水流中3分鐘。 13. Water washing: The test substrate was immersed in a water stream for 3 minutes.
14.熱水洗滌：將試驗基板浸潰於60℃之溫水中，充分水洗3分鐘，擦掉水予以乾燥。 14. Hot water washing: The test substrate was immersed in warm water of 60 ° C, washed thoroughly for 3 minutes, and wiped off with water to dry.
經過該等步驟獲得無電解鍍金試驗基板。 Through these steps, an electroless gold plating test substrate is obtained.
根據JIS K 5600之試驗方法試驗上述獲得之評價基板之硬化塗膜，且觀測塗膜沒有刮傷之最高硬度。 The hardened coating film of the evaluation substrate obtained above was tested according to the test method of JIS K 5600, and the highest hardness of the coating film without scratching was observed.
在20℃下將上述獲得之評價基板之硬化塗膜浸漬於PMA(丙二醇單甲基醚乙酸酯)中20分鐘後，立即進行膠帶剝離試驗，針對阻劑層之膨脹‧剝離進行評價。 The hardened coating film of the evaluation substrate obtained above was immersed in PMA (propylene glycol monomethyl ether acetate) at 20 ° C for 20 minutes, and immediately subjected to a tape peeling test to evaluate the expansion and peeling of the resist layer.
○：無膨脹、剝離。 ○: No swelling or peeling.
△：僅稍有剝離。 △: only slightly peeled off.
×：塗膜大幅剝離。 ×: The coating film was largely peeled off.
在20℃下將上述獲得之評價基板之硬化塗膜浸漬於10Vol%之H2SO4中20分鐘後，立即進行膠帶剝離試驗，針對阻劑層之膨脹‧剝離進行評價。 The hardened coating film of the evaluation substrate obtained above was immersed in 10% by volume of H 2 SO 4 at 20 ° C for 20 minutes, and immediately subjected to a tape peeling test to evaluate the expansion and peeling of the resist layer.
○：無膨脹、剝離。 ○: No swelling or peeling.
△：僅稍有剝離。 △: only slightly peeled off.
×：塗膜大幅剝離。 ×: The coating film was largely peeled off.
在20℃下將上述獲得之評價基板之硬化塗膜浸漬於10vol%之NaOH中20分鐘後，立即進行膠帶剝離試驗，針對阻劑層之膨脹‧剝離進行評價。 After the hardened coating film of the evaluation substrate obtained above was immersed in 10 vol% of NaOH for 20 minutes at 20 ° C, the tape peeling test was immediately performed, and the expansion and detachment of the resist layer were evaluated.
○：無膨脹、剝離。 ○: No swelling or peeling.
△：僅稍有剝離。 △: only slightly peeled off.
×：塗膜大幅剝離。 ×: The coating film was largely peeled off.
使上述獲得之評價基板進而於150℃加熱2小時，如下述般判斷銅電路上之變色程度。 The evaluation substrate obtained above was further heated at 150 ° C for 2 hours, and the degree of discoloration on the copper circuit was judged as follows.
○：完全未變色 ○: No discoloration at all
×：見到稍有變色 ×: I saw a slight discoloration.
××：見到變色 ××: see color change
由上述表1所示之評價結果所了解，可知藉由使用奈米化過熱乾燥蒸氣進行熱硬化，可抑制銅上之變色，且可形成耐酸性、無電解鍍金耐性優異之樹脂絕緣層。 As is understood from the results of the evaluation shown in the above Table 1, it is understood that by using the nano-heated dry steam to perform thermal curing, discoloration on the copper can be suppressed, and a resin insulating layer excellent in acid resistance and electroless gold plating resistance can be formed.
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| JP6658648B2 (en) * | 2017-03-28 | 2020-03-04 | 味の素株式会社 | Photosensitive resin composition |
| JP6677203B2 (en) * | 2017-03-28 | 2020-04-08 | 味の素株式会社 | Photosensitive resin composition, photosensitive film, photosensitive film with support, printed wiring board, and semiconductor device |
| WO2019043952A1 (en) * | 2017-09-04 | 2019-03-07 | シライ電子工業株式会社 | Ink drying method and ink drying device |
| JP7322988B2 (en) | 2018-09-27 | 2023-08-08 | 味の素株式会社 | Resin composition, photosensitive film, photosensitive film with support, printed wiring board and semiconductor device |
| CN112898225A (en) * | 2020-12-09 | 2021-06-04 | 大丰跃龙化学有限公司 | Synthesis method of 1, 2-benzisothiazolin-3-ketone |
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