TW202206540A - Curable resin composition, dry film, cured product, wiring board, and electronic component - Google Patents

Curable resin composition, dry film, cured product, wiring board, and electronic component Download PDF

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TW202206540A
TW202206540A TW110113194A TW110113194A TW202206540A TW 202206540 A TW202206540 A TW 202206540A TW 110113194 A TW110113194 A TW 110113194A TW 110113194 A TW110113194 A TW 110113194A TW 202206540 A TW202206540 A TW 202206540A
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type epoxy
resin composition
epoxy resin
curable resin
metal
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TW110113194A
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Chinese (zh)
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関口翔也
石川信広
高谷康子
佐土原大祐
鈴木陽平
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日商太陽控股股份有限公司
日商傑希優股份有限公司
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Publication of TW202206540A publication Critical patent/TW202206540A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • H05K3/46—Manufacturing multilayer circuits

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Catalysts (AREA)

Abstract

Provided is a curable resin composition with which it is possible to achieve excellent adhesion between an insulation layer and a conductor layer, even when the surface irregularities (surface roughness) are small (e.g., even when Ra is 200nm or less). A curable resin composition according to the present invention comprises an epoxy resin, a catalyzing metal-containing silicon oligomer, a phenol resin and an active ester compound, the curable resin composition characterized in that: the epoxy resin contains a bisphenol A-type epoxy resin, a biphenyl aralkyl-type epoxy resin, and an epoxy resin other than the bisphenol A-type epoxy resin and biphenyl aralkyl-type epoxy resin; and the catalyzing metal-containing silicon oligomer is obtained by subjecting a tetraalkoxy silane and a polyvalent alcohol, in which a hydroxy group is bonded to at least the n and n+1 sites or n and n+2 sites (where n is an integer of at least 1), to a condensation reaction in the presence of a metal having catalytic properties with respect to electroless plating.

Description

硬化性樹脂組成物、乾膜、硬化物、配線板及電子零件Curable resin composition, dry film, cured product, wiring board and electronic parts

本發明係關於硬化性樹脂組成物、乾膜、硬化物、配線板及電子零件。The present invention relates to a curable resin composition, a dry film, a cured product, a wiring board, and an electronic component.

作為多層印刷配線板之製造方法，已知有將預浸物與銅箔壓製加工，於形成有電路之內層電路板(所謂的覆銅層合板)上交互堆疊絕緣層與導體層之增層方式之製造技術。例如，提出有於形成有電路之內層電路板上塗佈環氧樹脂組成物，加熱硬化而形成絕緣層之後，於該絕緣層表面以粗化劑形成凹凸狀之粗化面後，藉由無電解鍍敷與電解鍍敷之處理形成導體層之方法(參照專利文獻1及專利文獻2)。As a method of manufacturing a multilayer printed wiring board, there is known a build-up layer in which an insulating layer and a conductor layer are alternately stacked on an inner-layer circuit board (so-called copper-clad laminate) on which a circuit is formed by pressing a prepreg and a copper foil. method of manufacturing technology. For example, it is proposed to coat an epoxy resin composition on an inner-layer circuit board on which a circuit is formed, heat and harden to form an insulating layer, and then use a roughening agent to form a roughened surface of the insulating layer on the surface of the insulating layer. A method of forming a conductor layer by treatment of electroless plating and electrolytic plating (refer to Patent Document 1 and Patent Document 2).

又，提出有於形成有電路之內層電路板上疊合環氧樹脂組成物之接著薄膜，加熱硬化而形成絕緣層後，於該絕緣層表面以粗化劑形成凹凸狀之粗化面後，將導體層藉由無電解鍍敷與電解鍍敷之處理所形成的多層印刷配線板之製造法(參照專利文獻3)。 如此的提案之技術均為藉由將絕緣層之表面粗面化，而提高鍍敷層(導體電路層)與絕緣層之密著性。 [先前技術文獻] [專利文獻]Furthermore, it is proposed to laminate an adhesive film of an epoxy resin composition on an inner-layer circuit board on which circuits are formed, heat and harden to form an insulating layer, and then use a roughening agent to form a roughened surface of the insulating layer on the surface of the insulating layer. , a method of manufacturing a multilayer printed wiring board in which a conductor layer is formed by electroless plating and electrolytic plating (refer to Patent Document 3). In such a proposed technique, the adhesion between the plating layer (conductor circuit layer) and the insulating layer is improved by roughening the surface of the insulating layer. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開平7-304931號公報 [專利文獻2]日本特開平7-304933號公報 [專利文獻3]日本特開平11-87927號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 7-304931 [Patent Document 2] Japanese Patent Application Laid-Open No. 7-304933 [Patent Document 3] Japanese Patent Application Laid-Open No. 11-87927

[發明所欲解決之課題][The problem to be solved by the invention]

但是，近年來之高精細的導體電路圖型中，例如，於導體電路形成時將抗鍍劑下不需要的無電解鍍敷部分以蝕刻處理進行去除時，可能有蝕刻液進入絕緣層表面之凹部，因侵蝕導體層之電路底部而使導體電路剝離的情況，係有無法精度良好地形成微細的導體電路之問題。 又，亦有因絕緣層之表面凹凸而使導體層與絕緣層之接觸面積增大，故特別是高頻之電信號之傳輸損耗增大的問題。However, in recent high-definition conductor circuit patterns, for example, when an unnecessary electroless plated portion under the plating resist is removed by etching during the formation of the conductor circuit, an etching solution may enter the recessed portion on the surface of the insulating layer. However, when the conductor circuit is peeled off due to erosion of the circuit bottom of the conductor layer, there is a problem that a fine conductor circuit cannot be formed accurately. In addition, there is also a problem that the contact area between the conductor layer and the insulating layer is increased due to the uneven surface of the insulating layer, so the transmission loss of the electrical signal especially at high frequencies increases.

進一步地，於配線板中之層合構造中，由於在絕緣層形成表面凹凸，故為了使上下導體層電性絕緣，所必要之層的厚度係增加凹凸之高度的量，配線板之輕薄化變得困難。 由如此的問題來看，欲得到更為薄膜且更高精細之配線板，在不將絕緣層粗面化之下實現與導體電路之優良密著性的技術受到需求。Further, in the laminate structure in the wiring board, since the surface unevenness is formed on the insulating layer, in order to electrically insulate the upper and lower conductor layers, the thickness of the necessary layer is increased by the height of the unevenness, and the wiring board becomes lighter and thinner. becomes difficult. In view of such a problem, in order to obtain a thinner and higher-definition wiring board, there is a need for a technique for realizing excellent adhesion to the conductor circuit without roughening the insulating layer.

因而，本發明之課題為提供即使表面凹凸(表面粗度)小(例如即使Ra為200nm以下)，亦可得到絕緣層與導體層之優良的密著性之硬化性樹脂組成物。 [用以解決課題之手段]Therefore, an object of the present invention is to provide a curable resin composition that can obtain excellent adhesion between the insulating layer and the conductor layer even if the surface unevenness (surface roughness) is small (eg, even if Ra is 200 nm or less). [means to solve the problem]

本發明者等人深入研究的結果，發現藉由含有特定之環氧樹脂、特定之含觸媒金屬矽寡聚物、酚樹脂，與活性酯化合物之硬化性樹脂組成物，可解決前述課題，而完成本發明。亦即，本發明係如以下所述。As a result of intensive research by the present inventors, it was found that the aforementioned problems can be solved by a curable resin composition containing a specific epoxy resin, a specific catalyst-containing metal silicon oligomer, a phenol resin, and an active ester compound, The present invention has been completed. That is, the present invention is as follows.

本發明之硬化性樹脂組成物，為一種硬化性樹脂組成物，其係含有環氧樹脂、含觸媒金屬矽寡聚物、酚樹脂與活性酯化合物之硬化性樹脂組成物，其特徵為，前述環氧樹脂，包含雙酚A型環氧樹脂、聯苯基芳烷基型環氧樹脂，與前述雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂， 前述含觸媒金屬矽寡聚物，為藉由使四烷氧基矽烷，與至少於n,n+1位或n,n+2位(惟n為1以上之整數)上鍵結有羥基之多元醇，在對無電解鍍敷具有觸媒性之金屬的存在下進行縮合反應而得到之寡聚物。The curable resin composition of the present invention is a curable resin composition, which is a curable resin composition containing an epoxy resin, a catalyst-containing metal silicon oligomer, a phenol resin and an active ester compound, and is characterized by: The aforementioned epoxy resins include bisphenol A type epoxy resins, biphenyl aralkyl type epoxy resins, and epoxy resins other than the aforementioned bisphenol A type epoxy resins and biphenyl aralkyl type epoxy resins , The aforementioned catalyst-containing metal-silicon oligomer is obtained by bonding tetraalkoxysilane to at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more) with hydroxyl groups The polyol is an oligomer obtained by a condensation reaction in the presence of a metal having catalytic properties for electroless plating.

本發明之硬化性樹脂組成物，亦可以如下者為特徵：前述雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂，為苯酚酚醛清漆型環氧樹脂及萘型環氧樹脂之至少任1種。The curable resin composition of the present invention may also be characterized in that the epoxy resins other than the aforementioned bisphenol A type epoxy resin and biphenyl aralkyl type epoxy resin are phenol novolak type epoxy resins and At least any one of naphthalene-type epoxy resins.

本發明之硬化性樹脂組成物，亦可以如下者為特徵：前述對無電解鍍敷具有觸媒性之金屬，為鐵、鎳、鈷、銅、鈀、銀、金、鉑之至少任1種。The curable resin composition of the present invention may be characterized in that the metal having catalytic properties for electroless plating is at least any one of iron, nickel, cobalt, copper, palladium, silver, gold, and platinum .

本發明之硬化性樹脂組成物，可製成於薄膜上形成由前述硬化性樹脂組成物所構成之樹脂層而成的乾膜。The curable resin composition of the present invention can be used as a dry film in which a resin layer composed of the curable resin composition described above is formed on a film.

前述硬化性樹脂組成物或前述乾膜可硬化而成為硬化物。The curable resin composition or the dry film can be cured to form a cured product.

本發明之硬化物，可製成具有含有硬化物之絕緣層與含有鍍敷金屬之導體層的配線板。The cured product of the present invention can be formed into a wiring board having an insulating layer containing the cured product and a conductor layer containing a plated metal.

本發明之硬化物，可製成具有含有硬化物之絕緣層與含有鍍敷金屬之導體層的電子零件。 [發明之效果]The cured product of the present invention can be made into an electronic component having an insulating layer containing the cured product and a conductor layer containing a plated metal. [Effect of invention]

可提供即使表面凹凸(表面粗度)小(例如即使Ra為200nm以下)，亦可得到絕緣層與導體層之優良的密著性之硬化性樹脂組成物。Even if the surface unevenness (surface roughness) is small (for example, even if Ra is 200 nm or less), the curable resin composition which can obtain the excellent adhesiveness of an insulating layer and a conductor layer can be provided.

詳述本發明之硬化性樹脂組成物中所含有的各成分及各成分之含量，以及本發明之硬化性樹脂組成物之使用方法。Each component contained in the curable resin composition of the present invention, the content of each component, and the method of using the curable resin composition of the present invention will be described in detail.

再者，本發明之硬化性樹脂組成物，可遵照公知方法製造，例如可藉由將各成分混合及分散而得到。In addition, the curable resin composition of this invention can be manufactured according to a well-known method, for example, it can be obtained by mixing and dispersing each component.

又，本說明書中，固體成分意指構成硬化性樹脂組成物，或各原料之溶劑(特別是有機溶劑)以外之組成物的成分，或其質量或體積。In addition, in this specification, solid content means the component which comprises the curable resin composition, or the composition other than the solvent (especially organic solvent) of each raw material, or its mass or volume.

本說明書中，單表示化合物名時，係包含其全部的異構物。In the present specification, when a compound name is simply expressed, all isomers thereof are included.

＜＜＜硬化性樹脂組成物＞＞＞ ＜＜成分＞＞ 本發明之硬化性樹脂組成物，含有雙酚A型環氧樹脂、聯苯基芳烷基型環氧樹脂、前述雙酚A型環氧樹脂與聯苯基芳烷基型環氧樹脂以外之環氧樹脂、含觸媒金屬矽寡聚物、酚樹脂，與活性酯化合物， 前述含觸媒金屬矽寡聚物，為藉由使四烷氧基矽烷，與至少於n,n+1位或n,n+2位(惟n為1以上之整數)上鍵結有羥基之多元醇，在對無電解鍍敷具有觸媒性之金屬的存在下進行縮合反應而得到之寡聚物。＜＜＜Curable resin composition＞＞＞ ＜＜Ingredients＞＞ The curable resin composition of the present invention contains bisphenol A type epoxy resin, biphenyl aralkyl type epoxy resin, other than the aforementioned bisphenol A type epoxy resin and biphenyl aralkyl type epoxy resin Epoxy resins, catalyzed metal silicon oligomers, phenolic resins, and active ester compounds, The aforementioned catalyst-containing metal-silicon oligomer is obtained by bonding tetraalkoxysilane to at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more) with hydroxyl groups The polyol is an oligomer obtained by a condensation reaction in the presence of a metal having catalytic properties for electroless plating.

＜環氧樹脂＞ 本發明之環氧樹脂，含有雙酚A型環氧樹脂與聯苯基芳烷基型環氧樹脂，進一步地含有前述雙酚A型環氧樹脂與聯苯基芳烷基型環氧樹脂以外之環氧樹脂。藉由合併使用如此的特定之環氧樹脂，本發明之硬化性樹脂組成物，可得到良好之無電解鍍銅的析出性，及絕緣層與導體層之優良密著性。如此的效果，可認為係藉由前述環氧樹脂之併用，組成物中所含有的矽寡聚物之分子構造中的金屬物種之配位形態會安定化之故。＜Epoxy resin＞ The epoxy resin of the present invention contains a bisphenol A type epoxy resin and a biphenyl aralkyl type epoxy resin, and further contains in addition to the aforementioned bisphenol A type epoxy resin and a biphenyl aralkyl type epoxy resin of epoxy resin. By using such a specific epoxy resin in combination, the curable resin composition of the present invention can obtain good precipitation properties of electroless copper plating and good adhesion between the insulating layer and the conductor layer. Such an effect is considered to be due to the fact that the coordination state of the metal species in the molecular structure of the silicon oligomer contained in the composition is stabilized by the combined use of the aforementioned epoxy resins.

雙酚A型環氧樹脂，可使用公知慣用之雙酚A型環氧樹脂。其中由於可得到與矽寡聚物之良好的相溶性，故尤以分子量370~470、環氧當量170~270為佳。The bisphenol A type epoxy resin can be a well-known and conventional bisphenol A type epoxy resin. Among them, the molecular weight of 370-470 and the epoxy equivalent weight of 170-270 are particularly preferred because of good compatibility with silicon oligomers.

聯苯基芳烷基型環氧樹脂，可使用公知慣用之聯苯基芳烷基型環氧樹脂。其中，由於可得到作為硬化物之優良耐熱性或與導體層之良好密著性，故尤以分子量1,000~3,000、環氧當量200~300為佳。As the biphenyl aralkyl type epoxy resin, a well-known and conventional biphenyl aralkyl type epoxy resin can be used. Among them, the molecular weight of 1,000-3,000 and the epoxy equivalent weight of 200-300 are particularly preferred, since excellent heat resistance as a cured product or good adhesion to the conductor layer can be obtained.

雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂，可列舉雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚E型環氧樹脂、雙酚M型環氧樹脂、雙酚P型環氧樹脂、雙酚Z型環氧樹脂等之雙酚型環氧樹脂；雙酚A酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆環氧樹脂等之酚醛清漆型環氧樹脂；聯苯基型環氧樹脂、芳基伸烷基型環氧樹脂、四苯酚基乙烷型環氧樹脂、萘型環氧樹脂、蒽型環氧樹脂、苯氧基型環氧樹脂、二環戊二烯型環氧樹脂、降莰烯型環氧樹脂、三羥基苯基甲烷型環氧樹脂、乙內醯脲型環氧樹脂、四苯酚基乙烷型環氧樹脂、溴化環氧樹脂、氫化(雙酚)型樹脂、環氧丙基胺型環氧樹脂、脂環式環氧樹脂、鄰苯二甲酸二環氧丙酯樹脂、四環氧丙基二甲苯醯基乙烷樹脂、甲基丙烯酸環氧丙酯共聚合系環氧樹脂、環己基馬來醯亞胺與甲基丙烯酸環氧丙酯之共聚合環氧樹脂、環氧改質之聚丁二烯橡膠衍生物、CTBN改質環氧樹脂、三羥甲基丙烷聚環氧丙基醚、苯基-1,3-二環氧丙基醚、1,6-己二醇二環氧丙基醚、乙二醇或丙二醇之二環氧丙基醚、山梨醇聚環氧丙基醚、參(2,3-環氧基丙基)異三聚氰酸酯、三環氧丙基參(2-羥基乙基)異三聚氰酸酯等之環氧樹脂等。此等之環氧樹脂，可單獨或組合2種以上來使用。Epoxy resins other than bisphenol A type epoxy resin and biphenyl aralkyl type epoxy resin include bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, Bisphenol-type epoxy resins such as bisphenol M-type epoxy resin, bisphenol P-type epoxy resin, bisphenol Z-type epoxy resin, etc.; bisphenol A novolac epoxy resin, phenol novolak epoxy resin, Novolac epoxy resins such as cresol novolac epoxy resins; biphenyl epoxy resins, aryl alkylene epoxy resins, tetraphenol ethane epoxy resins, naphthalene epoxy resins, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, trihydroxyphenylmethane type epoxy resin, hydantoin type epoxy resin, Tetraphenol ethane type epoxy resin, brominated epoxy resin, hydrogenated (bisphenol) type resin, glycidylamine type epoxy resin, alicyclic epoxy resin, diglycidyl phthalate Resin, tetraglycidyl xylyl ethane resin, glycidyl methacrylate copolymer epoxy resin, cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin , Epoxy modified polybutadiene rubber derivatives, CTBN modified epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, 1,6 - Diglycidyl ether of hexanediol, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, gins (2,3-epoxypropyl) isocyanuric acid Epoxy resin such as ester, triglycidyl ginseng (2-hydroxyethyl) isocyanurate, etc. These epoxy resins can be used alone or in combination of two or more.

此等之中，雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂，就更加提高無電解鍍銅之析出性，及絕緣層與導體層之密著性而言，尤較佳使用苯酚酚醛清漆型環氧樹脂及萘型環氧樹脂之至少任1種。 此等可單獨或組合2種來使用。Among them, epoxy resins other than bisphenol A type epoxy resin and biphenyl aralkyl type epoxy resin can further improve the precipitation property of electroless copper plating and the adhesion between the insulating layer and the conductor layer. In particular, at least any one of a phenol novolac type epoxy resin and a naphthalene type epoxy resin is preferably used. These can be used individually or in combination of 2 types.

＜含觸媒金屬矽寡聚物＞ 本發明之含觸媒金屬矽寡聚物，為藉由使四烷氧基矽烷，與至少於n,n+1位或n,n+2位(惟n為1以上之整數)上鍵結有羥基之多元醇，於對無電解鍍敷具有觸媒性之金屬的存在下進行縮合反應而得到之寡聚物，係以式1表示。

Figure 02_image001
式1之R1 為烷基，R2 ~R5 為氫、烷基、烷氧基或式2表示之構造，M為金屬元素，n為1以上之整數。
Figure 02_image003
式2之R6 為烷基，R7 ~R10 為氫、烷基、烷氧基，或式2表示之構造，k為1以上之整數。<Catalyst-containing metal-silicon oligomer> The catalyst-containing metal-silicon oligomer of the present invention is prepared by combining tetraalkoxysilane with at least n, n+1 positions or n, n+2 positions (only An oligomer obtained by condensation reaction of a polyol having a hydroxyl group bonded to n is an integer of 1 or more) in the presence of a metal having catalytic properties for electroless plating is represented by formula 1.
Figure 02_image001
R 1 in Formula 1 is an alkyl group, R 2 to R 5 are hydrogen, an alkyl group, an alkoxy group or a structure represented by Formula 2, M is a metal element, and n is an integer of 1 or more.
Figure 02_image003
R 6 in Formula 2 is an alkyl group, R 7 to R 10 are hydrogen, an alkyl group, an alkoxy group, or a structure represented by Formula 2, and k is an integer of 1 or more.

R1 為烷基，只要不阻礙本發明之效果則無特別限定，例如可為甲基、乙基、異丙基等。R 1 is an alkyl group and is not particularly limited as long as the effect of the present invention is not inhibited. For example, it may be a methyl group, an ethyl group, an isopropyl group, or the like.

R2 ~R5 為氫、烷基、烷氧基，或式2表示之構造，R2 ~R5 ，可為相同構造、亦可為不同構造。R 2 to R 5 are hydrogen, an alkyl group, an alkoxy group, or a structure represented by Formula 2, and R 2 to R 5 may have the same structure or different structures.

烷基並無特別限定，可為甲基、乙基、異丙基等。The alkyl group is not particularly limited, and may be a methyl group, an ethyl group, an isopropyl group, or the like.

烷氧基並無特別限定，可為甲基烷氧基、乙基烷氧基、異丙基烷氧基等。The alkoxy group is not particularly limited, and may be a methylalkoxy group, an ethylalkoxy group, an isopropylalkoxy group, or the like.

式2表示之構造中之R6 為烷基，R7 ~R10 為氫、烷基、烷氧基，或式2表示之構造，k為1以上之整數。可為於式2之構造(設為式2之構造A)之R7 ~R10 上，進一步鍵結有式2之構造(設為式2之構造B)之構造。亦即，可於式2之R7 ~R10 上進一步鍵結式2之構造，而於分支鏈形成重複構造。又，只要不阻礙本發明之效果，k之值並無特別限定，例如可為5~10、較佳為5~7。k之值為該範圍時，使硬化性樹脂組成物硬化時，可成為機械特性優良者。特別是可使硬化物之韌性成為優良者。 再者，以式2之構造A的k為ka、式2之構造B的k為kb時，ka與kb可為相同之值亦可為不同之值。 又，亦可於式2之構造B的R7 ~R10 上進一步鍵結式2之構造，而成為使分支重複的構造。In the structure represented by the formula 2, R 6 is an alkyl group, R 7 to R 10 are hydrogen, an alkyl group, an alkoxy group, or the structure represented by the formula 2, and k is an integer of 1 or more. The structure of Formula 2 (set as Structure B of Formula 2) may be further bonded to R 7 to R 10 of the structure of Formula 2 (set as Structure A of Formula 2). That is, the structure of Formula 2 can be further bonded to R 7 to R 10 of Formula 2 to form a repeating structure in the branch chain. In addition, the value of k is not particularly limited as long as the effect of the present invention is not inhibited, and for example, it may be 5 to 10, preferably 5 to 7. When the value of k is within this range, when the curable resin composition is cured, it can be excellent in mechanical properties. In particular, the toughness of the hardened product can be made excellent. In addition, when k of the structure A of Formula 2 is ka, and k of the structure B of Formula 2 is kb, ka and kb may be the same value or different values. Moreover, the structure of Formula 2 may be further bonded to R 7 to R 10 of Structure B of Formula 2, so that the branch may be repeated.

式1中及式2中之M為金屬元素。作為金屬元素，只要不阻礙本發明之效果，則無特別限定，例如，可列舉就鍍敷之析出反應而言有自我催化作用之鐵、鎳、鈷、銅、鈀、銀、金、鉑等。此等之觸媒金屬之中，尤以鐵、鎳、鈷、銅、鈀為佳；更佳為鐵、鎳、銅、鈀；特佳為鈀。M in Formula 1 and Formula 2 is a metal element. The metal element is not particularly limited as long as it does not inhibit the effect of the present invention. For example, iron, nickel, cobalt, copper, palladium, silver, gold, platinum, etc., which have a self-catalytic effect on the precipitation reaction of plating, can be mentioned. . Among these catalyst metals, iron, nickel, cobalt, copper, and palladium are particularly preferred; iron, nickel, copper, and palladium are more preferred; and palladium is particularly preferred.

n為1以上之整數。只要不阻礙本發明之效果，n之值並無特別限定，例如可為5~10、較佳為5~7。n之值為該範圍時，使硬化性樹脂組成物硬化時，可成為機械特性優良者。特別是可使硬化物之韌性成為優良者。n is an integer of 1 or more. The value of n is not particularly limited as long as the effect of the present invention is not inhibited, and it may be, for example, 5 to 10, preferably 5 to 7. When the value of n is in this range, when the curable resin composition is cured, it can be excellent in mechanical properties. In particular, the toughness of the hardened product can be improved.

再者，於式1之R2 ~R5 的任一者上，具有式2之重複構造時，n與k之合計，例如可為5~10、較佳為5~7。再者，於式2之構造上，進一步鍵結有式2時，如上所述，當存在有ka、kb、kc･･･時，n+ka+kb+kc+･･･之合計值，可為5~10、較佳為5~7。Furthermore, when any one of R 2 to R 5 in Formula 1 has the repeating structure of Formula 2, the sum of n and k may be, for example, 5-10, preferably 5-7. Furthermore, in the structure of Equation 2, when Equation 2 is further bonded, as described above, when there are ka, kb, kc･･･, the total value of n+ka+kb+kc+･･･ can be It is 5-10, Preferably it is 5-7.

以下詳述本發明之含觸媒金屬矽寡聚物之製造方法之一例。An example of the manufacturing method of the catalyst-containing metal silicon oligomer of the present invention is described in detail below.

含觸媒金屬矽寡聚物之製造所用的聚烷氧基矽烷，並無特別限定，例如可列舉組合複數個甲氧基、乙氧基、異丙氧基之聚烷氧基，具體而言，可列舉二甲氧基矽烷、二乙氧基矽烷、二異丙氧基矽烷、三甲氧基矽烷、三乙氧基矽烷、三異丙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、四異丙氧基矽烷、甲氧基乙氧基矽烷、甲氧基異丙氧基矽烷、乙氧基異丙氧基矽烷等。又，可包含於此等聚烷氧基矽烷之矽上，單獨或複數組合地附加氫、甲基、乙基、異丙基者。能夠以此等之組合，來選擇式1之R1 、R2 ~R5 。The polyalkoxysilane used for the production of the catalyst-containing metal silicon oligomer is not particularly limited. , dimethoxysilane, diethoxysilane, diisopropoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, tetramethoxysilane, tetraethoxysilane Silane, tetraisopropoxysilane, methoxyethoxysilane, methoxyisopropoxysilane, ethoxyisopropoxysilane, etc. Moreover, it is possible to include hydrogen, methyl group, ethyl group, and isopropyl group added to the silicon of these polyalkoxysilanes alone or in a plurality of combinations. These combinations can be used to select R 1 , R 2 to R 5 in Formula 1.

又，含觸媒金屬矽寡聚物之製造所用的至少於n,n+1位或n,n+2位(惟n為1以上之整數)上鍵結有羥基之多元醇，並無特別限定，例如，可列舉n為1~3之整數之2元~4元醇、較佳可列舉n為1~2之整數之2~3元醇等。此等多元醇之具體例子，例如可列舉乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、2-甲基-1,3-丙二醇、1,2-戊二醇、1,3-戊二醇、2,3-戊二醇、2,4-戊二醇等之2元醇；甘油等之3元醇等；赤藻糖醇等之4元醇。此等之多元醇之中尤以2元醇為佳、更佳為乙二醇及/或1,3-丙二醇、特佳為乙二醇。此等多元醇可單獨，或組合複數種使用。In addition, the polyol having hydroxyl groups bonded to at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more) used in the production of catalyst-containing metal silicon oligomers is not particularly Limited, for example, divalent to tetravalent alcohols in which n is an integer of 1 to 3, preferably divalent to trivalent alcohols in which n is an integer of 1 to 2, and the like are mentioned. Specific examples of these polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol, for example. , 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol and other dihydric alcohols; glycerin Trivalent alcohols such as erythritol, etc.; tetravalent alcohols such as erythritol. Among these polyhydric alcohols, dihydric alcohols are particularly preferred, ethylene glycol and/or 1,3-propanediol are more preferred, and ethylene glycol is particularly preferred. These polyols may be used alone or in combination.

進一步地，使用於含觸媒金屬矽寡聚物的金屬，並非就聚烷氧基矽烷與多元醇之縮合反應而言具有催化作用之金屬，而是可為後述鍍敷處理中具有自我催化作用之金屬(有略稱為觸媒金屬者)。具體而言，可為上述之鐵、鎳、鈷、銅、鈀、銀、金、鉑等之金屬。因此，係與WO2014/207885或WO2014/207886中所稱之金屬觸媒相異者。Further, the metal used in the catalyst-containing metal silicon oligomer is not a metal having a catalytic effect on the condensation reaction of polyalkoxysilane and a polyol, but can have an autocatalytic effect in the plating process described later. The metal (abbreviated as catalyst metal). Specifically, the above-mentioned metals such as iron, nickel, cobalt, copper, palladium, silver, gold, and platinum can be used. Therefore, it is different from the metal catalyst mentioned in WO2014/207885 or WO2014/207886.

再者，觸媒金屬較佳為於縮合反應時，以溶解於上述多元醇之狀態存在，此時，例如較佳為利用氯化鐵、氯化鎳、氯化銅、氯化鈀、氯化金(III)、氯化銀(I)、氯化鉑(IV)等之含有觸媒金屬之金屬鹽。再者，觸媒金屬難溶解於多元醇時，可預先溶解於鹽酸等之無機酸。此等觸媒金屬可單獨，或組合複數種來使用，此時較佳至少含有鈀。Furthermore, the catalyst metal is preferably present in a state of being dissolved in the above-mentioned polyol during the condensation reaction. Metal salts containing catalyst metals such as gold(III), silver(I) chloride, platinum(IV) chloride, etc. Furthermore, when the catalyst metal is hardly dissolved in the polyol, it can be dissolved in a mineral acid such as hydrochloric acid in advance. These catalytic metals may be used alone or in combination, and in this case, at least palladium is preferably contained.

使聚烷氧基矽烷與多元醇在觸媒金屬之存在下進行縮合反應之方法並無特別限定，例如可於上述多元醇中添加觸媒金屬為0.01~20g/kg、較佳為0.1~10g/kg並使其溶解後，一邊攪拌一邊加熱至反應溫度，進一步添加四烷氧基矽烷來進行反應。反應溫度為25~150℃、較佳為30~70℃，反應時間為30分鐘~8小時、較佳為2小時~4小時。再者，反應時，使聚烷氧基矽烷與多元醇以莫耳比4：1~1：4、較佳為1：2~1：4進行反應一事係重要的。藉此，聚烷氧基矽烷與聚烷氧基矽烷之間係攝入多元醇。The method for condensing polyalkoxysilane and polyol in the presence of catalyst metal is not particularly limited. For example, catalyst metal can be added to the above-mentioned polyol in an amount of 0.01~20g/kg, preferably 0.1~10g. /kg and dissolved, it was heated to the reaction temperature while stirring, and tetraalkoxysilane was further added and reacted. The reaction temperature is 25 to 150° C., preferably 30 to 70° C., and the reaction time is 30 minutes to 8 hours, preferably 2 hours to 4 hours. In addition, it is important that the polyalkoxysilane and the polyol are reacted at a molar ratio of 4:1 to 1:4, preferably 1:2 to 1:4, during the reaction. Thereby, a polyol is incorporated between the polyalkoxysilane and the polyalkoxysilane.

再者，上述反應時會生成醇，但因為藉由不分餾該醇，聚合反應會被控制，故較佳為不分餾醇。In addition, although alcohol is produced|generated in the said reaction, it is preferable not to fractionate alcohol because the polymerization reaction will be controlled by not fractionating this alcohol.

又，上述反應中，使聚烷氧基矽烷與多元醇進行縮合反應之前會分離為2層，但反應結束時會變為1層，因此可於成為1層的時間點終結反應。In the above reaction, the polyalkoxysilane and the polyol are separated into two layers until the condensation reaction is performed, but when the reaction is completed, it becomes one layer. Therefore, the reaction can be terminated at the time of becoming one layer.

如此方式所得之含觸媒金屬矽寡聚物，為於聚烷氧基矽烷2~4個，與多元醇1~13個進行縮合反應後之矽寡聚物中攝入有觸媒金屬者。The catalyst-containing metal-silicon oligomer obtained in this way is a silicon oligomer obtained by condensation reaction of 2-4 polyalkoxysilanes and 1-13 polyols with a catalyst metal incorporated therein.

再者，含觸媒金屬矽寡聚物，為四烷氧基矽烷之烷氧基，與多元醇中存在的n,n+1位或n,n+2位之羥基之1個或2個進行縮合反應而得者，例如具有如下述(a)~(d)之部分構造。又，推測其係於含觸媒金屬矽寡聚物中，觸媒金屬存在於氧原子間，形成以觸媒金屬為頂點的5員環構造或6員環構造，而經安定化者。因此，本發明之含觸媒金屬矽寡聚物於生成後，即使經過1年亦觀察不到觸媒金屬的沈澱。Furthermore, the catalyst-containing metal silicon oligomer is the alkoxy group of tetraalkoxysilane, and one or two hydroxyl groups at the n, n+1 position or n, n+2 position present in the polyol Those obtained by a condensation reaction have, for example, the following partial structures (a) to (d). In addition, it is presumed that the catalyst metal is present between oxygen atoms in a catalyst metal-silicon oligomer to form a 5-membered ring structure or a 6-membered ring structure with the catalyst metal as a vertex, and it is stabilized. Therefore, after the catalyst-containing metal silicon oligomer of the present invention is formed, the precipitation of the catalyst metal is not observed even after one year.

Figure 02_image005
Figure 02_image005

含觸媒金屬矽寡聚物，可藉由1HNMR、29SiNMR等之NMR、IR、MASS等之公知方法鑑定。具體而言，若為NMR，可藉由以1HNMR確認藉由聚烷氧基矽烷與多元醇之縮合反應所生成的醇，進一步地以29SiNMR確認含觸媒金屬矽寡聚物中之矽之數目，來鑑定本發明之含觸媒金屬矽寡聚物。又，於矽寡聚物中攝入有觸媒金屬，可藉由生成矽寡聚物後，一定期間經過後，例如1年經過後，未觀察到觸媒金屬之沈澱來確認。The catalyst-containing metal silicon oligomer can be identified by known methods such as NMR, IR, and MASS such as 1HNMR and 29SiNMR. Specifically, in the case of NMR, the alcohol produced by the condensation reaction of polyalkoxysilane and polyol can be confirmed by 1HNMR, and the number of silicon in the catalyst-containing metal silicon oligomer can be confirmed by 29SiNMR. , to identify the catalyst-containing metal silicon oligomer of the present invention. In addition, the incorporation of the catalyst metal into the silicon oligomer can be confirmed by the fact that no precipitation of the catalyst metal is observed after a certain period of time, such as one year, after the silicon oligomer is formed.

樹脂及/或彈性體，可列舉不具有熱硬化性及/或光硬化性之樹脂及/或彈性體，例如可列舉聚酯系樹脂、苯氧基系樹脂、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、聚醯亞胺樹脂、聚醯胺樹脂、丙烯酸樹脂、聚醯胺醯亞胺樹脂或氟樹脂等。Resins and/or elastomers include resins and/or elastomers that do not have thermosetting properties and/or photohardening properties, such as polyester-based resins, phenoxy-based resins, ethylene-vinyl acetate copolymers, Ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, polyimide resin, polyamide resin, acrylic resin, polyamideimide resin or fluororesin, etc.

＜酚樹脂＞ 酚樹脂為與上述環氧樹脂產生硬化反應的成分。本發明之硬化性樹脂組成物，藉由含有酚樹脂，可得到機械特性優良的硬化物。＜Phenolic resin＞ The phenol resin is a component that undergoes a hardening reaction with the above-mentioned epoxy resin. Since the curable resin composition of the present invention contains a phenol resin, a cured product excellent in mechanical properties can be obtained.

酚樹脂並無特別限定，可為2官能、亦可為3官能以上。酚樹脂，例如可列舉苯酚酚醛清漆樹脂、烷基苯酚酚醛清漆樹脂、含有三嗪構造之苯酚酚醛清漆樹脂、雙酚A酚醛清漆樹脂、含有二環戊二烯構造之酚樹脂、Xylok型酚樹脂、萜烯改質酚樹脂、聚乙烯基酚類、含有萘構造之酚樹脂、含有茀構造之酚樹脂等。此等可單獨或組合複數種來使用。The phenol resin is not particularly limited, and may be bifunctional or trifunctional or more. Phenol resins include, for example, phenol novolac resins, alkylphenol novolac resins, phenol novolac resins containing a triazine structure, bisphenol A novolac resins, phenol resins containing a dicyclopentadiene structure, and Xylok-type phenol resins , terpene-modified phenol resins, polyvinyl phenols, phenolic resins containing naphthalene structure, phenolic resins containing fenugreek structure, etc. These can be used alone or in combination.

＜活性酯化合物＞ 活性酯化合物，為與上述環氧樹脂產生硬化反應之成分。本發明之硬化性樹脂組成物，藉由含有活性酯化合物，可得到硬化物之低介電特性優良的硬化物。<Active ester compound> The active ester compound is a component that causes a hardening reaction with the above epoxy resin. Since the curable resin composition of the present invention contains an active ester compound, a cured product excellent in low dielectric properties of the cured product can be obtained.

作為活性酯化合物，只要係具有活性酯基者即可，較佳為分子內具有至少2個活性酯基之化合物。The active ester compound may be any compound as long as it has an active ester group, and is preferably a compound having at least two active ester groups in the molecule.

作為活性酯化合物，就提高所得硬化物之耐熱性等之觀點，較佳為使羧酸化合物及/或硫代羧酸化合物，與羥基化合物及/或硫醇化合物進行反應所得之活性酯化合物。作為活性酯化合物，更佳為使羧酸化合物，與選自由具有酚性羥基之芳香族化合物(酚化合物或萘酚化合物等)及硫醇化合物所成之群的1種或2種以上進行反應所得之活性酯化合物；特佳為使羧酸化合物與具有酚性羥基之芳香族化合物進行反應而得到，且分子內具有至少2個活性酯基之芳香族化合物。The active ester compound is preferably an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound from the viewpoint of improving the heat resistance of the cured product obtained. As the active ester compound, it is more preferable to react a carboxylic acid compound with one or two or more kinds selected from the group consisting of an aromatic compound having a phenolic hydroxyl group (a phenol compound, a naphthol compound, etc.) and a thiol compound The obtained active ester compound is particularly preferably an aromatic compound obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group, and having at least two active ester groups in the molecule.

用以形成活性酯化合物之羧酸化合物之具體例子，可列舉安息香酸、乙酸、琥珀酸、馬來酸、依康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。此等之中，就提高所得電絕緣層之耐熱性的觀點，尤佳為琥珀酸、馬來酸、依康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸；更佳為鄰苯二甲酸、間苯二甲酸、對苯二甲酸；又更佳為間苯二甲酸、對苯二甲酸。Specific examples of the carboxylic acid compound used to form the active ester compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. acid etc. Among these, from the viewpoint of improving the heat resistance of the obtained electrical insulating layer, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are particularly preferred; Phthalic acid, isophthalic acid, terephthalic acid; more preferably isophthalic acid, terephthalic acid.

用以形成活性酯化合物之硫代羧酸化合物之具體例子，可列舉硫代乙酸、硫代安息香酸等。Specific examples of the thiocarboxylic acid compound used to form the active ester compound include thioacetic acid, thiobenzoic acid, and the like.

用以形成活性酯化合物之羥基化合物之具體例子，可列舉二羥基苯、雙酚A、雙酚F、雙酚S、酸式酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、甲酚、萘酚、二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、苯三醇、二環戊二烯基二酚、苯酚酚醛清漆等。Specific examples of the hydroxy compound used to form the active ester compound include dihydroxybenzene, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylbenzene Alkylated bisphenol S, phenol, cresol, naphthol, dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, benzenetriol, dicyclopentadienyl dicyclopentadienyl Phenol, phenol novolac, etc.

此等之中，就提高活性酯化合物之溶解性，並且提高所得硬化物之耐熱性的觀點，作為用以形成活性酯化合物之羥基化合物，較佳為二羥基萘、二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯基二酚、苯酚酚醛清漆；更佳為二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、二環戊二烯基二酚、苯酚酚醛清漆；又更佳為二環戊二烯基二酚、苯酚酚醛清漆。Among these, from the viewpoint of improving the solubility of the active ester compound and improving the heat resistance of the resulting cured product, the hydroxy compound for forming the active ester compound is preferably dihydroxynaphthalene, dihydroxynaphthalene, and dihydroxydihydroxydihydroxynaphthalene. Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, phenol novolac; more preferably dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Benzophenone, dicyclopentadienyl diphenol, phenol novolak; more preferably, dicyclopentadienyl diphenol, phenol novolak.

用以形成活性酯化合物之硫醇化合物之具體例子，可列舉苯二硫醇、三嗪二硫醇等。Specific examples of the thiol compound for forming the active ester compound include benzenedithiol, triazinedithiol, and the like.

活性酯化合物之製造方法並無特別限定，可藉由公知方法製造。例如，可藉由前述羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而得到。The manufacturing method of an active ester compound is not specifically limited, It can manufacture by a well-known method. For example, it can be obtained by the condensation reaction of the aforementioned carboxylic acid compound and/or thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound.

本發明中，作為活性酯化合物，例如可使用日本特開2002-12650號公報揭示之具備活性酯基之芳香族化合物及日本特開2004-277460號公報揭示之多官能性聚酯，或市售品。市售品例如可列舉商品名「EXB9451、EXB9460、EXB9460S、Epiclon HPC-8000-65T」(以上、DIC公司製、「Epiclon」為註冊商標)、商品名「DC808」(Japan Epoxy Resin公司製)、商品名「YLH1026」(Japan Epoxy Resin公司製)等。此等可單獨或組合2種以上來使用。In the present invention, as the active ester compound, for example, an aromatic compound having an active ester group disclosed in Japanese Patent Laid-Open No. 2002-12650 and a polyfunctional polyester disclosed in Japanese Patent Laid-Open No. 2004-277460, or commercially available Taste. Examples of commercially available products include trade names "EXB9451, EXB9460, EXB9460S, Epiclon HPC-8000-65T" (the above, manufactured by DIC Corporation, "Epiclon" is a registered trademark), trade names "DC808" (manufactured by Japan Epoxy Resin Corporation), Trade name "YLH1026" (manufactured by Japan Epoxy Resin Co., Ltd.) and the like. These can be used alone or in combination of two or more.

＜其他添加物＞ 本發明之硬化性樹脂組成物，可依用途，添加上述必須成分以外之其他成分，例如慣用之添加物。其他之慣用之添加物並無特別限定，例如可列舉樹脂及/或彈性體、無機填充劑、硬化促進劑、著色劑、消泡劑/調平劑、密著性賦予劑、搖變劑、偶合劑、難燃劑等。又，本發明之硬化性樹脂組成物，亦可依需要含有有機溶劑等。＜Other additives＞ In the curable resin composition of the present invention, other components other than the above-mentioned essential components, such as conventional additives, may be added according to the application. Other commonly used additives are not particularly limited, for example, resins and/or elastomers, inorganic fillers, hardening accelerators, colorants, defoaming agents/leveling agents, adhesion imparting agents, thixotropic agents, Coupling agent, flame retardant, etc. Moreover, the curable resin composition of this invention may contain an organic solvent etc. as needed.

樹脂及/或彈性體，可列舉不具有熱硬化性及/或光硬化性之樹脂及/或彈性體，例如可列舉聚酯系樹脂、苯氧基系樹脂、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、聚醯亞胺樹脂、聚醯胺樹脂、丙烯酸樹脂、聚醯胺醯亞胺樹脂或氟樹脂等。Resins and/or elastomers include resins and/or elastomers that do not have thermosetting properties and/or photohardening properties, such as polyester-based resins, phenoxy-based resins, ethylene-vinyl acetate copolymers, Ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, polybutadiene resin, polycarbonate resin, polyimide resin, polyamide resin, acrylic resin, polyamideimide resin or fluororesin, etc.

無機填充劑，可列舉硫酸鋇、鈦酸鋇、二氧化矽(無定形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽等)、滑石、黏土、碳酸鎂、碳酸鈣、氧化鋁、氫氧化鋁、氧化鋁、氮化矽、氮化硼、氮化鋁等。Inorganic fillers include barium sulfate, barium titanate, silica (amorphous silica, crystalline silica, fused silica, spherical silica, etc.), talc, clay, magnesium carbonate, carbonic acid Calcium, aluminum oxide, aluminum hydroxide, aluminum oxide, silicon nitride, boron nitride, aluminum nitride, etc.

無機填充劑，就比重小，可於硬化性樹脂組成物中以高的比例摻合，低熱膨脹性優良的觀點，較佳為二氧化矽、特佳為球狀二氧化矽。此等可單獨或組合2種以上來使用。The inorganic filler is preferably small in specific gravity, can be blended in a high proportion in the curable resin composition, and is excellent in low thermal expansion, and is preferably silica, and particularly preferably spherical silica. These can be used alone or in combination of two or more.

無機填充劑之平均粒徑較佳為3μm以下、更佳為1μm以下。再者，無機填充劑之平均粒徑，可藉由雷射繞射式粒子徑分布測定裝置求得。The average particle diameter of the inorganic filler is preferably 3 μm or less, more preferably 1 μm or less. In addition, the average particle diameter of an inorganic filler can be calculated|required by the laser diffraction particle diameter distribution measuring apparatus.

硬化促進劑，為促進上述環氧樹脂之間的硬化反應，或環氧樹脂與酚樹脂及活性酯化合物之硬化反應的成分，例如可列舉咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2-苯基咪唑、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等之咪唑衍生物；二氰二胺、苄基二甲基胺、4-(二甲基胺基)-N,N-二甲基苄基胺、4-甲氧基-N,N-二甲基苄基胺、4-甲基-N,N-二甲基苄基胺等之胺化合物；己二酸二醯肼、癸二酸二醯肼等之肼化合物；三苯基膦等之磷化合物；胍胺、甲基胍胺(acetoguanamine)、苯并胍胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪･異三聚氰酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪･異三聚氰酸加成物等之S-三嗪衍生物等。此等可單獨或組合2種以上來使用。The hardening accelerator is a component that promotes the hardening reaction between the above epoxy resins, or the hardening reaction between epoxy resins, phenol resins and active ester compounds, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl Imidazole derivatives such as yl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy Amine compounds such as base-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.; hydrazine compounds such as dihydrazine adipic acid, dihydrazine sebacate, etc. ; phosphorus compounds such as triphenylphosphine; guanamine, methyl guanamine (acetoguanamine), benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-tri Azine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine･isocyanuric acid adduct, 2,4 -S-triazine derivatives such as diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adducts, etc. These can be used alone or in combination of two or more.

著色劑例如可列舉酞菁藍、酞菁綠、碘綠、雙偶氮黃、結晶紫、氧化鈦、碳黑、萘黑等。此等可單獨或組合2種以上來使用。As a coloring agent, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc. are mentioned, for example. These can be used alone or in combination of two or more.

增黏劑例如可列舉石棉、有機皂土(Orben)、有機性搬土(benton)等。此等可單獨或組合2種以上來使用。Examples of the tackifier include asbestos, organic bentonite (Orben), and organic bentonite. These can be used alone or in combination of two or more.

消泡劑例如可列舉聚矽氧系消泡劑、氟系消泡劑、高分子系消泡劑等。此等可單獨或組合2種以上來使用。As an antifoaming agent, a polysiloxane type antifoaming agent, a fluorine type antifoaming agent, a polymer type antifoaming agent, etc. are mentioned, for example. These can be used alone or in combination of two or more.

密著性賦予劑例如可列舉噻唑系密著性賦予劑、***系密著性賦予劑、矽烷偶合劑等。此等可單獨或組合2種以上來使用。Examples of the adhesion-imparting agent include thiazole-based adhesion-imparting agents, triazole-based adhesion-imparting agents, and silane coupling agents. These can be used alone or in combination of two or more.

有機溶劑例如可列舉丙酮、甲基乙基酮、環己酮等之酮類；乙酸乙酯、乙酸丁酯、賽珞蘇乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯等之乙酸酯類；賽珞蘇、丁基賽珞蘇等之賽珞蘇類；卡必醇、丁基卡必醇等之卡必醇類；甲苯、二甲苯等之芳香族烴，此外可列舉二甲基甲醯胺、二甲基乙醯胺等。此等可單獨或組合2種以上來使用。Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, celosyl acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetates such as esters; serosols such as serosol and butyl carbitol; carbitols such as carbitol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene, etc. Dimethylformamide, dimethylacetamide, etc. are mentioned. These can be used alone or in combination of two or more.

＜＜摻合量＞＞ 硬化性樹脂組成物中，雙酚A型環氧樹脂、聯苯基芳烷基型環氧樹脂、雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂、含觸媒金屬矽寡聚物、酚樹脂、活性酯化合物及其他成分之摻合量並無特別限定。＜＜Amount of compounding＞＞ In the curable resin composition, epoxy resins other than bisphenol A type epoxy resin, biphenyl aralkyl type epoxy resin, bisphenol A type epoxy resin and biphenyl aralkyl type epoxy resin, The blending amount of catalyst-containing metal silicon oligomer, phenol resin, active ester compound and other components is not particularly limited.

雙酚A型環氧樹脂，相對於環氧樹脂之總量(以不揮發成分為基準)而言，例如可為40~70質量%、較佳可為50~60質量%，聯苯基芳烷基型環氧樹脂，相對於環氧樹脂之總量(以不揮發成分為基準)而言，例如可為20~50質量%、較佳可為30~40質量%，雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂，例如可為1~20質量%、較佳可為5~15質量%。Bisphenol A-type epoxy resin can be, for example, 40 to 70 mass %, preferably 50 to 60 mass %, relative to the total amount of epoxy resin (based on non-volatile components), and biphenyl aromatic The alkyl type epoxy resin can be, for example, 20 to 50 mass %, preferably 30 to 40 mass %, relative to the total amount of the epoxy resin (based on the non-volatile content), and the bisphenol A ring The epoxy resin other than the oxygen resin and the biphenyl aralkyl type epoxy resin may be, for example, 1 to 20% by mass, or preferably 5 to 15% by mass.

含觸媒金屬矽寡聚物，例如，相對於環氧樹脂100份而言，可為0.1~100份、較佳可為0.5~75份、更佳可為5~50份。若為如此的範圍，則鍍敷之析出與密著性更加提高。For example, relative to 100 parts of epoxy resin, the metal silicon oligomer containing catalyst can be 0.1-100 parts, preferably 0.5-75 parts, and more preferably 5-50 parts. Within such a range, the precipitation and adhesion of the plating are further improved.

較佳的硬化性樹脂組成物無特別限定，環氧樹脂中所含有的環氧基之環氧當量(Eq1)，與酚樹脂中所含有的羥基之羥基當量(Eq2)及活性酯中所含有的活性酯基當量(Eq3)之和之比{(Eq2+Eq3)/Eq1}可為0.5~1.4，更佳為0.6~1.2。該比落在如此的範圍時，硬化性樹脂組成物之硬化物，可具有優良之拉伸特性、低熱膨脹性、絕緣信賴性。The preferred curable resin composition is not particularly limited. The epoxy equivalent (Eq1) of the epoxy group contained in the epoxy resin, the hydroxyl equivalent (Eq2) of the hydroxyl group contained in the phenol resin, and the active ester are contained. The ratio of the sum of the active ester equivalents (Eq3) of {(Eq2+Eq3)/Eq1} can be 0.5~1.4, more preferably 0.6~1.2. When the ratio falls within such a range, the cured product of the curable resin composition can have excellent tensile properties, low thermal expansion properties, and insulation reliability.

又，酚樹脂與活性酯之摻合比，並無特別限定，例如，酚樹脂之摻合量與活性酯之摻合量之比(酚樹脂之摻合量：活性酯之摻合量)可為1：15~9：1、較佳可為1：12~7：3、更佳可為1：10~6：4。藉由使該比落在如此的範圍，硬化性樹脂組成物之硬化物，可具有優良之拉伸特性、低熱膨脹性、絕緣信賴性。藉由對含有硬化性樹脂組成物之絕緣層賦予柔軟性(延伸性)，絕緣層與導體層之密著性進一步提高。In addition, the blending ratio of the phenol resin and the active ester is not particularly limited. For example, the ratio of the blending amount of the phenol resin to the blending amount of the active ester (the blending amount of the phenol resin: the blending amount of the active ester) can be It is 1:15~9:1, preferably 1:12~7:3, more preferably 1:10~6:4. By setting the ratio within such a range, the cured product of the curable resin composition can have excellent tensile properties, low thermal expansion properties, and insulation reliability. By imparting flexibility (extensibility) to the insulating layer containing the curable resin composition, the adhesion between the insulating layer and the conductor layer is further improved.

＜＜＜使用方法＞＞＞ 接著，說明本發明之硬化性樹脂組成物之具體的使用方法。＜＜＜How to use＞＞＞ Next, the specific usage method of the curable resin composition of this invention is demonstrated.

＜＜硬化物＞＞ 硬化物，係藉由將上述本發明之硬化性樹脂組成物(包含後述乾膜中所含有的樹脂層)硬化而得到。＜＜hardened product＞＞ The cured product is obtained by curing the above-mentioned curable resin composition of the present invention (including the resin layer contained in the dry film described later).

使硬化性樹脂組成物硬化之方法並無特別限定，可因應硬化性樹脂組成物之組成而適當變更。作為一例，係經過於如上述之對象物上塗佈(例如以塗抹器等之塗佈)硬化性樹脂組成物之步驟後，依需要實施將硬化性樹脂組成物乾燥之乾燥步驟，並實施藉由加熱(例如以惰性氣體烘箱、加熱板、真空烘箱、真空壓製機等之加熱)而熱硬化之步驟即可。再者，各步驟中之實施條件(例如塗佈膜厚、乾燥溫度及時間、加熱硬化溫度及時間等)，係依硬化性樹脂組成物之組成或用途等而適當變更即可。The method of hardening the curable resin composition is not particularly limited, and can be appropriately changed according to the composition of the curable resin composition. As an example, after the step of applying (for example, applying with an applicator) the curable resin composition on the object as described above, a drying step of drying the curable resin composition is performed as necessary, and a The step of thermal hardening by heating (for example, heating in an inert gas oven, a hot plate, a vacuum oven, a vacuum press, etc.) is sufficient. In addition, the implementation conditions (for example, coating film thickness, drying temperature and time, heat curing temperature and time, etc.) in each step may be appropriately changed according to the composition and application of the curable resin composition.

＜＜乾膜＞＞ 本發明之乾膜，為將上述硬化性樹脂組成物塗佈或含浸於基材而得到者。＜＜Dry film＞＞ The dry film of the present invention is obtained by coating or impregnating the above-mentioned curable resin composition on a substrate.

此處，基材可列舉銅箔等之金屬箔；聚醯亞胺薄膜、聚酯薄膜、聚萘二甲酸乙二酯(PEN)薄膜等之薄膜；玻璃布、聚芳醯胺纖維等之纖維。Here, the base material includes metal foils such as copper foils; films such as polyimide films, polyester films, and polyethylene naphthalate (PEN) films; and fibers such as glass cloth and polyaramid fibers. .

乾膜例如可藉由於聚對苯二甲酸乙二酯薄膜上塗佈本發明之硬化性樹脂組成物並乾燥，依需要層合聚丙烯薄膜而得到。The dry film can be obtained by, for example, coating the curable resin composition of the present invention on a polyethylene terephthalate film, drying it, and laminating a polypropylene film as necessary.

＜＜配線板＞＞ 本發明之配線板，具有上述之硬化物。更具體而言，本發明之配線板，具有藉由上述硬化物所形成的絕緣層，與藉由鍍敷處理而於該硬化物上所形成的導體層。換言之，該導體層，為含有鍍敷金屬之導體層，亦可表述為鍍敷層。本發明之配線板，較佳為多層印刷配線板。＜＜Wiring Board＞＞ The wiring board of the present invention has the above-mentioned cured product. More specifically, the wiring board of this invention has the insulating layer formed by the said hardened|cured material, and the conductor layer formed on this hardened|cured material by a plating process. In other words, the conductor layer is a conductor layer containing a plated metal, and can also be expressed as a plated layer. The wiring board of the present invention is preferably a multilayer printed wiring board.

配線板之製造方法例如可列舉(a)將本發明之硬化性樹脂組成物，直接塗佈於形成有電路的內層電路基板，並進行乾燥、硬化之方法，或(b)將本發明之乾膜，加熱疊合於形成有電路的內層電路基板之方法(加熱疊合而一體成形，其後於烘箱中硬化之方法)或進行熱板壓製之方法等。The manufacturing method of the wiring board includes, for example, (a) a method of directly applying the curable resin composition of the present invention to an inner-layer circuit board on which a circuit is formed, and drying and curing, or (b) applying the curable resin composition of the present invention to Dry film, the method of heating and laminating on the inner layer circuit substrate with the circuit formed (the method of heating and laminating to form an integral body, and then the method of curing in the oven) or the method of hot-plate pressing, etc.

如此的製造方法當中，將乾膜進行疊合或熱板壓製之方法，由於內層電路所致之凹凸係於加熱熔融時消除，並在該情況下硬化，故最終可得到平坦的表面狀態之多層配線板，故較佳。Among such manufacturing methods, in the method of laminating the dry film or pressing the hot plate, since the unevenness caused by the inner layer circuit is eliminated during heating and melting, and is hardened in this case, a flat surface state can be finally obtained. Multilayer wiring boards are preferred.

又，於形成有電路的內層電路基板上進行疊合或熱板壓製由本發明之硬化性樹脂組成物所構成之乾膜時，亦可將形成有銅箔或電路的內層電路基板同時進行層合。In addition, when laminating or hot-pressing a dry film composed of the curable resin composition of the present invention on the inner-layer circuit board on which the circuit is formed, the inner-layer circuit board on which the copper foil or the circuit is formed may be simultaneously performed. Laminate.

於如此方式所得之層合基板上，以CO2 雷射或UV-YAG雷射等之雷射或鑽頭開孔(洞)。孔(洞)，可為以導通基板之表面與背面為目的之貫通孔(貫穿孔)、亦可為以導通內層之電路與層間絕緣層表面之電路為目的之有底洞(通孔，via hole)。On the laminated substrate obtained in this way, holes (holes) are made with a laser such as a CO 2 laser or a UV-YAG laser or a drill. A hole (hole) can be a through hole (through hole) for the purpose of conducting the surface and back of the substrate, or a bottomed hole (through hole, via hole).

有底洞(通孔)的情況時，於開孔後，依需要以粗面化處理液將洞的內壁或底部所存在之殘渣(膠渣)予以去除後，較佳為進行電漿處理。When there is a bottom hole (through hole), after the hole is opened, the residue (smear) existing on the inner wall or bottom of the hole is removed with a roughening treatment liquid as required, and then plasma treatment is preferably performed. .

絕緣層，通常係以表面之算術平均表面粗度Ra(根據JIS B 0601)成為400nm左右的方式被粗面化處理。但是，考慮對高頻通信(例如5G通信等)的適應時，通常要求Ra為200nm以下。The insulating layer is generally roughened so that the arithmetic mean surface roughness Ra (based on JIS B 0601) of the surface becomes about 400 nm. However, when considering adaptation to high-frequency communication (eg, 5G communication, etc.), Ra is generally required to be 200 nm or less.

此點，藉由本發明之硬化性樹脂組成物所形成之絕緣層的情況，即使表面之粗度小，與導體層之密著性亦優良，故於製造配線板時，即使不進行粗面化處理(使用處理液等之濕式蝕刻或使用電漿等之乾式蝕刻)亦可。其結果，藉由本發明之硬化性樹脂組成物所形成之絕緣層，即使表面之算術平均表面粗度Ra為200nm以下，亦不易產生導體層之剝離等，故可較佳地使用作為如上述之高頻通信用之基板材料。再者，本發明之配線板之製造方法，依基板之用途不同，亦可包含粗面化處理。In this regard, in the case of the insulating layer formed by the curable resin composition of the present invention, even if the surface roughness is small, the adhesion to the conductor layer is excellent, so that when manufacturing the wiring board, even if it is not roughened A treatment (wet etching using a treatment liquid or the like, or dry etching using a plasma or the like) may also be used. As a result, the insulating layer formed of the curable resin composition of the present invention does not easily peel off the conductor layer even if the arithmetic mean surface roughness Ra of the surface is 200 nm or less, so it can be preferably used as the above-mentioned Substrate material for high frequency communication. Furthermore, the manufacturing method of the wiring board of the present invention may also include roughening treatment depending on the use of the substrate.

本發明中，以無電解鍍敷與電解鍍敷之處理於絕緣層表面形成導體層之前，較佳對絕緣層表面照射至少照射強度10mW/cm2 以上之紫外線。藉此，與構成導體層之鍍敷層之密著性進一步提高。此時之紫外線之主波長係310nm左右以下、較佳為260nm左右以下、更佳為150~200nm左右。特佳為紫外線波長包含約184nm與約254nm 2種。In the present invention, before forming the conductor layer on the surface of the insulating layer by electroless plating and electrolytic plating, it is preferable to irradiate the surface of the insulating layer with ultraviolet rays with an irradiation intensity of at least 10 mW/cm 2 or more. Thereby, the adhesiveness with the plating layer which comprises a conductor layer is further improved. The dominant wavelength of the ultraviolet rays at this time is about 310 nm or less, preferably about 260 nm or less, and more preferably about 150 to 200 nm. It is especially preferable that the wavelength of ultraviolet rays includes two kinds of about 184 nm and about 254 nm.

紫外線之光源，可使用低壓水銀燈、準分子雷射、障壁放電燈、介電體障壁放電燈、微波無電極放電燈、瞬時放電燈等。例如使用低壓水銀燈時，184.9nm、253.7nm之主波長特別有效。又，使用準分子燈時，具體而言較期望為Ar2*(126nm)、Kr2*(146nm)、F2*(153nm)、ArBr*(165nm)、Xe2*(172nm)、ArCl*(175nm)、ArF(193nm)、KrBr*(207nm)、KrCl*(222nm)、KrF(248nm)、Xel*(253nm)、Cl2*(259nm)、XeBr*(283nm)、Br2*(289nm)、XeCl*(308nm)之波長之光。特別是Xe2*與KrCl*具有安定性，波長亦較小，能量大，因此表面改質效果大而較佳。As the light source of ultraviolet rays, low-pressure mercury lamps, excimer lasers, barrier discharge lamps, dielectric barrier discharge lamps, microwave electrodeless discharge lamps, and instantaneous discharge lamps can be used. For example, when using a low-pressure mercury lamp, the dominant wavelengths of 184.9 nm and 253.7 nm are particularly effective. When using an excimer lamp, specifically, Ar2*(126nm), Kr2*(146nm), F2*(153nm), ArBr*(165nm), Xe2*(172nm), ArCl*(175nm), ArF(193nm), KrBr*(207nm), KrCl*(222nm), KrF(248nm), Xel*(253nm), Cl2*(259nm), XeBr*(283nm), Br2*(289nm), XeCl*(308nm) ) of the wavelength of light. Especially Xe2* and KrCl* have stability, small wavelength and high energy, so the surface modification effect is large and better.

紫外線之照射時間，雖依所用之樹脂材料、紫外線之強度(照射量)而異，(紫外線之強度為5~20mW/cm2 左右時)，可於10秒~30分鐘左右之範圍適當調整、更佳為20秒~10分鐘左右。Although the irradiation time of ultraviolet rays varies depending on the resin material used and the intensity of ultraviolet rays (irradiation dose), (when the intensity of ultraviolet rays is about 5~20mW/cm 2 ), it can be properly adjusted within the range of about 10 seconds to 30 minutes. More preferably, it is about 20 seconds to 10 minutes.

再者，紫外線之照射，亦可於進行無電解鍍敷之處理之前進行複數次。In addition, the irradiation of an ultraviolet-ray may be performed several times before performing the process of electroless plating.

接著，於絕緣層表面，藉由減成法或半加成法等形成導體電路。不管何種方法，均可於無電解鍍敷處理或電解鍍敷處理之後，或實施兩方之鍍敷處理之後，以鍍敷金屬之壓力去除、強度提高為目的，實施於約80~180℃、10~60分鐘左右之稱為退火處理的熱處理。Next, a conductor circuit is formed on the surface of the insulating layer by a subtractive method, a semi-additive method, or the like. Regardless of the method, it can be performed at about 80 to 180° C. for the purpose of removing the pressure of the plated metal and improving the strength after the electroless plating treatment, the electrolytic plating treatment, or both the plating treatments. , 10 to 60 minutes of heat treatment called annealing treatment.

此處所用的鍍敷金屬，係銅、錫、焊料、鎳等，無特別限制，亦可組合複數種來使用。The plating metal used here is copper, tin, solder, nickel, etc., and is not particularly limited, and a plurality of them may be used in combination.

對絕緣層之表面實施鍍銅時，較佳為實施無電解鍍銅，接著實施電解鍍銅，形成特定厚度之導體層(銅層)。無電解鍍銅，為用以形成用來實施電解鍍銅之饋電層者，通常係形成為0.1~2.0μm左右之厚度。再者，鍍銅相較於鍍鎳等而言，係有與樹脂之密著性低的困難點，但對遵照本發明所形成之絕緣層表面實施鍍銅來形成導體層時，可得到優良的密著強度。When copper plating is performed on the surface of the insulating layer, electroless copper plating is preferably performed, followed by electrolytic copper plating to form a conductor layer (copper layer) with a specific thickness. Electroless copper plating is used to form a feed layer for performing electrolytic copper plating, and is usually formed to a thickness of about 0.1 to 2.0 μm. Furthermore, compared with nickel plating, copper plating has a difficulty in that the adhesion to resin is low, but when copper plating is applied to the surface of the insulating layer formed in accordance with the present invention to form a conductor layer, excellent results can be obtained. adhesion strength.

對絕緣層之表面所實施之無電解鍍敷及電解鍍敷只要係公知方法即可，不限定於特定方法，較佳為無電解鍍敷處理步驟之觸媒包含鈀-錫混合觸媒，且觸媒之1次粒子徑為10nm以下。又，較佳為無電解鍍敷處理步驟之鍍敷組成含有次磷酸作為還原劑。The electroless plating and electrolytic plating performed on the surface of the insulating layer are not limited to a specific method as long as it is a known method. Preferably, the catalyst in the electroless plating treatment step includes a palladium-tin mixed catalyst, and The primary particle diameter of the catalyst is 10 nm or less. Furthermore, it is preferable that the plating composition of the electroless plating treatment step contains hypophosphorous acid as a reducing agent.

關於無電解鍍敷，例如可應用日本特開平8-253869號公報、日本特開2002-57456號公報、日本特開2000-212762號公報等記載之方法。For electroless plating, methods described in, for example, Japanese Patent Laid-Open No. 8-253869, Japanese Patent Laid-Open No. 2002-57456, and Japanese Patent Laid-Open No. 2000-212762 can be applied.

又，可依需要重複複數次絕緣層及導體電路層之形成，藉以製造所期望之多層印刷配線板。In addition, the formation of the insulating layer and the conductor circuit layer can be repeated as many times as necessary, thereby producing a desired multilayer printed wiring board.

＜＜電子零件＞＞ 如此的硬化物，可使用於電子零件用等。＜＜Electronic parts＞＞ Such a cured product can be used for electronic parts and the like.

具有硬化物之電子零件並無特別限定，較佳可列舉適於以第5世代通信系統(5G)為代表之大容量高速通信或汽車的ADAS(先進駕駛系統)之毫米波雷達等。 [實施例]The electronic parts having the hardened material are not particularly limited, but preferably include millimeter-wave radars suitable for large-capacity high-speed communications represented by fifth-generation communication systems (5G) or ADAS (advanced driving systems) in automobiles. [Example]

以下使用實施例而更詳細說明本發明。再者，表中之摻合量係表示作為固體成分成分之質量份。The present invention will be described in more detail below using examples. In addition, the compounding quantity in a table|surface shows the mass part as a solid content.

＜含觸媒金屬矽寡聚物之合成＞ 將預先溶解於1.7g鹽酸之氯化鈀1.7g，添加至乙二醇336g後，攪拌使其溶解。於其中添加四乙氧基矽烷564g，以加熱包(mantle heater)加溫至50℃同時攪拌2小時，進行縮合反應而得到反應物。再者，該反應時所生成的醇並未分餾。又，該反應之前，乙二醇與四乙氧基矽烷並未混溶，而是分離為2層，但2小時縮合反應後係成為單一層。因此，可知該反應之反應率為100%(以下將之稱為「含有Pd之矽寡聚物」)。<Synthesis of Catalyst-Containing Metal Silicon Oligomers> After adding 1.7 g of palladium chloride previously dissolved in 1.7 g of hydrochloric acid to 336 g of ethylene glycol, the mixture was stirred and dissolved. To this was added 564 g of tetraethoxysilane, and the mixture was heated to 50° C. with a mantle heater while stirring for 2 hours, and a condensation reaction was performed to obtain a reactant. Furthermore, the alcohol produced during this reaction is not fractionated. In addition, before this reaction, ethylene glycol and tetraethoxysilane were not miscible, but separated into two layers, but after the condensation reaction for 2 hours, it became a single layer. Therefore, it can be seen that the reaction rate of this reaction is 100% (hereinafter referred to as "Pd-containing silicon oligomer").

作為硬化性樹脂組成物之原料，係使用以下者。As the raw material of the curable resin composition, the following were used.

＜＜原料＞＞ ＜樹脂成分＞ ・環氧樹脂 jER828(三菱化學(股)製、雙酚A型環氧樹脂、環氧當量190g/eq) NC-3000H(日本化藥(股)製、聯苯基芳烷基型環氧樹脂、環氧當量280g/eq) HP-4032(DIC(股)製、萘型環氧樹脂、環氧當量150g/eq) N-740(DIC(股)製、苯酚酚醛清漆型環氧樹脂、環氧當量253g/eq) ・酚樹脂 LA-3018-50P(DIC(股)製、含有胺基三嗪環之甲酚酚醛清漆型酚樹脂、酚性羥基當量150g/eq、甲基乙基酮溶液、不揮發成分50質量%、表1中之記載係不計揮發成分) ・活性酯化合物 HPC-8000-65T(DIC(股)製、活性酯基當量220g/eq、不揮發成分65質量%、表1中之記載係不計揮發成分) ・無機填充劑 Admafine SC2050((股)Admatechs)球狀二氧化矽(平均粒徑0.5μm) ・硬化促進劑 Curezol 2E4MZ(四國化成工業(股)製) ・添加劑 KBM-403(信越化學工業(股)製) ・含觸媒金屬矽寡聚物 含有Pd之矽寡聚物＜＜Ingredients＞＞ ＜Resin composition＞ ・Epoxy resin jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent 190g/eq) NC-3000H (made by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin, epoxy equivalent 280g/eq) HP-4032 (made by DIC (stock), naphthalene type epoxy resin, epoxy equivalent 150g/eq) N-740 (manufactured by DIC Corporation, phenol novolac epoxy resin, epoxy equivalent 253 g/eq) ・Phenolic resin LA-3018-50P (manufactured by DIC Corporation), cresol novolak-type phenol resin containing an amino triazine ring, phenolic hydroxyl equivalent 150 g/eq, methyl ethyl ketone solution, non-volatile content 50% by mass, table The records in 1 are excluding volatile components) ・Active ester compound HPC-8000-65T (manufactured by DIC Co., Ltd., active ester group equivalent 220 g/eq, non-volatile content 65% by mass, the description in Table 1 is excluding volatile content) ・Inorganic filler Admafine SC2050 ((stock) Admatechs) spherical silica (average particle size 0.5μm) ・Hardening accelerator Curezol 2E4MZ (Shikoku Chemical Industry Co., Ltd.) ·additive KBM-403 (Shin-Etsu Chemical Industry Co., Ltd.) ・Containing catalyst metal silicon oligomer Silicon oligomers containing Pd

＜＜硬化性樹脂組成物之調製＞＞ 將上述各原料以表1所示摻合量進行摻合，製造各實施例及各比較例之硬化性樹脂組成物。＜＜Preparation of curable resin composition＞ The above-mentioned respective raw materials were blended in the blending amounts shown in Table 1, and the curable resin compositions of respective Examples and respective Comparative Examples were produced.

＜＜評估用樣品之製作＞＞ 使用上述製造之各實施例及比較例之各硬化性樹脂組成物，遵照以下流程製作評估用之樣品。＜＜Preparation of samples for evaluation＞＞ Using each curable resin composition of each Example and Comparative Example produced above, samples for evaluation were produced according to the following procedure.

＜絕緣層之形成＞ 首先，將各硬化性樹脂組成物使用自轉/公轉混合器，充分攪拌、脫泡後，以塗抹器於PET薄膜上塗佈使硬化後之理論膜厚成為40μm，以乾燥爐於90℃乾燥10分鐘，製作源自各硬化性樹脂組成物之乾膜。接著，將所製作之各乾膜於覆銅層合板上以真空疊合，於100℃、0.5MPa進行疊合，將PET薄膜剝離後，以乾燥爐於180℃加熱30分鐘，於覆銅層合板上形成含有源自各硬化性樹脂組成物之硬化物的絕緣層。<Formation of insulating layer> First, each curable resin composition was thoroughly stirred and defoamed using an autorotation/revolution mixer, then coated on a PET film with an applicator so that the theoretical film thickness after curing was 40 μm, and dried in a drying oven at 90° C. for 10 minutes, to prepare dry films derived from the respective curable resin compositions. Next, the prepared dry films were laminated on the copper-clad laminate by vacuum lamination at 100° C. and 0.5 MPa. After peeling the PET film, the dry film was heated at 180° C. for 30 minutes in a drying furnace to form the copper-clad layer. An insulating layer containing a cured product derived from each curable resin composition is formed on the plywood.

(Ra之測定) 遵照以下方法測定所形成之各絕緣層表面之平均粗度Ra。 (測定方法) 測定機器：白色干涉顯微鏡(Bruker Contour GT-I) 測定條件：VSI模式、50倍鏡頭、測定範圍174.6× 130.9μm、以5點測定部位之平均值為測定值。 其測定結果示於表1。(Measurement of Ra) The average roughness Ra of the surface of each insulating layer formed was measured according to the following method. (test methods) Measuring machine: White interference microscope (Bruker Contour GT-I) Measurement conditions: VSI mode, 50x lens, measurement range 174.6 × 130.9 μm, the average value of 5 measurement points is the measurement value. The measurement results are shown in Table 1.

＜導體層之形成＞ 接著，對上述所形成之絕緣層面實施無電解鍍敷處理及電解鍍敷處理，形成由饋電層與電解鍍敷層所構成的導體層。具體而言，作為無電解鍍敷處理，係於清潔劑處理液(JCU製、PB-120)中60℃浸漬5分鐘，於觸媒賦予處理液(JCU製、PB-332)中60℃浸漬5分鐘，於還原處理液(JCU製、ES-400)中35℃浸漬5分鐘，於無電解鍍敷處理液(JCU製、PB-507F)中35℃浸漬15分鐘藉以形成由無電解鍍敷層所構成的饋電層。之後，作為電解鍍敷處理，於5%硫酸水溶液中室溫浸漬10秒，於硫酸銅鍍敷液(JCU製、CU-BRITE21)中以室溫45分鐘、電流密度3A/dm2 之條件形成電解鍍敷層。<Formation of Conductor Layer> Next, an electroless plating treatment and an electrolytic plating treatment are performed on the insulating layer formed above to form a conductor layer composed of a feeding layer and an electrolytic plating layer. Specifically, as an electroless plating treatment, immersion at 60° C. for 5 minutes in a detergent treatment solution (manufactured by JCU, PB-120), and immersion at 60° C. in a catalyst-imparting treatment solution (manufactured by JCU, PB-332) 5 minutes, immersed in a reduction treatment solution (manufactured by JCU, ES-400) at 35°C for 5 minutes, and immersed in an electroless plating treatment solution (manufactured by JCU, PB-507F) at 35°C for 15 minutes to form an electroless plating The feed layer composed of layers. Then, as an electrolytic plating treatment, immersion in a 5% sulfuric acid aqueous solution at room temperature for 10 seconds, followed by a copper sulfate plating solution (manufactured by JCU, CU-BRITE21) for 45 minutes at room temperature and a current density of 3 A/dm 2 Electrolytic plating layer.

如以上般進行，製作具有絕緣層，與設置於絕緣層上之導體層的評估用樣品(基板)。As described above, an evaluation sample (substrate) having an insulating layer and a conductor layer provided on the insulating layer was produced.

＜＜評估＞＞ ＜鍍敷析出性之評估＞ 對於各評估用樣品，算出相對於絕緣層整面(m2 )而言，所析出之導體層之面積(m2 )的比例來進行評估。其評估結果示於表1。<<Evaluation>><Evaluation of Plating Precipitation Properties> For each evaluation sample, the ratio of the area (m 2 ) of the deposited conductor layer with respect to the entire surface (m 2 ) of the insulating layer was calculated and evaluated. The evaluation results thereof are shown in Table 1.

＜鍍敷密著性之評估＞ 對於各評估用樣品，以剝離強度試驗來進行鍍敷密著性之評估。剝離強度係如以下般實施。首先，對各樣品之鍍銅層切出寬10mm、長60mm之切口。將該一方的端部剝離，並且以夾具夾住剝離部位，以桌上型拉伸試驗器(島津製作所製EZ-SX)以90度之角度、50mm/分鐘之速度剝下鍍銅層35mm之長度，測定剝離強度(N/cm)。 其測定結果示於表1。<Evaluation of plating adhesion> For each evaluation sample, the evaluation of the plating adhesion was performed by a peel strength test. The peel strength was implemented as follows. First, the copper plating layer of each sample was cut with a width of 10 mm and a length of 60 mm. The one end was peeled off, and the peeled part was clamped with a clamp, and a 35 mm portion of the copper plating layer was peeled off at an angle of 90 degrees and a speed of 50 mm/min with a desktop tensile tester (EZ-SX, manufactured by Shimadzu Corporation). length, and the peel strength (N/cm) was measured. The measurement results are shown in Table 1.

再者，就比較例1之樣品而言，未得到可實施剝離強度試驗之鍍銅層。In addition, in the sample of the comparative example 1, the copper plating layer which can perform a peel strength test was not obtained.

Figure 02_image007
Figure 02_image007

由表1所示結果明顯可知，除了變更硬化性樹脂組成物之成分以外係以相同條件來製造絕緣層時，於應用本發明之硬化性樹脂組成物的試樣中，確認到可形成即使表面粗度小(即使Ra為200nm以下)，與導體層之密著性亦良好的絕緣層。As is apparent from the results shown in Table 1, when the insulating layer was produced under the same conditions except that the components of the curable resin composition were changed, it was confirmed that even the surface was An insulating layer with a small thickness (even if Ra is 200 nm or less) and good adhesion to the conductor layer.

Claims (7)

一種硬化性樹脂組成物，其係含有環氧樹脂、含觸媒金屬矽寡聚物、酚樹脂與活性酯化合物之硬化性樹脂組成物，其特徵為 前述環氧樹脂，包含雙酚A型環氧樹脂、聯苯基芳烷基型環氧樹脂，與前述雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂， 前述含觸媒金屬矽寡聚物，為藉由使四烷氧基矽烷，與至少於n,n+1位或n,n+2位(惟n為1以上之整數)上鍵結有羥基之多元醇，在對無電解鍍敷具有觸媒性之金屬的存在下進行縮合反應而得到之寡聚物。A curable resin composition, which is a curable resin composition containing an epoxy resin, a catalyst-containing metal silicon oligomer, a phenol resin and an active ester compound, characterized by: The aforementioned epoxy resins include bisphenol A type epoxy resins, biphenyl aralkyl type epoxy resins, and epoxy resins other than the aforementioned bisphenol A type epoxy resins and biphenyl aralkyl type epoxy resins , The aforementioned catalyst-containing metal-silicon oligomer is obtained by bonding tetraalkoxysilane to at least n, n+1 positions or n, n+2 positions (only n is an integer of 1 or more) with hydroxyl groups The polyol is an oligomer obtained by a condensation reaction in the presence of a metal having catalytic properties for electroless plating. 如請求項1之硬化性樹脂組成物，其中前述雙酚A型環氧樹脂及聯苯基芳烷基型環氧樹脂以外之環氧樹脂，為苯酚酚醛清漆型環氧樹脂及萘型環氧樹脂之至少任1種。The curable resin composition of claim 1, wherein the epoxy resins other than the bisphenol A type epoxy resin and the biphenyl aralkyl type epoxy resin are phenol novolac type epoxy resin and naphthalene type epoxy resin At least any one of resins. 如請求項1或2之硬化性樹脂組成物，其中前述對無電解鍍敷具有觸媒性之金屬，為鐵、鎳、鈷、銅、鈀、銀、金、鉑之至少任1種。The curable resin composition according to claim 1 or 2, wherein the metal having catalytic properties for electroless plating is at least any one of iron, nickel, cobalt, copper, palladium, silver, gold, and platinum. 一種乾膜，其係於薄膜上形成由如請求項1至3中任一項之硬化性樹脂組成物構成的樹脂層而成。A dry film formed by forming a resin layer composed of the curable resin composition according to any one of claims 1 to 3 on a film. 一種硬化物，其係使如請求項1至3中任一項之硬化性樹脂組成物，或如請求項4之乾膜硬化而成。A cured product obtained by curing the curable resin composition according to any one of claims 1 to 3, or the dry film according to claim 4. 一種配線板，其具有含有如請求項5之硬化物的絕緣層與含有鍍敷金屬之導體層。A wiring board having an insulating layer containing the cured product as claimed in claim 5 and a conductor layer containing a plated metal. 一種電子零件，其具有含有如請求項5之硬化物的絕緣層與含有鍍敷金屬之導體層。An electronic component having an insulating layer containing the hardened product as claimed in claim 5 and a conductor layer containing a plated metal.
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