TW202236907A - Laminate for semi-additive manufacturing and printed wiring board using same - Google Patents
Laminate for semi-additive manufacturing and printed wiring board using same Download PDFInfo
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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
- H05K3/24—Reinforcing the conductive pattern
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
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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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
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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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
Abstract
Description
本發明係關於一種用於將基材兩面進行電性連接之平面狀之半加成工法用積層體及使用其之印刷配線板。The present invention relates to a planar semi-additive laminate for electrically connecting both sides of a base material and a printed wiring board using the same.
印刷配線板係於絕緣基材之表面形成有電路圖案金屬層者。近年來，隨著電子機器產品之小型化、輕量化要求不斷提高，印刷配線板（膜）之薄型化、及電路配線之高精細化要求亦日益提高。以往，作為製造電路配線之方法，業界廣泛使用減成法，該方法係於形成於絕緣性基材上之銅層之表面形成電路圖案形狀之蝕刻抗蝕劑，對無需電路之部分之銅層進行蝕刻，藉此形成銅配線。然而，減成法中，配線邊緣部分之銅容易殘留，當配線間距離因電路配線之高密度化而變短時，存在短路或缺乏配線間之絕緣可靠性等問題。又，若為了防止短路，或為了提高絕緣可靠性而進一步進行蝕刻，則蝕刻液會包繞抗蝕劑下部而致使側面蝕刻進行，結果存在配線寬度方向變細之問題。尤其於混合存在配線密度不同之區域時，存在於配線密度較低之區域之微細配線亦有若進行蝕刻則會消失等問題。進而，藉由減成法所獲得之配線之截面形狀非矩形，而成為邊緣向基材側延展之梯形或三角形之形狀，因此成為寬度在厚度方向不同之配線，作為電氣傳輸路徑而言亦存在問題。A printed wiring board is one in which a circuit pattern metal layer is formed on the surface of an insulating base material. In recent years, as the miniaturization and lightweight requirements of electronic equipment products continue to increase, the requirements for thinning printed wiring boards (films) and high-precision circuit wiring are also increasing. In the past, as a method of manufacturing circuit wiring, the subtractive method was widely used in the industry. This method is to form an etching resist in the shape of a circuit pattern on the surface of a copper layer formed on an insulating substrate, and to remove the copper layer on the part that does not need a circuit. Etching is performed, whereby copper wiring is formed. However, in the subtractive method, the copper at the edge of the wiring is likely to remain. When the distance between the wiring is shortened due to the high density of the circuit wiring, there are problems such as short circuit or lack of insulation reliability between the wiring. In addition, if further etching is performed to prevent short circuits or to improve insulation reliability, the etchant surrounds the lower portion of the resist and side etching progresses, resulting in a problem that the wiring becomes thinner in the width direction. In particular, when areas with different wiring densities are mixed, there is a problem that the fine wiring existing in the area with low wiring density will disappear if it is etched. Furthermore, the cross-sectional shape of the wiring obtained by the subtractive method is not a rectangle, but a trapezoidal or triangular shape whose edge extends toward the base material side, so it becomes a wiring whose width varies in the thickness direction, and also exists as an electrical transmission path question.
作為解決該等問題並製作微細配線電路之方法，業界提出了一種半加成法。於半加成法中，預先於絕緣性基材上形成導電性晶種層，再於該晶種層上之非電路形成部形成鍍覆抗蝕劑。經由導電性晶種層以電鍍方式形成配線部後，將抗蝕劑剝離，去除非電路形成部之晶種層，藉此形成微細配線。根據該方法，由於使鍍層沿著抗蝕劑之形狀析出，故而可使配線之截面形狀成為矩形，又，不論圖案之疏密如何，均可使目標寬度之配線析出，因此適於形成微細配線。As a method of solving these problems and producing a fine wiring circuit, a semi-additive method has been proposed in the industry. In the semi-additive method, a conductive seed layer is formed in advance on an insulating base material, and then a plating resist is formed on a non-circuit forming portion on the seed layer. After the wiring part is formed by electroplating through the conductive seed layer, the resist is peeled off, and the seed layer of the non-circuit forming part is removed, thereby forming fine wiring. According to this method, since the plating layer is deposited along the shape of the resist, the cross-sectional shape of the wiring can be made into a rectangle, and the wiring of the target width can be deposited regardless of the density of the pattern, so it is suitable for forming fine wiring. .
於半加成法中，已知一種藉由使用鈀觸媒之無電解鍍銅、或無電解鍍鎳而於絕緣性基材上形成導電性晶種層之方法。關於該等方法，例如於使用增層膜之情形時，為了確保膜基材與鍍銅膜之密接性，而進行被稱為除膠渣（desmear）粗化之使用過錳酸等烈性藥劑之基材表面粗化，自所形成之空隙中形成鍍膜，藉此利用定錨效應（anchor effect）而確保絕緣性基材與鍍膜之密接性。然而，若對基材表面進行粗化，則存在難以形成微細配線，又，高頻傳輸特性劣化等問題。因此，業界研究了減小粗化之程度，但於低粗化之情形時，存在無法獲得所形成之配線與基材間之所需密接強度之問題。Among the semi-additive methods, there is known a method of forming a conductive seed layer on an insulating substrate by electroless copper plating or electroless nickel plating using a palladium catalyst. Regarding these methods, for example, in the case of using a build-up film, in order to ensure the adhesion between the film substrate and the copper plating film, it is called desmear (desmear) roughening using a strong chemical such as permanganic acid. The surface of the base material is roughened, and a coating film is formed from the formed gap, so as to use the anchor effect (anchor effect) to ensure the adhesion between the insulating base material and the coating film. However, if the surface of the substrate is roughened, there are problems such as difficulty in forming fine wiring and deterioration of high-frequency transmission characteristics. Therefore, the industry has studied to reduce the degree of roughening, but in the case of low roughening, there is a problem that the required adhesion strength between the formed wiring and the substrate cannot be obtained.
另一方面，亦已知一種於聚醯亞胺膜上實施無電解鍍鎳而形成導電晶種之技術。於該情形時，藉由將聚醯亞胺膜浸漬於強鹼，而使表層之醯亞胺環開環，使膜表面變得親水性化，同時形成供水滲透之改質層，使鈀觸媒滲透至該改質層中，進行無電解鍍鎳，藉此形成鎳之晶種層（例如參照專利文獻1）。於該技術中，藉由自聚醯亞胺最表層之改質層中形成鍍鎳層而獲得了密接強度，但該改質層處於已使醯亞胺環開環之狀態，因此存在以下問題，即，膜表層成為在物理性、化學性方面脆弱之結構。On the other hand, there is also known a technique of performing electroless nickel plating on a polyimide film to form a conductive seed crystal. In this case, by immersing the polyimide membrane in a strong alkali, the imide ring on the surface is opened to make the surface of the membrane hydrophilic, and at the same time, a modified layer for water penetration is formed, so that palladium contacts The medium penetrates into the modified layer, and electroless nickel plating is performed to form a nickel seed layer (for example, refer to Patent Document 1). In this technique, the adhesion strength is obtained by forming a nickel plating layer from the modified layer of the outermost layer of polyimide, but the modified layer is in a state where the imide ring has been opened, so there are the following problems , that is, the film surface layer has a physically and chemically fragile structure.
相對於此，作為不進行表面粗化、或不於表層形成改質層之方法，亦已知一種藉由濺鍍法而於絕緣性基材上形成鎳、或鈦等導電性晶種之方法（例如參照專利文獻2）。該方法雖然能夠於不使基材表面粗化之情況下形成晶種層，但存在下述問題，亦即，需要使用昂貴之真空裝置，需要較大之初始投資，基材尺寸或形狀受限，生產性較低且步驟繁雜等。On the other hand, as a method of not roughening the surface or forming a modified layer on the surface, there is also known a method of forming conductive seeds such as nickel or titanium on an insulating substrate by sputtering. (For example, refer to Patent Document 2). Although this method can form a seed layer without roughening the surface of the substrate, it has the following problems, that is, an expensive vacuum device needs to be used, a large initial investment is required, and the size or shape of the substrate is limited. , low productivity and complicated steps, etc.
作為解決濺鍍法之問題之方法，業界提出了一種利用含有金屬粒子之導電性油墨之塗布層作為導電性晶種層之方法（例如參照專利文獻3）。據載，該技術為以下技術：於由膜或片所構成之絕緣性基材上，塗布分散有粒徑為1～500 nm之金屬粒子之導電性油墨，進行熱處理，藉此將上述所塗布之導電性油墨中之金屬粒子作為金屬層固定於絕緣性基材上而形成導電晶種層，進而於該導電晶種層上進行鍍覆。As a method of solving the problem of the sputtering method, a method of using a coating layer of a conductive ink containing metal particles as a conductive seed layer has been proposed (for example, refer to Patent Document 3). According to reports, this technology is the following technology: on an insulating substrate composed of a film or sheet, a conductive ink dispersed with metal particles with a particle size of 1 to 500 nm is coated, and heat treatment is performed, whereby the above-mentioned coated The metal particles in the conductive ink are fixed on the insulating substrate as a metal layer to form a conductive seed layer, and then plated on the conductive seed layer.
於專利文獻3中，提出了藉由半加成法來形成圖案，據實施例記載，塗布分散有銅粒子之導電性油墨，並進行熱處理而形成銅導電晶種層，將形成有該導電晶種層之基材用作半加成工法用基材，於導電晶種層上形成感光性抗蝕劑，經過曝光、顯影，以電鍍銅之方式使圖案形成部之膜厚增加，將抗蝕劑剝離後，對銅導電晶種層進行蝕刻而加以去除。又，於先前研究之藉由半加成工法而形成印刷配線板之情形時，將「在絕緣性基材上設置有較薄之銅箔或鍍銅膜作為導電性晶種之基材」用作半加成工法用基材。
如此，如銅導電性晶種層與銅電路圖案之組合般，導電性晶種層與電路圖案導電層由同種金屬形成之情形時，在去除非圖案形成部之導電性晶種層時，電路圖案導電層亦同時被蝕刻，因此得知電路圖案變得又細又薄，且電路導電層之表面粗糙度亦變大，其等成為在製造高密度配線、高頻傳輸用配線時所應解決之問題。
針對該等問題，本發明人等發明了一種技術，其係於絕緣性基材之表面上形成導電性銀粒子層，將該形成有導電性銀粒子之基材用作半加成工法用基材，藉此於晶種層蝕刻步驟中不會發生電路圖案變細或薄膜化，而形成設計再現性良好且具有平滑電路層表面之印刷配線板。（非專利文獻1、2）
該技術不僅能夠於單面形成電路，且亦能夠將兩面之電路加以連接，或能夠進行多層化並與內層印刷配線基材之導體電路層進行連接，但為了將兩面、或與內層之導體電路層進行連接，而在絕緣性基材之兩面具有導電性銀粒子層之半加成工法用基材形成孔來進行兩面連接時，若採用以往使用之藉由直接鍍覆法進行之兩面電性連接步驟，則會在將導電性晶種層上所吸附之鈀、導電性聚合物、碳等導電性物質去除之微蝕刻步驟中，導電性銀粒子層受損而致使導電性降低，因此有難以用作電路圖案形成之導電性晶種層之情形。
[先前技術文獻]
[專利文獻]
In
[專利文獻1]國際公開第2009/004774號 [專利文獻2]日本特開平9-136378號公報 [專利文獻3]日本特開2010-272837號公報 [非專利文獻1]村川昭、深澤憲正、富士川亘、白髮潤：“利用以銀奈米粒子為基底之半加成法之銅圖案形成技術”，第28次微電子學研討會論文集，pp285-288，2018. [非專利文獻2]村川昭、新林昭太、深澤憲正、富士川亘、白髮潤：“利用以銀為晶種層之半加成法之銅配線形成”，第33次電子安裝學會春季講演大會論文集，11B2-03，2019. [Patent Document 1] International Publication No. 2009/004774 [Patent Document 2] Japanese Patent Application Laid-Open No. 9-136378 [Patent Document 3] Japanese Unexamined Patent Publication No. 2010-272837 [Non-Patent Document 1] Akira Murakawa, Kenmasa Fukasawa, Wataru Fujikawa, Jun Shirafa: "Copper Pattern Formation Technology Utilizing the Semi-Additive Method Using Silver Nanoparticles as a Substrate", Proceedings of the 28th Symposium on Microelectronics , pp285-288, 2018. [Non-Patent Document 2] Akira Murakawa, Shota Shinbayashi, Kenmasa Fukasawa, Wataru Fujikawa, Jun Shirafa: "Formation of Copper Wiring Using the Semi-Additive Method Using Silver as a Seed Layer", 33rd Spring Lecture Conference of the Society of Electronics Manufacturers Proceedings, 11B2-03, 2019.
[發明所欲解決之課題][Problem to be Solved by the Invention]
本發明所欲解決之課題在於：提供一種用以與內層印刷配線基材之導體電路層進行電性連接而形成多層印刷配線板之半加成工法用積層體、及使用其之印刷配線板，該半加成工法用積層體無需利用鉻酸或過錳酸進行表面粗化，無需利用鹼來形成表面改質層等，且不使用真空裝置，即可形成具有基材與導體電路之高密接性、底切較少、設計再現性良好，且具有作為電路配線良好之矩形截面形狀的配線。 [解決課題之技術手段] The problem to be solved by the present invention is to provide a semi-additive laminate for forming a multi-layer printed wiring board by electrically connecting the conductor circuit layer of the inner printed wiring substrate, and a printed wiring board using the same , the semi-additive method uses a laminate without using chromic acid or permanganic acid for surface roughening, without using alkali to form a surface modification layer, etc., and without using a vacuum device, it can form a high Adhesiveness, less undercut, good design reproducibility, and wiring having a rectangular cross-sectional shape that is good as circuit wiring. [Technical means to solve the problem]
本發明人等為了解決上述課題進行了努力研究，結果發現：藉由使用在絕緣性基材（A）之兩表面上依序積層有導電性銀粒子層（M1）及銅層（M2）且上述銅層（M2）之層厚為0.1 μm～2 μm之積層體，可無需複雜之表面粗化或表面改質層之形成，且不使用真空裝置，即可形成以下所述之與內層印刷配線基材之導體電路層進行了電性連接之印刷配線板，該印刷配線板具有基材與導體電路之高密接性、底切較少、設計再現性良好，且具有作為電路配線良好之矩形截面形狀，從而完成了本發明。The inventors of the present invention conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that by using a layer of conductive silver particles (M1) and a copper layer (M2) sequentially laminated on both surfaces of the insulating substrate (A) and The layered body of the above-mentioned copper layer (M2) with a layer thickness of 0.1 μm to 2 μm can form the following inner layer without complicated surface roughening or surface modification layer formation, and without using a vacuum device. A printed wiring board in which the conductive circuit layer of the printed wiring base material is electrically connected. The printed wiring board has high adhesion between the base material and the conductive circuit, less undercut, good design reproducibility, and good circuit wiring Rectangular cross-sectional shape, thus completing the present invention.
即，本發明之提供內容如下： 1.一種半加成工法用積層體，其係用以將基材表面之導電電路層（CM1）與內層印刷配線基材之導體電路層（CM2）進行電性連接而製造多層印刷配線板者，且特徵在於： 於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2），且上述銅層（M2）之層厚為0.1 μm～2 μm。 That is, the content provided by the present invention is as follows: 1. A laminate for semi-additive processing, which is used to electrically connect the conductive circuit layer (CM1) on the surface of the substrate and the conductive circuit layer (CM2) of the inner printed wiring substrate to manufacture multilayer printed wiring boards , and is characterized by: A conductive silver particle layer (M1) and a copper layer (M2) are sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material. ), and the layer thickness of the copper layer (M2) is 0.1 μm to 2 μm.
2.如1所記載之半加成工法用積層體，其於上述絕緣層（A）之表面（S1）與導電性銀粒子層（M1）之間進而具有底塗層（B）。2. The laminate for the semi-additive method described in 1, which further has an undercoat layer (B) between the surface (S1) of the insulating layer (A) and the conductive silver particle layer (M1).
3.一種半加成工法用積層體，其係用以將基材表面之導電電路層（CM1）與內層印刷配線基材之導體電路層（CM2）進行電性連接而製造多層印刷配線板者，且特徵在於上述半加成工法用積層體為以下基材： 於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面具有導電性銀粒子層（M1）， 進而具有自絕緣層（A）達至導體電路層（CM2）之孔，且 上述孔之表面經鈀、導電性聚合物、碳中之任一種而確保了導電性。 3. A laminate for semi-additive processing, which is used to electrically connect the conductive circuit layer (CM1) on the surface of the substrate and the conductive circuit layer (CM2) of the inner printed wiring substrate to manufacture multilayer printed wiring boards , and it is characterized in that the laminated body for the above-mentioned semi-additive process is the following base material: There is a conductive silver particle layer (M1) on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, further has holes from the insulating layer (A) to the conductor circuit layer (CM2), and Conductivity is ensured on the surface of the above-mentioned pores by any one of palladium, conductive polymer, and carbon.
4.如3所記載之半加成工法用積層體，其於上述絕緣層（A）與導電性銀粒子層（M1）之間進而具有底塗層（B）。4. The laminate for the semi-additive method described in 3, which further has an undercoat layer (B) between the insulating layer (A) and the conductive silver particle layer (M1).
5.如1至4中任一項所記載之半加成工法用積層體，其中，構成上述銀粒子層（M1）之銀粒子為經高分子分散劑被覆者。5. The laminate for the semi-additive process according to any one of 1 to 4, wherein the silver particles constituting the silver particle layer (M1) are coated with a polymer dispersant.
6.如2或4所記載之半加成工法用積層體，其中，上述2或上述4中所記載之底塗層（B）為由具有反應性官能基[X]之樹脂構成之層，上述高分子分散劑為具有反應性官能基[Y]者，上述反應性官能基[X]與上述反應性官能基[Y]可藉由反應而相互形成鍵。6. The laminate for the semi-additive process described in 2 or 4, wherein the undercoat layer (B) described in the above 2 or 4 is a layer composed of a resin having a reactive functional group [X], The above-mentioned polymer dispersant has a reactive functional group [Y], and the above-mentioned reactive functional group [X] and the above-mentioned reactive functional group [Y] can form a bond with each other through a reaction.
7.如6所記載之半加成工法用積層體，其中，上述反應性官能基[Y]為含鹼性氮原子之基。7. The laminate for semi-addition process according to 6, wherein the reactive functional group [Y] is a group containing a basic nitrogen atom.
8.如6所記載之半加成工法用積層體，其中，上述具有反應性官能基[Y]之高分子分散劑為選自由聚伸烷基亞胺、及具有包含氧伸乙基單元之聚氧伸烷基結構之聚伸烷基亞胺所組成之群中之一種以上。8. The laminate for the semi-addition method as described in 6, wherein the above-mentioned polymer dispersant having the reactive functional group [Y] is selected from polyalkylene imines and those having oxyethylene units. One or more of the group consisting of polyalkyleneimines having a polyoxyalkylene structure.
9.如6所記載之半加成工法用積層體，其中，上述反應性官能基[X]為選自由酮基、乙醯乙醯基、環氧基、羧基、N-烷醇基（N-alkylol group）、異氰酸基、乙烯基、（甲基）丙烯醯基、烯丙基所組成之群中之一種以上。9. The semi-additive method laminate as described in 6, wherein the reactive functional group [X] is selected from a ketone group, an acetoacetyl group, an epoxy group, a carboxyl group, an N-alkanol group (N -alkylol group), isocyanate group, vinyl group, (meth)acryl group, allyl group composed of one or more.
10.一種印刷配線板，其特徵在於：為使用1至9中任一項所記載之半加成工法用積層體而形成者。10. A printed wiring board characterized in that it is formed by using the laminate for semi-additive process described in any one of 1 to 9.
11.一種多層印刷配線板，其係基材表面之導電電路層（CM1）與內層印刷配線基材之導體電路層（CM2）經電性連接者，且特徵在於： 於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2），且上述銅層（M2）之層厚為0.1 μm～2 μm， 上述多層印刷配線板進而具有自絕緣層（A）達至導體電路層（CM2）之孔，且 上述孔之表面具有積層有鈀、導電性聚合物、碳中之任一種、及銅層之與內層印刷配線基材之導體電路層（CM2）連接之連接結構。 11. A multi-layer printed wiring board, which is electrically connected to the conductive circuit layer (CM1) on the surface of the substrate and the conductive circuit layer (CM2) of the inner printed wiring substrate, and is characterized in that: A conductive silver particle layer (M1) and a copper layer (M2) are sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material. ), and the layer thickness of the above copper layer (M2) is 0.1 μm to 2 μm, The above-mentioned multilayer printed wiring board further has holes extending from the insulating layer (A) to the conductor circuit layer (CM2), and The surface of the hole has a connection structure that is laminated with any one of palladium, conductive polymer, carbon, and copper layer to connect with the conductor circuit layer (CM2) of the inner printed wiring substrate.
12.如11所記載之印刷配線板，其於上述絕緣層（A）與銀粒子層（M1）之間進而具有底塗層（B）。12. The printed wiring board according to 11, further having an undercoat layer (B) between the insulating layer (A) and the silver particle layer (M1).
13.一種半加成工法用積層體之製造方法，其係用以製造3至9中任一項所記載之多層印刷配線板者，且特徵在於具有：
步驟1，其於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2），且上述銅層（M2）之層厚為0.1 μm～2 μm之積層體，
形成自絕緣層（A）達至導體電路層（CM2）之孔；
步驟2，其於具有上述自絕緣層（A）達至導體電路層（CM2）之孔之基材之表面上，賦予鈀、導電性聚合物、碳中之任一種，使孔表面導電化；及
步驟3，其對上述銅層（M2）進行蝕刻，使導電性銀粒子層（M1）露出。
13. A method for manufacturing a laminate for semi-additive processing, which is used to manufacture the multilayer printed wiring board described in any one of 3 to 9, and is characterized in that it has:
Step 1, on the surface of the insulating layer (A) laminated on the inner printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, the conductive silver particle layer (M1) and the conductive silver particle layer (M1) are sequentially laminated. Copper layer (M2), and the layer thickness of the above-mentioned copper layer (M2) is 0.1 μm to 2 μm laminated body,
Forming holes from the insulating layer (A) to the conductor circuit layer (CM2);
Step 2, on the surface of the substrate having the above-mentioned holes reaching from the insulating layer (A) to the conductor circuit layer (CM2), any one of palladium, conductive polymer, and carbon is given to make the surface of the holes conductive; and
14.如13所記載之半加成工法用積層體之製造方法，其於絕緣性基材（A）與銀粒子層（M1）之間進而積層底塗層（B）。14. The method for producing a laminate for a semi-additive process according to 13, wherein an undercoat layer (B) is further laminated between an insulating base material (A) and a silver particle layer (M1).
15.一種10所記載之多層印刷配線板之製造方法，其特徵在於具有：
步驟1，其於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2），且上述銅層（M2）之層厚為0.1 μm～2 μm之積層體，
形成自絕緣層（A）達至導體電路層（CM2）之孔；
步驟2，其於具有上述自絕緣層（A）達至導體電路層（CM2）之孔之基材之表面上，賦予鈀、導電性聚合物、碳中之任一種，使孔表面導電化；
步驟3，其對上述銅層（M2）進行蝕刻，使導電性銀粒子層（M1）露出；
步驟4，其於上述導電性銀粒子層（M1）上形成圖案抗蝕劑；
步驟5，其藉由電鍍銅，而將表層與內層之導體電路層（CM2）進行電性連接，同時形成電路圖案；及
步驟6，其剝離圖案抗蝕劑，利用蝕刻液去除非導體電路圖案形成部之上述銀粒子層（M1）。
15. A method for manufacturing the multilayer printed wiring board described in 10, characterized in that it has:
Step 1, on the surface of the insulating layer (A) laminated on the inner printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, the conductive silver particle layer (M1) and the conductive silver particle layer (M1) are sequentially laminated. Copper layer (M2), and the layer thickness of the above-mentioned copper layer (M2) is 0.1 μm to 2 μm laminated body,
Forming holes from the insulating layer (A) to the conductor circuit layer (CM2);
Step 2, on the surface of the substrate having the above-mentioned holes reaching from the insulating layer (A) to the conductor circuit layer (CM2), any one of palladium, conductive polymer, and carbon is given to make the surface of the holes conductive;
16.如10所記載之印刷配線板，其於上述絕緣性基材（A）與銀粒子層（M1）之間進而具有底塗層（B）。 [發明之效果] 16. The printed wiring board according to 10, further having an undercoat layer (B) between the insulating base material (A) and the silver particle layer (M1). [Effect of Invention]
藉由使用本發明之半加成工法用積層體，可不使用真空裝置，而設計再現性良好地製造在各種平滑基材上之密接性較高、具有平滑之表面，且具有良好之矩形截面形狀之電路配線的與內層印刷配線基材之導體電路層進行了電性連接之印刷配線板。因此，藉由使用本發明之技術，可低成本地提供經多層化之高密度、高性能、能應對高頻傳輸之印刷配線板，在印刷配線領域中產業上之利用性較高。又，使用本發明之半加成工法用積層體所製造之印刷配線板不僅可用於通常之印刷配線板，亦可用於基材表面具有經圖案化之金屬層之各種電子構件，例如亦可應用於連接器、電磁波屏蔽、RFID等天線、膜電容器等。By using the laminate for the semi-additive process of the present invention, it can be manufactured with good design reproducibility without using a vacuum device. It has high adhesion on various smooth substrates, has a smooth surface, and has a good rectangular cross-sectional shape. A printed wiring board in which the circuit wiring is electrically connected to the conductor circuit layer of the inner printed wiring substrate. Therefore, by using the technology of the present invention, a multilayered high-density, high-performance printed wiring board capable of high-frequency transmission can be provided at low cost, and the industrial applicability in the field of printed wiring is high. In addition, the printed wiring board manufactured by the laminated body using the semi-additive process of the present invention can be used not only for ordinary printed wiring boards, but also for various electronic components with a patterned metal layer on the surface of the substrate. For example, it can also be used For connectors, electromagnetic wave shielding, antennas such as RFID, film capacitors, etc.
本發明之半加成工法用積層體之特徵在於：於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2），且 上述銅層（M2）之層厚為0.1 μm～2 μm。 The laminated body for the semi-additive process of the present invention is characterized in that it is sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material. There are conductive silver particle layer (M1) and copper layer (M2), and The layer thickness of the said copper layer (M2) is 0.1 micrometer - 2 micrometers.
又，本發明之更佳之態樣之半加成工法用積層體之特徵在於：於上述絕緣層（A）與導電性銀粒子層（M1）之間進而具有底塗層（B）。Moreover, the layered body for the semi-additive method of the more preferable aspect of this invention is characterized by further having an undercoat layer (B) between the said insulating layer (A) and electroconductive silver particle layer (M1).
本發明之半加成工法用積層體係於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之上述絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及銅層（M2）者，且上述絕緣層（A）、導電性銀粒子層（M1）、及銅層（M2）可形成於上述內層印刷配線基材之單面，亦可積層於兩面。The semi-additive method of the present invention uses a laminated system to sequentially laminate the conductive circuit layer (CM2) on the surface of the above-mentioned insulating layer (A) laminated on the inner layer printed wiring substrate formed on the insulating material. Silver particle layer (M1) and copper layer (M2), and the above-mentioned insulating layer (A), conductive silver particle layer (M1), and copper layer (M2) can be formed on one side of the above-mentioned inner layer printed wiring substrate , can also be stacked on both sides.
作為上述絕緣層（A）之材料，例如可例舉：聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醯胺樹脂、聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚萘二甲酸乙二酯樹脂、聚碳酸酯樹脂、丙烯腈-丁二烯-苯乙烯（ABS）樹脂、聚芳酯樹脂、聚縮醛樹脂、聚（甲基）丙烯酸甲酯等丙烯酸樹脂、聚偏二氟乙烯樹脂、聚四氟乙烯樹脂、聚氯乙烯樹脂、聚偏二氯乙烯樹脂、接枝共聚化有丙烯酸樹脂之氯乙烯樹脂、聚乙烯醇樹脂、聚乙烯樹脂、聚丙烯樹脂、胺酯樹脂（urethane resin）、環烯烴樹脂、聚苯乙烯、液晶聚合物（LCP）、聚醚醚酮（PEEK）樹脂、聚苯硫醚（PPS）、聚苯碸（PPSU）、纖維素奈米纖維、矽、碳化矽、氮化鎵、藍寶石、陶瓷、玻璃、類鑽碳（DLC）、氧化鋁等。Examples of the material for the insulating layer (A) include: polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate Diester resin, polyethylene naphthalate resin, polycarbonate resin, acrylonitrile-butadiene-styrene (ABS) resin, polyarylate resin, polyacetal resin, polymethyl(meth)acrylate Acrylic resin, polyvinylidene fluoride resin, polytetrafluoroethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride resin graft copolymerized with acrylic resin, polyvinyl alcohol resin, polyethylene resin, Polypropylene resin, urethane resin, cycloolefin resin, polystyrene, liquid crystal polymer (LCP), polyether ether ketone (PEEK) resin, polyphenylene sulfide (PPS), polyphenylene sulfide (PPSU) , cellulose nanofibers, silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, diamond-like carbon (DLC), alumina, etc.
又，作為上述絕緣層（A），亦可較佳地使用含有熱硬化性樹脂及無機填充材之樹脂基材。作為上述熱硬化性樹脂，例如可例舉：環氧樹脂、酚樹脂、不飽和醯亞胺樹脂、氰酸酯樹脂、異氰酸酯樹脂、苯并
作為上述絕緣層（A）之形態，可使用成形為膜、片、板狀之市售材料，亦可使用由上述樹脂之溶液、熔融液、分散液成形為平面狀之材料。又，可將上述樹脂之溶液、熔融液、分散液塗布於形成有導體電路層（CM2）之印刷配線基材上而製作上述絕緣層（A）。As the form of the above-mentioned insulating layer (A), commercially available materials formed into films, sheets, and plates can be used, and materials formed into planar shapes from solutions, melts, and dispersions of the above-mentioned resins can also be used. In addition, the above-mentioned insulating layer (A) can be produced by applying a solution, a melt, or a dispersion of the above-mentioned resin on the printed wiring base material on which the conductive circuit layer (CM2) is formed.
上述絕緣層（A）可以單層形式使用，亦可積層複數層而使用。於積層複數層之情形時，可積層單一材料，亦可將不同之材料積層複數層。The above-mentioned insulating layer (A) may be used as a single layer or may be used by laminating a plurality of layers. In the case of laminating multiple layers, a single material may be laminated, or multiple layers of different materials may be laminated.
上述絕緣層（A）可直接積層於形成有導體電路層（CM2）之印刷配線基材上，亦可經由接著劑層而積層。作為接著劑層，只要為具有絕緣性者，即可無特別限制地使用，可較佳地使用作為搭接片或層間接著片而市售之材料。於使用絕緣性之上述接著劑層時，就相當於上述將不同之材料積層複數層之情形，可將所積層之絕緣材料整體用作上述絕緣層（A）。The said insulating layer (A) may be laminated|stacked directly on the printed wiring base material in which the conductor circuit layer (CM2) was formed, and may be laminated|stacked via an adhesive agent layer. As the adhesive layer, any one can be used without particular limitation as long as it has insulating properties, and a material commercially available as a bridging sheet or an interlayer adhesive sheet can be preferably used. When using the above-mentioned insulating adhesive layer, it is equivalent to the above-mentioned case where a plurality of layers of different materials are laminated, and the entire laminated insulating material can be used as the above-mentioned insulating layer (A).
於使用上述市售之搭接片或層間接著片作為接著劑層，於上述形成有導體電路層（CM2）之內層印刷配線基材上積層上述絕緣層（A）之情形時，只要在產品之目錄、說明書或使用說明書等中所記載之順序、加熱加壓條件下進行積層即可。When the above-mentioned commercially available bonding sheet or interlayer bonding sheet is used as the adhesive layer to laminate the above-mentioned insulating layer (A) on the above-mentioned inner layer printed wiring substrate on which the conductive circuit layer (CM2) is formed, as long as the product is Lamination can be carried out in the order described in the catalog, instruction manual or instruction manual, under heat and pressure conditions.
關於本發明中所使用之上述形成有導體電路層（CM2）之內層印刷配線基材，可視需要適當地選擇剛性基材、可撓性基材而使用，可使用市售之各種在覆銅積層板材料之銅箔形成有電路圖案者。Regarding the above-mentioned inner layer printed wiring substrate formed with the conductive circuit layer (CM2) used in the present invention, rigid substrates and flexible substrates can be appropriately selected for use according to needs, and various commercially available copper-clad substrates can be used. The copper foil of the laminate material is formed with a circuit pattern.
關於上述銀粒子層（M1），在使用本發明之印刷配線板用積層體來製造印刷配線板時，上述銀粒子層（M1）成為藉由鍍覆步驟來形成下述成為配線圖案之導電電路層（CM1）時之鍍覆底層。Regarding the above-mentioned silver particle layer (M1), when a printed wiring board is manufactured using the laminate for a printed wiring board of the present invention, the above-mentioned silver particle layer (M1) becomes a conductive circuit that forms the following wiring pattern by a plating step Layer (CM1) is the plating bottom layer.
於構成上述銀粒子層（M1）之銀粒子中，可在能夠正常地實施下述鍍覆步驟之範圍含有銀以外之金屬粒子，但自能夠進一步提高下述非電路形成部之蝕刻去除性之方面而言，銀以外之金屬粒子之比率較佳為相對於銀100質量份為5質量份以下，更佳為2質量份以下。In the silver particles constituting the above-mentioned silver particle layer (M1), metal particles other than silver may be contained in the range where the following plating step can be normally performed, but the etching removal property of the following non-circuit formation part can be further improved. On the other hand, the ratio of metal particles other than silver is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of silver.
作為將上述銀粒子層（M1）形成於平面狀之上述絕緣層（A）之兩面的方法，例如可例舉於上述絕緣層（A）上之兩面塗布銀粒子分散液之方法。關於上述銀粒子分散液之塗布方法，只要能夠良好地形成銀粒子層（M1），便無特別限制，只要根據所使用之絕緣層（A）之形狀、尺寸、剛柔之程度等適當地選擇各種塗布方法即可。作為具體之塗布方法，例如可列舉：凹版法、膠版法、柔版法、移印法、凹版膠版法、凸版法、凸版反轉法、網版法、微觸法、反向法、氣動刮刀塗布法、刮刀塗布法、氣刀塗布法、擠壓式塗布法、含浸塗布法、轉移輥塗布法、接觸式塗布法、澆鑄塗布法、噴霧塗布法、噴墨法、模嘴塗布法、旋轉塗布法、棒式塗布法、浸漬塗布法等。此時，上述銀粒子層（M1）可同時形成於上述絕緣層（A）之兩面，亦可在形成於上述絕緣層（A）之一面後再形成於另一面。As a method of forming the silver particle layer (M1) on both surfaces of the planar insulating layer (A), for example, a method of coating a silver particle dispersion on both surfaces of the insulating layer (A) may be mentioned. Regarding the coating method of the above-mentioned silver particle dispersion liquid, as long as the silver particle layer (M1) can be formed well, there is no special limitation, as long as it is properly selected according to the shape, size, rigidity, etc. of the insulating layer (A) used Various coating methods are sufficient. Specific coating methods include gravure, offset, flexo, pad printing, gravure offset, letterpress, letterpress reverse, screen, micro-contact, reverse, and air scraper. Coating method, knife coating method, air knife coating method, extrusion coating method, dip coating method, transfer roll coating method, contact coating method, cast coating method, spray coating method, inkjet method, die coating method, rotary Coating method, rod coating method, dip coating method, etc. In this case, the silver particle layer ( M1 ) may be formed on both surfaces of the insulating layer (A) at the same time, or may be formed on the other surface after being formed on one side of the insulating layer (A).
對於上述絕緣層（A）、及形成於上述絕緣層（A）上之底塗層（B），可在塗布銀粒子分散液前進行表面處理，以提高銀粒子分散液之塗布性，提高鍍覆步驟中所形成之導電電路層（CM1）對基材之密接性。作為上述絕緣層（A）之表面處理方法，只要不使表面之粗糙度變大，引起微間距圖案形成性或由粗糙表面造成之信號傳輸損耗方面之問題，便無特別限制，只要適當地選擇各種方法即可。作為此種表面處理方法，例如可例舉：UV處理、氣相臭氧處理、液相臭氧處理、電暈處理、電漿處理等。該等表面處理方法可用一種方法進行，亦可併用兩種以上之方法。For the above-mentioned insulating layer (A) and the undercoat layer (B) formed on the above-mentioned insulating layer (A), surface treatment can be carried out before coating the silver particle dispersion to improve the applicability of the silver particle dispersion and improve the plating performance. The adhesion of the conductive circuit layer (CM1) formed in the coating step to the substrate. The surface treatment method for the insulating layer (A) is not particularly limited as long as it does not increase the surface roughness, causing problems in fine-pitch pattern formation or signal transmission loss caused by the rough surface, as long as it is properly selected. Various methods are available. As such a surface treatment method, UV treatment, gas-phase ozone treatment, liquid-phase ozone treatment, corona treatment, plasma treatment, etc. are mentioned, for example. These surface treatment methods may be performed by one method, or two or more methods may be used in combination.
將上述銀粒子分散液塗布於上述絕緣層（A）上、或上述底塗層（B）上後，對塗布膜進行乾燥，藉此使銀粒子分散液中所含之溶劑揮發，而於上述絕緣層（A）上、或上述底塗層（B）上形成上述銀粒子層（M1）。After coating the above-mentioned silver particle dispersion on the above-mentioned insulating layer (A) or on the above-mentioned undercoat layer (B), the coating film is dried, whereby the solvent contained in the silver particle dispersion is volatilized, and the above-mentioned The silver particle layer ( M1 ) is formed on the insulating layer (A) or on the undercoat layer (B).
上述乾燥之溫度及時間只要根據所使用之基材之耐熱溫度、下述用於上述金屬粒子分散液中之溶劑之種類進行適當選擇即可，溫度為20～350℃之範圍，時間較佳為1～200分鐘之範圍。又，為了於基材上形成密接性優異之銀粒子層（M1），上述乾燥溫度更佳為0～250℃之範圍。The temperature and time of the above-mentioned drying can be appropriately selected according to the heat-resistant temperature of the substrate used and the type of solvent used in the metal particle dispersion mentioned below. The temperature is in the range of 20-350°C, and the time is preferably The range of 1 to 200 minutes. Moreover, in order to form the silver particle layer (M1) excellent in adhesiveness on a base material, it is more preferable that the said drying temperature is the range of 0-250 degreeC.
關於形成有上述銀粒子層（M1）之上述絕緣層（A）、或形成有上述底塗層（B）之上述絕緣層（A），可視需要於上述乾燥後進而進行退火，以降低銀粒子層之電阻，或者提高上述絕緣層（A）或上述底塗層（B）與上述銀粒子層（M1）之密接性。退火之溫度及時間只要根據所使用之基材之耐熱溫度、所需電阻、生產性等進行適當選擇即可，只要於60～350℃之範圍進行1分鐘～2週之時間即可。又，若處於60～180℃之溫度範圍，則較佳為1分鐘～2週之時間，若處於180～350℃之範圍，則較佳為設為1分鐘～5小時左右。Regarding the above-mentioned insulating layer (A) formed with the above-mentioned silver particle layer (M1) or the above-mentioned insulating layer (A) formed with the above-mentioned undercoat layer (B), annealing may be performed after the above-mentioned drying to reduce the silver particle size. layer resistance, or improve the adhesion between the insulating layer (A) or the primer layer (B) and the silver particle layer (M1). The temperature and time of annealing can be properly selected according to the heat-resistant temperature of the substrate used, the required resistance, productivity, etc., and it only needs to be carried out in the range of 60-350°C for 1 minute to 2 weeks. Moreover, if it is in the temperature range of 60-180 degreeC, it is preferable to set it as time of 1 minute - 2 weeks, and if it is in the range of 180-350 degreeC, it is preferable to set it as about 1 minute to 5 hours.
關於上述乾燥，可進行送風，亦可不特別進行送風。又，乾燥可於大氣中進行，亦可於氮、氬等不活性氣體之置換環境下或氣流下進行，亦可於真空下進行。Regarding the above drying, air blowing may or may not be performed in particular. In addition, drying may be carried out in the atmosphere, may be carried out in an atmosphere of replacement of an inert gas such as nitrogen or argon or under air flow, or may be carried out under vacuum.
關於塗布膜之乾燥，除了在塗布場所進行自然乾燥以外，亦可於送風、恆溫乾燥器等乾燥器內進行。又，於上述絕緣層（A）為捲膜或捲片之情形時，可繼塗布步驟後，於所設置之非加熱或加熱空間內使捲材連續地移動，藉此進行乾燥、焙燒。作為此時之乾燥、焙燒之加熱方法，例如可例舉使用烘箱、熱風式乾燥爐、紅外線乾燥爐、雷射照射、微波、光照射（閃光照射裝置）等之方法。該等加熱方法可藉由一種進行，亦可併用兩種以上。The drying of the coated film may be performed in a drier such as a blower or a constant temperature drier, in addition to natural drying at the coating place. Also, when the insulating layer (A) is a rolled film or sheet, after the coating step, the rolled material can be continuously moved in a non-heated or heated space provided for drying and firing. As the heating method of drying and baking at this time, methods using an oven, a hot-air drying oven, an infrared drying oven, laser irradiation, microwaves, light irradiation (flash irradiation device), and the like may, for example, be mentioned. These heating methods may be performed by 1 type, and may use 2 or more types together.
形成於上述絕緣層（A）上或上述底塗層（B）上之上述金屬粒子層（M1）之形成量較佳為0.01～30 g/m 2之範圍，更佳為0.01～10 g/m 2之範圍。又，自藉由下述鍍覆步驟進行之導電電路層（CM1）之形成變得容易，藉由下述蝕刻進行之晶種層去除步驟變得容易之方面而言，上述形成量進而較佳為0.05～5 g/m 2之範圍。 The formation amount of the above-mentioned metal particle layer (M1) formed on the above-mentioned insulating layer (A) or on the above-mentioned undercoat layer (B) is preferably in the range of 0.01 to 30 g /m2, more preferably 0.01 to 10 g/m2 The range of m2. In addition, the formation amount is more preferable in terms of the ease of formation of the conductive circuit layer (CM1) by the following plating step and the ease of the seed layer removal step by the following etching. It is in the range of 0.05 to 5 g/m 2 .
上述銀粒子層（M1）之形成量可使用螢光X射線法、原子吸光法、ICP法等公知慣用之分析手法進行確認。The formation amount of the said silver particle layer (M1) can be confirmed using well-known and usual analysis methods, such as a fluorescent X-ray method, an atomic absorption method, and an ICP method.
又，於對下述抗蝕劑層利用活性光對電路圖案進行曝光之步驟中，為了抑制來自上述銀粒子層（M1）之活性光之反射，可於能夠形成上述銀粒子層（M1），能夠正常地實施下述電鍍，且能夠確保下述蝕刻去除性之範圍，在上述銀粒子層（M1）中含有吸收上述活性光之石墨或碳、花青化合物、酞青化合物、二硫醇金屬錯合物、萘醌化合物、二亞銨化合物、偶氮化合物等吸收光之顏料、或者色素作為光吸收劑。該等顏料或色素只要根據所使用之上述活性光之波長進行適當選擇即可。又，該等顏料或色素可使用一種，亦可併用兩種以上。進而，為了於上述銀粒子層（M1）中含有該等顏料或色素，只要於下述銀粒子分散液中摻合該等顏料或色素即可。In addition, in the step of exposing the circuit pattern with active light to the following resist layer, in order to suppress the reflection of active light from the above-mentioned silver particle layer (M1), the above-mentioned silver particle layer (M1) can be formed, The range in which the following electroplating can be normally performed and the following etching removability can be ensured, the above-mentioned silver particle layer (M1) contains graphite or carbon, cyanine compound, phthalocyanine compound, metal dithiol that absorbs the above-mentioned active light Light-absorbing pigments or pigments such as complexes, naphthoquinone compounds, diimonium compounds, and azo compounds are used as light absorbers. These pigments or pigments may be appropriately selected according to the wavelength of the above-mentioned active light to be used. In addition, these pigments or pigments may be used alone, or two or more kinds may be used in combination. Furthermore, in order to contain these pigments or coloring matter in the said silver particle layer (M1), what is necessary is just to mix these pigments or coloring matter in the following silver particle dispersion liquid.
用於形成上述銀粒子層（M1）之銀粒子分散液係銀粒子分散於溶劑中而成者。作為上述銀粒子之形狀，只要為能夠良好地形成銀粒子層（M1）者，便無特別限制，可使用球狀、透鏡狀、多面體狀、平板狀、桿狀、線狀等各種形狀之銀粒子。該等銀粒子可使用單一形狀之一種，亦可併用形狀不同之兩種以上。The silver particle dispersion liquid used for forming the said silver particle layer (M1) is what disperse|distributed the silver particle in the solvent. The shape of the above-mentioned silver particles is not particularly limited as long as it can form the silver particle layer (M1) well, and various shapes of silver such as spherical, lens, polyhedral, flat, rod, and linear can be used. particle. These silver particles may use one type of a single shape, and may use two or more types of different shapes together.
於上述銀粒子之形狀為球狀或多面體狀之情形時，其平均粒徑較佳為1～20,000 nm之範圍。又，於形成微細電路圖案之情形時，自銀粒子層（M1）之均質性進一步提高，亦可進一步提高下述蝕刻液去除性之方面而言，其平均粒徑更佳為1～200 nm之範圍，進而較佳為1～50 nm之範圍。再者，關於奈米尺寸粒子之「平均粒徑」係指利用分散良溶劑對上述金屬粒子進行稀釋，藉由動態光散射法所測得之體積平均值。於該測定中，可使用MICROTRAC公司製造之「Nanotrac UPA-150」。When the shape of the above-mentioned silver particles is spherical or polyhedral, the average particle diameter is preferably in the range of 1 to 20,000 nm. In addition, in the case of forming a fine circuit pattern, the average particle diameter is more preferably 1 to 200 nm in terms of further improving the homogeneity of the silver particle layer (M1) and further improving the removability of the etching solution described below. The range, and more preferably the range of 1 to 50 nm. Furthermore, the "average particle diameter" of the nanometer-sized particles refers to the volume average value measured by the dynamic light scattering method by diluting the above-mentioned metal particles with a good dispersion solvent. In this measurement, "Nanotrac UPA-150" manufactured by MICROTRAC Corporation can be used.
另一方面，於銀粒子具有透鏡狀、桿狀、線狀等形狀之情形時，其短徑較佳為1～200 nm之範圍，更佳為2～100 nm之範圍，進而較佳為5～50 nm之範圍。On the other hand, when the silver particles have a shape such as a lens, a rod, or a wire, the minor axis is preferably in the range of 1 to 200 nm, more preferably in the range of 2 to 100 nm, and even more preferably in the range of 5 nm. ~50 nm range.
上述銀粒子較佳為以銀粒子作為主成分者，但只要不妨礙下述鍍覆步驟，或不使下文所述之上述銀粒子層（M1）之蝕刻液去除性受損，便亦可將構成上述銀粒子之銀之一部分置換成其他金屬，或混合銀以外之金屬成分。The above-mentioned silver particles are preferably made of silver particles as the main component, but as long as the following plating step is not hindered, or the etching solution removability of the above-mentioned silver particle layer (M1) described below is not impaired, it can also be Part of the silver constituting the silver particles is replaced with other metals, or a metal component other than silver is mixed.
作為所置換或混合之金屬，可例舉選自由金、鉑、鈀、釕、錫、銅、鎳、鐵、鈷、鈦、銦及銥所組成之群中之一種以上之金屬元素。The metal to be substituted or mixed may be one or more metal elements selected from the group consisting of gold, platinum, palladium, ruthenium, tin, copper, nickel, iron, cobalt, titanium, indium and iridium.
相對於上述銀粒子，所置換或混合之金屬之比率較佳為於上述銀粒子中為5質量%以下，就上述銀粒子層（M1）之鍍覆性、蝕刻液去除性之觀點而言，更佳為2質量%以下。The ratio of the metal to be substituted or mixed with respect to the above-mentioned silver particles is preferably 5% by mass or less in the above-mentioned silver particles. More preferably, it is 2 mass % or less.
用於形成上述銀粒子層（M1）之銀粒子分散液係將銀粒子分散於各種溶劑中而成者，該分散液中之銀粒子之粒徑分布可統一為單分散，又，亦可為處於上述平均粒徑範圍之粒子之混合物。The silver particle dispersion used to form the above-mentioned silver particle layer (M1) is obtained by dispersing silver particles in various solvents. The particle size distribution of the silver particles in the dispersion can be uniformly monodispersed, or can be A mixture of particles within the above average particle size range.
作為上述銀粒子之分散液中所使用之溶劑，可使用水性介質或有機溶劑。作為上述水性介質，例如可例舉：蒸餾水、離子交換水、純水、超純水、及上述水與有機溶劑混合之混合物。As a solvent used for the dispersion liquid of the said silver particle, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion-exchanged water, pure water, ultrapure water, and a mixture of the above water and an organic solvent.
作為上述與水混合之有機溶劑，例如可例舉：甲醇、乙醇、正丙醇、異丙醇、乙基卡必醇、乙基賽珞蘇、丁基賽珞蘇等醇溶劑；丙酮、甲基乙基酮等酮溶劑；乙二醇、二乙二醇、丙二醇等伸烷基二醇溶劑；聚乙二醇、聚丙二醇、聚四亞甲基二醇等聚伸烷基二醇溶劑；N-甲基-2-吡咯啶酮等內醯胺溶劑等。 又，作為單獨使用有機溶劑時之有機溶劑，可例舉：醇化合物、醚化合物、酯化合物、酮化合物等。 As the above-mentioned organic solvent mixed with water, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosulfur, and butyl cellosulfate; Ketone solvents such as ethyl ethyl ketone; alkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol; polyalkylene glycol solvents such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Lactamic solvents such as N-methyl-2-pyrrolidone, etc. Moreover, as an organic solvent in the case of using an organic solvent alone, an alcohol compound, an ether compound, an ester compound, a ketone compound, etc. are mentioned.
作為上述醇溶劑或醚溶劑，例如可例舉：甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、庚醇、己醇、辛醇、壬醇、癸醇、十一醇、十二醇、十三醇、十四醇、十五醇、硬脂醇、烯丙醇、環己醇、松油醇、萜品醇、二氫萜品醇、2-乙基-1,3-己二醇、乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、甘油、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、二乙二醇單***、二乙二醇單甲醚、二乙二醇單丁醚、四乙二醇單丁醚、丙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、丙二醇單丙醚、二丙二醇單丙醚、丙二醇單丁醚、二丙二醇單丁醚、三丙二醇單丁醚等。Examples of the aforementioned alcohol solvent or ether solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, heptanol, hexanol, octanol, and Alcohol, Nonyl Alcohol, Decyl Alcohol, Undecyl Alcohol, Dodecyl Alcohol, Tridecyl Alcohol, Myristyl Alcohol, Pentadecyl Alcohol, Stearyl Alcohol, Allyl Alcohol, Cyclohexanol, Terpineol, Terpineol, Dihydro Terpineol, 2-ethyl-1,3-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol Monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, etc.
作為上述酮溶劑，例如可例舉：丙酮、環己酮、甲基乙基酮等。又，作為上述酯溶劑，例如可例舉：乙酸乙酯、乙酸丁酯、乙酸-3-甲氧基丁酯、乙酸-3-甲氧基-3-甲基丁酯等。進而，作為其他有機溶劑，可列舉甲苯等烴溶劑、尤其是碳原子數8以上之烴溶劑。As said ketone solvent, acetone, cyclohexanone, methyl ethyl ketone, etc. are mentioned, for example. Moreover, as said ester solvent, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, etc. are mentioned, for example. Furthermore, examples of other organic solvents include hydrocarbon solvents such as toluene, especially hydrocarbon solvents having 8 or more carbon atoms.
作為上述碳原子數8以上之烴溶劑，例如可例舉辛烷、壬烷、癸烷、十二烷、十三烷、十四烷、環辛烷、二甲苯、1,3,5-三甲苯、乙基苯、十二基苯、四氫萘、三甲基苯環己烷等非極性溶劑，可視需要與其他溶劑進行組合而使用。進而，亦可併用作為混合溶劑之礦油精、溶劑油等溶劑。Examples of the above-mentioned hydrocarbon solvent having 8 or more carbon atoms include octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, 1,3,5-tridecane, Non-polar solvents such as toluene, ethylbenzene, dodecylbenzene, tetralin, and trimethylbenzenecyclohexane can be used in combination with other solvents as necessary. Furthermore, solvents, such as mineral spirits and mineral spirits, which are mixed solvents, can also be used together.
上述溶劑只要為能使銀粒子穩定地分散，能於上述絕緣層（A）、或下文所述之形成於上述絕緣層（A）上之底塗層（B）上良好地形成上述銀粒子層（M1）者，便無特別限制。又，上述溶劑可使用一種，亦可併用兩種以上。As long as the above-mentioned solvent can stably disperse the silver particles, the above-mentioned silver particle layer can be favorably formed on the above-mentioned insulating layer (A) or the undercoat layer (B) formed on the above-mentioned insulating layer (A) described below. (M1), there are no special restrictions. In addition, the above-mentioned solvents may be used alone, or two or more kinds may be used in combination.
關於上述銀粒子分散液中之銀粒子之含有率，只要使用上述各種塗布方法以上述絕緣層（A）上之上述銀粒子層（M1）之形成量成為0.01～30 g/m 2之範圍之方式進行適當調整，並以使黏度具有與上述各種塗布方法相匹配之最佳之塗布適應性之方式進行調整即可，但較佳為0.1～50質量%之範圍，更佳為0.5～20質量%之範圍。 Regarding the content of silver particles in the above-mentioned silver particle dispersion liquid, the formation amount of the above-mentioned silver particle layer (M1) on the above-mentioned insulating layer (A) is within the range of 0.01 to 30 g /m2 using the above-mentioned various coating methods. Appropriate adjustments can be made in such a way that the viscosity has the best coating adaptability to match the above-mentioned various coating methods, but it is preferably in the range of 0.1-50% by mass, more preferably 0.5-20% by mass % range.
上述銀粒子分散液較佳為上述銀粒子不會在上述各種溶劑中進行凝集、融合、沉澱而保持長期之分散穩定性，較佳為含有用以使銀粒子分散於上述各種溶劑中之分散劑。作為此種分散劑，較佳為具有與金屬粒子配位之官能基之分散劑，例如可例舉具有羧基、胺基、氰基、乙醯乙醯基、含磷原子之基、硫醇基、氰硫基、甘胺酸基（glycinato group）等官能基之分散劑。The above-mentioned silver particle dispersion is preferably such that the above-mentioned silver particles do not undergo aggregation, fusion, and precipitation in the above-mentioned various solvents and maintain long-term dispersion stability, and preferably contains a dispersant for dispersing the silver particles in the above-mentioned various solvents . Such a dispersant is preferably a dispersant having a functional group that coordinates with the metal particles, for example, a carboxyl group, an amine group, a cyano group, an acetoacetyl group, a phosphorus atom-containing group, or a thiol group. , thiocyanate, glycine group (glycinato group) and other functional groups of the dispersant.
作為上述分散劑，可使用市售或獨自合成之低分子量或高分子量之分散劑，只要根據使金屬粒子分散之溶劑、或供塗布金屬粒子分散液之上述絕緣層（A）之種類等，並視目的進行適當選擇即可。例如可較佳地使用：十二烷硫醇（dodecanthiol）、1-辛硫醇、三苯基膦、十二胺、聚乙二醇、聚乙烯吡咯啶酮、聚伸乙基亞胺、聚乙烯吡咯啶酮；肉豆蔻酸、辛酸、硬脂酸等脂肪酸；膽酸、甘草酸、松脂酸等具有羧基之多環式烴化合物等。此處，於下述底塗層（B）上形成銀粒子層（M1）之情形時，自該等2層之密接性變得良好之方面而言，較佳為使用具有下述反應性官能基[Y]之化合物，該反應性官能基[Y]能夠與用於下述底塗層（B）之樹脂所具有之反應性官能基[X]形成鍵。As the above-mentioned dispersant, commercially available or self-synthesized low-molecular-weight or high-molecular-weight dispersants can be used, as long as it depends on the solvent used to disperse the metal particles, or the type of the above-mentioned insulating layer (A) for coating the metal particle dispersion liquid, etc., and Depending on the purpose, an appropriate selection can be made. For example, dodecanthiol (dodecanthiol), 1-octylthiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, poly Vinylpyrrolidone; myristic acid, octanoic acid, stearic acid and other fatty acids; cholic acid, glycyrrhizic acid, rosinic acid and other polycyclic hydrocarbon compounds with carboxyl groups, etc. Here, when the silver particle layer (M1) is formed on the undercoat layer (B) described below, it is preferable to use a silver particle layer having the following reactive functional A compound of the group [Y] capable of forming a bond with the reactive functional group [X] of the resin used for the undercoat layer (B) described below.
作為具有反應性官能基[Y]之化合物，例如可例舉具有胺基、醯胺基、烷醇醯胺基、羧基、羧酸酐基、羰基、乙醯乙醯基、環氧基、脂環環氧基、氧環丁烷環、乙烯基、烯丙基、（甲基）丙烯醯基、（封端化）異氰酸基、(烷氧基)矽基等之化合物、矽倍半氧烷化合物等。尤其自能夠進一步提高底塗層（B）與金屬粒子層（M1）之密接性之方面而言，上述反應性官能基[Y]較佳為含鹼性氮原子之基。作為上述含鹼性氮原子之基，例如可例舉：亞胺基、一級胺基、二級胺基等。As a compound having a reactive functional group [Y], for example, an amino group, an amide group, an alkanolamide group, a carboxyl group, a carboxylic anhydride group, a carbonyl group, an acetoacetyl group, an epoxy group, an alicyclic Compounds such as epoxy group, oxetane ring, vinyl group, allyl group, (meth)acryl group, (blocked) isocyanate group, (alkoxy) silicon group, etc., silsesquioxide alkanes etc. In particular, the reactive functional group [Y] is preferably a basic nitrogen atom-containing group from the viewpoint of further improving the adhesion between the undercoat layer (B) and the metal particle layer (M1). As the above-mentioned basic nitrogen atom-containing group, an imine group, a primary amino group, a secondary amino group, and the like may, for example, be mentioned.
上述含鹼性氮原子之基可於分散劑之1分子中存在單個或複數個。藉由在分散劑中含有複數個含鹼性氮原子之基，使得含鹼性氮原子之基之一部分以與金屬粒子之相互作用而有助於金屬粒子之分散穩定性，剩餘之含鹼性氮原子之基有助於提高與上述絕緣層（A）之密接性。又，於將具有反應性官能基[X]之樹脂用於下述底塗層（B）之情形時，分散劑中之含鹼性氮原子之基可與該反應性官能基[X]之間形成鍵，可進一步提高下述金屬圖案層（M2）在上述絕緣層（A）上之密接性，故較佳。The above-mentioned basic nitrogen atom-containing group may exist singly or in plural in one molecule of the dispersant. By containing a plurality of groups containing basic nitrogen atoms in the dispersant, part of the groups containing basic nitrogen atoms can interact with the metal particles to help the dispersion stability of the metal particles, and the rest contain basic nitrogen atoms. The nitrogen atom group contributes to the improvement of the adhesiveness with the above-mentioned insulating layer (A). Also, when a resin having a reactive functional group [X] is used for the undercoat layer (B) below, the basic nitrogen atom-containing group in the dispersant can be combined with the reactive functional group [X]. It is preferable to form a bond between them to further improve the adhesion of the metal pattern layer (M2) described below on the insulating layer (A).
關於上述分散劑，自能夠形成銀粒子分散液之穩定性、塗布性良好、及在上述絕緣層（A）上表現出良好之密接性的銀粒子層（M1）之方面而言，分散劑較佳為高分子分散劑，作為該高分子分散劑，較佳為：聚伸乙基亞胺、聚丙烯亞胺等聚伸烷基亞胺、對上述聚伸烷基亞胺加成聚氧伸烷基而成之化合物等。Regarding the above-mentioned dispersant, in terms of being able to form the silver particle layer (M1) with good stability and coating properties of the silver particle dispersion liquid and good adhesion on the above-mentioned insulating layer (A), the dispersant is better than It is preferably a polymer dispersant, and as the polymer dispersant, preferably: polyalkyleneimines such as polyethyleneimine and polypropyleneimine, and polyoxyalkyleneimines added to the above-mentioned polyalkyleneimines. Compounds made of alkyl groups, etc.
作為對上述聚伸烷基亞胺加成聚氧伸烷基而成之化合物，可為聚伸乙基亞胺與聚氧伸烷基呈直鏈狀鍵結而成者，亦可為對於由上述聚伸乙基亞胺所構成之主鏈，在其側鏈接枝聚氧伸烷基而成者。As a compound obtained by adding a polyoxyalkylene group to the above-mentioned polyalkyleneimine, a polyoxyalkylene imine and a polyoxyalkylene group may be linearly bonded, or may be obtained by adding a polyoxyalkylene group. The main chain composed of the above-mentioned polyethyleneimine is formed by grafting polyoxyalkylene groups on its side chains.
作為對上述聚伸烷基亞胺加成聚氧伸烷基而成之化合物之具體例，例如可例舉：聚伸乙基亞胺與聚氧乙烯之嵌段共聚物、使環氧乙烷與存在於聚伸乙基亞胺之主鏈中的亞胺基之一部分進行加成反應而導入有聚氧乙烯結構者、使聚伸烷基亞胺所具有之胺基、聚氧乙二醇所具有之羥基及環氧樹脂所具有之環氧基進行反應而成者等。Specific examples of compounds obtained by adding a polyoxyalkylene group to the above-mentioned polyalkyleneimine include, for example, block copolymers of polyethyleneimine and polyoxyethylene, ethylene oxide Addition reaction with part of the imine group present in the main chain of polyethyleneimine to introduce a polyoxyethylene structure, the amine group of polyalkyleneimine, polyoxyethylene glycol It is formed by reacting the hydroxyl group of epoxy resin with the epoxy group of epoxy resin.
作為上述聚伸烷基亞胺之市售品，可例舉日本觸媒股份有限公司製造之「EPOMIN（註冊商標）PAO系列」之「PAO2006W」、「PAO306」、「PAO318」、「PAO718」等。Examples of commercially available polyalkyleneimines include "PAO2006W", "PAO306", "PAO318", and "PAO718" of "EPOMIN (registered trademark) PAO series" manufactured by Nippon Shokubai Co., Ltd. .
上述聚伸烷基亞胺之數量平均分子量較佳為3,000～30,000之範圍。The number average molecular weight of the polyalkyleneimine is preferably in the range of 3,000 to 30,000.
關於使上述銀粒子分散所需之上述分散劑之使用量，相對於上述銀粒子100質量份較佳為0.01～50質量份之範圍，又，自能夠於上述絕緣層（A）上、或下述底塗層（B）上形成表現出良好之密接性之銀粒子層（M1）之方面而言，上述使用量相對於上述銀粒子100質量份較佳為0.1～10質量份之範圍，進而，自能夠提高上述銀粒子層（M1）之鍍覆性之方面而言，更佳為0.1～5質量份之範圍。The amount of the above-mentioned dispersant required to disperse the above-mentioned silver particles is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of the above-mentioned silver particles, and can be used on or under the above-mentioned insulating layer (A). In terms of forming the silver particle layer (M1) exhibiting good adhesion on the primer layer (B), the above-mentioned usage amount is preferably in the range of 0.1 to 10 parts by mass relative to 100 parts by mass of the above-mentioned silver particles, and further , The range of 0.1-5 mass parts is more preferable from the point which can improve the platability of the said silver particle layer (M1).
作為上述銀粒子分散液之製造方法，並無特別限制，可使用各種方法進行製造，例如可將使用低真空氣相蒸發法等氣相法所製造之銀粒子分散於溶劑中，亦可藉由液相對銀化合物進行還原而直接製備銀粒子分散液。不論是氣相、液相法，均可適當地視需要藉由更換溶劑或添加溶劑而變更製造時之分散液及塗布時之分散液之溶劑組成。氣相、液相法中，自分散液之穩定性或製造步驟之簡便性考慮，可尤佳地使用液相法。作為液相法，例如可藉由在上述高分子分散劑之存在下對銀離子進行還原而製造。The method for producing the above-mentioned silver particle dispersion is not particularly limited, and various methods can be used for production. For example, silver particles produced by a gas phase method such as a low vacuum vapor phase evaporation method can be used to disperse them in a solvent. The liquid phase reduces the silver compound to directly prepare the silver particle dispersion. Regardless of the gas-phase or liquid-phase method, the solvent composition of the dispersion liquid during production and the dispersion liquid during coating can be changed as appropriate by replacing or adding solvents as needed. Among the gas phase and liquid phase methods, the liquid phase method can be preferably used in view of the stability of the dispersion and the simplicity of the production steps. As a liquid phase method, it can manufacture by reducing silver ion in presence of the said polymer dispersant, for example.
於上述銀粒子分散液中，可進而視需要摻合界面活性劑、調平劑、黏度調整劑、成膜助劑、消泡劑、防腐劑等有機化合物。Organic compounds such as surfactants, leveling agents, viscosity regulators, film-forming aids, defoamers, and preservatives can be further blended into the above-mentioned silver particle dispersion liquid as needed.
作為上述界面活性劑，例如可例舉：聚氧乙烯壬基苯醚、聚氧乙烯月桂醚、聚氧乙烯苯乙烯基苯醚、聚氧乙烯山梨醇四油酸酯、聚氧乙烯-聚氧丙烯共聚物等非離子系界面活性劑；油酸鈉等脂肪酸鹽、烷基硫酸酯鹽、烷基苯磺酸鹽、烷基磺基琥珀酸鹽、萘磺酸鹽、聚氧乙烯烷基硫酸鹽、烷磺酸鈉鹽、烷基二苯醚磺酸鈉鹽等陰離子系界面活性劑；烷胺鹽、烷基三甲銨鹽、烷基二甲基苄基銨鹽等陽離子系界面活性劑等。Examples of the surfactant include: polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitan tetraoleate, polyoxyethylene-polyoxyethylene Non-ionic surfactants such as propylene copolymers; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates Anionic surfactants such as salt, alkanesulfonic acid sodium salt, alkyl diphenyl ether sulfonic acid sodium salt, etc.; cationic surfactants such as alkylamine salt, alkyltrimethylammonium salt, alkyldimethylbenzylammonium salt, etc. .
作為上述調平劑，可使用一般之調平劑，例如可例舉：聚矽氧系化合物、乙炔二醇系化合物、氟系化合物等。A general leveling agent can be used as said leveling agent, For example, a polysiloxane type compound, an acetylene glycol type compound, a fluorine type compound, etc. are mentioned.
作為上述黏度調整劑，可使用一般之增黏劑，例如可例舉：能夠藉由調整成鹼性而進行增黏之丙烯酸聚合物、合成橡膠乳膠、能夠藉由分子締合而進行增黏之胺酯樹脂、羥乙基纖維素、羧甲基纖維素、甲基纖維素、聚乙烯醇、氫化蓖麻油、醯胺蠟、氧化聚乙烯、金屬皂、二亞苄基山梨醇等。As the above-mentioned viscosity modifier, a general thickening agent can be used, for example, an acrylic polymer that can be adjusted to be alkaline and can be thickened, a synthetic rubber latex, and a compound that can be thickened by molecular association. Urethane resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, etc.
作為上述成膜助劑，可使用一般之成膜助劑，例如可例舉：二辛基磺基琥珀酸酯鈉鹽等陰離子系界面活性劑、山梨醇酐單油酸酯等疏水性非離子系界面活性劑、聚醚改質矽氧烷、聚矽氧油等。As the above-mentioned film-forming aids, general film-forming aids can be used, for example, anionic surfactants such as dioctyl sulfosuccinate sodium salt, hydrophobic nonionic surfactants such as sorbitan monooleate, etc. It is a surfactant, polyether modified siloxane, polysiloxane oil, etc.
作為上述消泡劑，可使用一般之消泡劑，例如可例舉：聚矽氧系消泡劑、非離子系界面活性劑、聚醚、高級醇、聚合物系界面活性劑等。As the antifoaming agent, general antifoaming agents can be used, for example, polysiloxane-based antifoaming agents, nonionic surfactants, polyethers, higher alcohols, polymer-based surfactants, and the like.
作為上述防腐劑，可使用一般之防腐劑，例如可例舉：異噻唑啉系防腐劑、三
又，作為本發明之半加成工法用積層體之更佳之態樣，可例舉於上述絕緣層（A）與導電性銀粒子層（M1）之間進而具有底塗層（B）之積層體。設置有該底塗層之半加成工法用積層體可進一步提高上述絕緣層（A）與導電電路層（CM1）之密接性，故較佳。Also, as a more preferable aspect of the laminate for the semi-additive process of the present invention, a laminate having an undercoat layer (B) between the insulating layer (A) and the conductive silver particle layer (M1) can be exemplified. body. The laminate for the semi-additive method provided with this primer layer is preferable because it can further improve the adhesion between the insulating layer (A) and the conductive circuit layer (CM1).
上述底塗層（B）可藉由以下方式而形成：於上述絕緣層（A）之表面之一部分或整面塗布底塗劑，去除上述底塗劑中所含之水性介質、有機溶劑等溶劑。此處，底塗劑係指為了提高絕緣層（A）與導電電路層（CM1）之密接性而使用者，係指使下述各種樹脂溶解或分散於溶劑中而成之液狀組成物。The above-mentioned undercoat layer (B) can be formed by applying a primer on a part or the entire surface of the above-mentioned insulating layer (A), and removing solvents such as aqueous media and organic solvents contained in the above-mentioned primer . Here, the primer is used to improve the adhesion between the insulating layer (A) and the conductive circuit layer (CM1), and refers to a liquid composition obtained by dissolving or dispersing the following resins in a solvent.
作為將上述底塗劑塗布於上述絕緣層（A）之方法，只要可良好地形成底塗層（B），便無特別限制，可根據所使用之絕緣層（A）之形狀、尺寸、剛柔程度等適當地選擇各種塗布方法。作為具體之塗布方法，例如可例舉：凹版法、膠版法、柔版法、移印法、凹版膠版法、凸版法、凸版反轉法、網版法、微觸法、反向法、氣動刮刀塗布法、刮刀塗布法、氣刀塗布法、擠壓式塗布法、含浸塗布法、轉移輥塗布法、接觸式塗布法、澆鑄塗布法、噴霧塗布法、噴墨法、模嘴塗布法、旋轉塗布法、棒式塗布法、浸漬塗布法等。The method of applying the primer to the insulating layer (A) is not particularly limited as long as the primer (B) can be formed satisfactorily. Various coating methods are appropriately selected according to the degree of softness and the like. As specific coating methods, for example, gravure method, offset method, flexo method, pad printing method, gravure offset method, letterpress method, letterpress reverse method, screen method, micro-contact method, reverse method, pneumatic method, etc. Blade coating method, blade coating method, air knife coating method, extrusion coating method, dip coating method, transfer roll coating method, contact coating method, casting coating method, spray coating method, inkjet method, die coating method, Spin coating method, rod coating method, dip coating method, etc.
又，作為於膜、片、板狀之上述絕緣層（A）之兩面塗布上述底塗劑之方法，只要可良好地形成底塗層（B），便無特別限制，只要適當地選擇上述所例示之塗布方法即可。此時，上述底塗層（B）可同時形成於上述絕緣層（A）之兩面，亦可在形成於上述絕緣層（A）之一面後再形成於另一面。In addition, as a method of coating the above-mentioned undercoating agent on both sides of the above-mentioned insulating layer (A) in the form of a film, a sheet, or a plate, there are no particular restrictions as long as the undercoat layer (B) can be formed well, as long as the above-mentioned ones are selected appropriately. The exemplified coating method will suffice. In this case, the undercoat layer (B) may be formed on both surfaces of the insulating layer (A) at the same time, or may be formed on the other surface after being formed on one side of the insulating layer (A).
上述絕緣層（A）可於塗布底塗劑前進行表面處理，以提高底塗劑之塗布性，或提高上述導電電路層（CM1）對基材之密接性。作為上述絕緣層（A）之表面處理方法，可使用與在上述絕緣層（A）上形成銀粒子層（M1）時之表面處理方法相同之方法。The above-mentioned insulating layer (A) can be surface-treated before applying the primer to improve the applicability of the primer, or to improve the adhesion of the above-mentioned conductive circuit layer (CM1) to the substrate. As a surface treatment method of the said insulating layer (A), the same method as the surface treatment method at the time of forming a silver particle layer (M1) on the said insulating layer (A) can be used.
作為將上述底塗劑塗布於絕緣層（A）之表面後，去除該塗布層中所含之溶劑而形成底塗層（B）之方法，例如一般之方法為使用乾燥機使其乾燥，使上述溶劑揮發。作為乾燥溫度，只要設定為能夠使上述溶劑揮發且不會對上述絕緣層（A）產生不良影響之範圍之溫度即可，可為室溫乾燥，亦可為加熱乾燥。具體之乾燥溫度較佳為20～350℃之範圍，更佳為60～300℃之範圍。又，乾燥時間較佳為1～200分鐘之範圍，更佳為1～60分鐘之範圍。As a method of forming the primer layer (B) by removing the solvent contained in the coating layer after applying the above-mentioned primer agent on the surface of the insulating layer (A), for example, the general method is to dry it with a drier, and make it The above-mentioned solvent evaporates. As drying temperature, what is necessary is just to set it as the temperature of the range which can volatilize the said solvent and does not exert a bad influence on the said insulating layer (A), and may dry at room temperature, and may heat dry. The specific drying temperature is preferably in the range of 20-350°C, more preferably in the range of 60-300°C. Also, the drying time is preferably in the range of 1 to 200 minutes, more preferably in the range of 1 to 60 minutes.
關於上述乾燥，可進行送風，亦可不特別進行送風。又，乾燥可於大氣中進行，亦可於氮、氬等置換環境或氣流下進行，亦可於真空下進行。Regarding the above drying, air blowing may or may not be performed in particular. In addition, drying may be performed in the atmosphere, may be performed in a nitrogen, argon, or other replacement atmosphere or air flow, or may be performed under vacuum.
於上述絕緣層（A）為單片之膜、片、板之情形時，除了在塗布場所進行自然乾燥以外，可於送風、恆溫乾燥器等乾燥器內進行。又，於上述絕緣層（A）為捲膜或捲片之情形時，可繼塗布步驟後，於所設置之非加熱或加熱空間內使捲材連續地移動，藉此進行乾燥。When the above-mentioned insulating layer (A) is a single film, sheet or plate, besides natural drying at the coating place, it can be carried out in a dryer such as a blower or a constant temperature dryer. Also, when the insulating layer (A) is a rolled film or sheet, drying can be carried out by continuously moving the rolled material in a non-heated or heated space provided after the coating step.
上述底塗層（B）之膜厚只要根據使用本發明所製造之印刷配線板之規格、用途進行適當選擇即可，自能夠進一步提高上述絕緣層（A）與上述金屬圖案層（M2）之密接性之方面而言，較佳為10 nm～30 μm之範圍，更佳為10 nm～1 μm之範圍，進而較佳為10 nm～500 nm之範圍。The film thickness of the primer layer (B) can be appropriately selected according to the specifications and uses of the printed wiring board manufactured by the present invention, since the gap between the insulating layer (A) and the metal pattern layer (M2) can be further improved. In terms of adhesion, it is preferably in the range of 10 nm to 30 μm, more preferably in the range of 10 nm to 1 μm, and still more preferably in the range of 10 nm to 500 nm.
關於形成底塗層（B）之樹脂，於使用具有反應性官能基[Y]者作為上述金屬粒子之分散劑時，較佳為具有相對於反應性官能基[Y]具有反應性之反應性官能基[X]之樹脂。作為上述反應性官能基[X]，例如可例舉：胺基、醯胺基、烷醇醯胺基、酮基、羧基、羧酸酐基、羰基、乙醯乙醯基、環氧基、脂環環氧基、氧環丁烷環、乙烯基、烯丙基、（甲基）丙烯醯基、（封端化）異氰酸基、(烷氧基)矽基等。又，亦可使用矽倍半氧烷化合物作為形成底塗層（B）之化合物。Regarding the resin forming the undercoat layer (B), when using a resin having a reactive functional group [Y] as a dispersant for the above-mentioned metal particles, it is preferable to have reactivity with respect to the reactive functional group [Y]. Resin with functional group [X]. Examples of the above-mentioned reactive functional group [X] include amine group, amide group, alkanolamide group, keto group, carboxyl group, carboxylic acid anhydride group, carbonyl group, acetylacetyl group, epoxy group, ester group, etc. Cycloepoxy, oxetane, vinyl, allyl, (meth)acryl, (blocked) isocyanate, (alkoxy) silyl, etc. Moreover, a silsesquioxane compound can also be used as a compound which forms an undercoat layer (B).
尤其於上述分散劑中之反應性官能基[Y]為含鹼性氮原子之基時，自能夠進一步提高上述絕緣層（A）上之導體電路層（CM2）之密接性之方面而言，形成底塗層（B）之樹脂較佳為具有酮基、羧基、羰基、乙醯乙醯基、環氧基、脂環環氧基、烷醇醯胺基、異氰酸基、乙烯基、（甲基）丙烯醯基、烯丙基作為反應性官能基[X]者。Especially when the reactive functional group [Y] in the above-mentioned dispersant is a group containing a basic nitrogen atom, from the aspect of further improving the adhesion of the conductor circuit layer (CM2) on the above-mentioned insulating layer (A), The resin forming the undercoat layer (B) preferably has a ketone group, a carboxyl group, a carbonyl group, an acetoacetyl group, an epoxy group, an alicyclic epoxy group, an alkanolamide group, an isocyanate group, a vinyl group, A (meth)acryl group or an allyl group is used as the reactive functional group [X].
作為形成上述底塗層（B）之樹脂，例如可例舉：胺酯樹脂、丙烯酸樹脂、以胺酯樹脂作為殼且以丙烯酸樹脂作為核之核-殼型複合樹脂、環氧樹脂、醯亞胺樹脂、醯胺樹脂、三聚氰胺樹脂、酚樹脂、脲甲醛樹脂、使聚異氰酸酯與苯酚等封端劑進行反應而獲得之封端異氰酸酯聚乙烯醇、聚乙烯吡咯啶酮等。再者，以胺酯樹脂作為殼且以丙烯酸樹脂作為核之核-殼型複合樹脂，例如可藉由在胺酯樹脂之存在下使丙烯酸單體聚合而獲得。又，該等樹脂可使用一種，亦可併用兩種以上。Examples of the resin forming the undercoat layer (B) include urethane resins, acrylic resins, core-shell composite resins with urethane resins as the shell and acrylic resins as the core, epoxy resins, acrylic resins, and acrylic resins. Amine resin, amide resin, melamine resin, phenol resin, urea-formaldehyde resin, isocyanate-blocked polyvinyl alcohol obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinylpyrrolidone, etc. Furthermore, a core-shell composite resin having an urethane resin as a shell and an acrylic resin as a core can be obtained, for example, by polymerizing an acrylic monomer in the presence of an urethane resin. In addition, these resins may be used singly or in combination of two or more kinds.
上述形成底塗層（B）之樹脂中，自能夠進一步提高絕緣層（A）上之導體電路層（CM2）之密接性之方面而言，較佳為藉由加熱而生成還原性化合物之樹脂。作為上述還原性化合物，例如可例舉：酚化合物、芳香族胺化合物、硫化合物、磷酸化合物、醛化合物等。該等還原性化合物中，較佳為酚化合物、醛化合物。Among the above-mentioned resins for forming the undercoat layer (B), resins that generate reducing compounds by heating are preferable in terms of further improving the adhesion of the conductive circuit layer (CM2) on the insulating layer (A) . As said reducing compound, a phenol compound, an aromatic amine compound, a sulfur compound, a phosphoric acid compound, an aldehyde compound, etc. are mentioned, for example. Among these reducing compounds, phenolic compounds and aldehyde compounds are preferred.
於將藉由加熱而生成還原性化合物之樹脂用於底塗劑之情形時，會於形成底塗層（B）時之加熱乾燥步驟中生成甲醛、苯酚等還原性化合物。作為藉由加熱而生成還原性化合物之樹脂之具體例，例如可例舉：使包含N-烷醇基（甲基）丙烯醯胺之單體聚合而成之樹脂、以胺酯樹脂作為殼且以使包含N-烷醇基（甲基）丙烯醯胺之單體聚合而成之樹脂作為核的核-殼型複合樹脂、脲-甲醛-甲醇縮合物、脲-三聚氰胺-甲醛-甲醇縮合物、聚N-烷氧基羥甲基（甲基）丙烯醯胺、聚（甲基）丙烯醯胺之甲醛加成物、三聚氰胺樹脂等藉由加熱而生成甲醛之樹脂；酚樹脂、苯酚封端異氰酸酯等藉由加熱而生成酚化合物之樹脂等。該等樹脂中，就提高密接性之觀點而言，較佳為以胺酯樹脂作為殼且以使包含N-烷醇基（甲基）丙烯醯胺之單體聚合而成之樹脂作為核的核-殼型複合樹脂、三聚氰胺樹脂、苯酚封端異氰酸酯。When a resin that generates a reducing compound by heating is used for the primer, reducing compounds such as formaldehyde and phenol are generated in the heating and drying step when forming the primer layer (B). Specific examples of resins that generate reducing compounds by heating include: resins obtained by polymerizing monomers containing N-alkanol (meth)acrylamide; urethane resins as shells; Core-shell composite resin, urea-formaldehyde-methanol condensate, urea-melamine-formaldehyde-methanol condensate , poly(N-alkoxymethylol)(meth)acrylamide, poly(meth)acrylamide formaldehyde adduct, melamine resin and other resins that generate formaldehyde by heating; phenol resin, phenol-capped Isocyanates, etc. are heated to produce resins such as phenolic compounds. Among these resins, from the viewpoint of improving adhesiveness, those having an urethane resin as a shell and a resin obtained by polymerizing a monomer containing N-alkanol group (meth)acrylamide as a core are preferable. Core-shell composite resin, melamine resin, phenol-blocked isocyanate.
再者，於本發明中，「（甲基）丙烯醯胺」意指「甲基丙烯醯胺」及「丙烯醯胺」之一者或兩者，「（甲基）丙烯酸」意指「甲基丙烯酸」及「丙烯酸」之一者或兩者。Furthermore, in the present invention, "(meth)acrylamide" means either or both of "methacrylamide" and "acrylamide", and "(meth)acrylic acid" means "methacrylamide". One or both of "acrylic acid" and "acrylic acid".
藉由加熱而生成還原性化合物之樹脂可藉由利用自由基聚合、陰離子聚合、陽離子聚合等聚合方法，使具有藉由加熱而生成還原性化合物之官能基之單體進行聚合而獲得。A resin that generates a reducing compound by heating can be obtained by polymerizing a monomer having a functional group that generates a reducing compound by heating by a polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization.
作為具有藉由加熱而生成還原性化合物之官能基之單體，例如可例舉N-烷醇基乙烯基單體，具體而言，可例舉：N-羥甲基（甲基）丙烯醯胺、N-甲氧基甲基（甲基）丙烯醯胺、N-乙氧基甲基（甲基）丙烯醯胺、N-丙氧基甲基（甲基）丙烯醯胺、N-異丙氧基甲基（甲基）丙烯醯胺、N-正丁氧基甲基（甲基）丙烯醯胺、N-異丁氧基甲基（甲基）丙烯醯胺、N-戊氧基甲基（甲基）丙烯醯胺、N-乙醇（甲基）丙烯醯胺、N-丙醇（甲基）丙烯醯胺等。As a monomer having a functional group that generates a reducing compound by heating, for example, an N-alkanol vinyl monomer, specifically, N-methylol (meth)acryl Amine, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-propoxymethyl(meth)acrylamide, N-iso Propoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isobutoxymethyl(meth)acrylamide, N-pentoxy Methyl(meth)acrylamide, N-ethanol(meth)acrylamide, N-propanol(meth)acrylamide, etc.
又，於製造上述藉由加熱而生成還原性化合物之樹脂時，亦可使（甲基）丙烯酸烷基酯等其他各種單體與具有藉由加熱而生成還原性化合物之官能基之單體等一起進行共聚。In addition, when producing the above-mentioned resin that generates a reducing compound by heating, other various monomers such as alkyl (meth)acrylates and monomers having a functional group that generates a reducing compound by heating can also be used. Copolymerize together.
於使用上述封端異氰酸酯作為形成上述底塗層（B）之樹脂之情形時，在異氰酸基間進行自反應而形成脲二酮鍵，或者異氰酸基與其他成分所具有之官能基形成鍵，藉此形成底塗層（B）。此時所形成之鍵可於塗布上述金屬粒子分散液前形成，亦可不於塗布上述金屬粒子分散液前形成，而於塗布上述金屬粒子分散液後藉由加熱而形成。When the above-mentioned blocked isocyanate is used as the resin forming the above-mentioned undercoat layer (B), self-reaction between isocyanate groups to form uretdione bonds, or isocyanate groups and functional groups of other components Bonds are formed, whereby the undercoat layer (B) is formed. The bonds formed at this time may be formed before coating the above-mentioned metal particle dispersion, or may not be formed before coating the above-mentioned metal particle dispersion, but may be formed by heating after coating the above-mentioned metal particle dispersion.
作為上述封端異氰酸酯，可例舉具有異氰酸基經封端劑封端而形成之官能基者。As said blocked isocyanate, what has the functional group which the isocyanate group blocked with the blocking agent is mentioned.
上述封端異氰酸酯較佳為封端異氰酸酯每1莫耳具有350～600 g/mol之範圍之上述官能基者。It is preferable that the said blocked isocyanate has the said functional group in the range of 350-600 g/mol per mol of blocked isocyanate.
就提高密接性之觀點而言，上述官能基較佳為在上述封端異氰酸酯之1分子中具有1～10個者，更佳為具有2～5個者。From a viewpoint of improving adhesiveness, it is preferable that the said functional group has 1-10 thing in 1 molecule of the said blocked isocyanate, and it is more preferable that it has 2-5 thing.
又，就提高密接性之觀點而言，上述封端異氰酸酯之數量平均分子量較佳為1,500～5,000之範圍，更佳為1,500～3,000之範圍。In addition, the number average molecular weight of the blocked isocyanate is preferably in the range of 1,500 to 5,000, more preferably in the range of 1,500 to 3,000, from the viewpoint of improving the adhesiveness.
進而，作為上述封端異氰酸酯，就進一步提高密接性之觀點而言，較佳為具有芳香環者。作為上述芳香環，可例舉苯基、萘基等。Furthermore, as said blocked isocyanate, it is preferable that it has an aromatic ring from a viewpoint of improving adhesiveness further. As said aromatic ring, a phenyl group, a naphthyl group, etc. are mentioned.
再者，上述封端異氰酸酯可藉由使異氰酸酯化合物所具有之異氰酸基之一部分或全部與封端劑進行反應而製造。In addition, the said blocked isocyanate can be manufactured by making some or all of the isocyanate groups which an isocyanate compound has react with a blocking agent.
作為成為上述封端異氰酸酯之原料之異氰酸酯化合物，例如可例舉：4,4’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、碳二亞胺改質二苯基甲烷二異氰酸酯、粗二苯基甲烷二異氰酸酯、伸苯基二異氰酸酯、甲伸苯基二異氰酸酯、萘二異氰酸酯等具有芳香環之聚異氰酸酯化合物；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛酮二異氰酸酯、二環己基甲烷二異氰酸酯、伸苯二甲基二異氰酸酯、四甲基伸苯二甲基二異氰酸酯等脂肪族聚異氰酸酯化合物或具有脂環式結構之聚異氰酸酯化合物等。又，亦可例舉上述聚異氰酸酯化合物之其等之縮二脲體、三聚異氰酸酯體、加成體等。Examples of isocyanate compounds used as raw materials for the above-mentioned blocked isocyanate include: 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenyl Methane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate and other polyisocyanate compounds with aromatic rings; hexamethylene diisocyanate, lysine diisocyanate, Aliphatic polyisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate or those with alicyclic structure polyisocyanate compounds, etc. Moreover, biuret body, isocyanurate body, adduct body, etc. of the said polyisocyanate compound etc. are also mentioned.
又，作為上述異氰酸酯化合物，亦可例舉使上文所例示之聚異氰酸酯化合物與具有羥基或胺基之化合物等進行反應而獲得者。Moreover, as said isocyanate compound, the thing obtained by making the polyisocyanate compound exemplified above and the compound etc. which have a hydroxyl group or an amino group react is also mentioned.
於向上述封端異氰酸酯中導入芳香環之情形時，較佳為使用具有芳香環之聚異氰酸酯化合物。又，具有芳香環之聚異氰酸酯化合物中，較佳為4,4’-二苯基甲烷二異氰酸酯、甲伸苯基二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯之三聚異氰酸酯體、甲伸苯基二異氰酸酯之三聚異氰酸酯體。When introducing an aromatic ring into the above-mentioned blocked isocyanate, it is preferable to use a polyisocyanate compound having an aromatic ring. Also, among the polyisocyanate compounds having an aromatic ring, 4,4'-diphenylmethane diisocyanate, cresylene diisocyanate, trimeric isocyanate of 4,4'-diphenylmethane diisocyanate, Trimeric isocyanate body of tolyl diisocyanate.
作為用於製造上述封端異氰酸酯之封端劑，例如可例舉：苯酚、甲酚等酚化合物；ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺等內醯胺化合物；甲醯胺肟、乙醛肟、丙酮肟、甲基乙基酮肟、甲基異丁基酮肟、環己酮肟等肟化合物；2-羥基吡啶、丁基賽珞蘇、丙二醇單甲醚、苄醇、甲醇、乙醇、正丁醇、異丁醇、丙二酸二甲酯、丙二酸二乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯丙酮、丁硫醇、十二硫醇、乙醯苯胺、乙醯胺（acetic acid amide）、琥珀醯亞胺、順丁烯二醯亞胺、咪唑、2-甲基咪唑、脲、硫脲、伸乙脲、二苯基苯胺、苯胺、咔唑、伸乙基亞胺、聚伸乙基亞胺、1H-吡唑、3-甲基吡唑、3,5-二甲基吡唑等。其中，較佳為藉由在70～200℃之範圍進行加熱而能夠解離並生成異氰酸基之封端劑，更佳為藉由在110～180℃之範圍進行加熱而能夠解離並生成異氰酸基之封端劑。具體而言，較佳為酚化合物、內醯胺化合物、肟化合物，尤佳為酚化合物，其原因在於：封端劑因加熱而發生脫離時會成為還原性化合物。Examples of the blocking agent used in the production of the above blocked isocyanate include: phenolic compounds such as phenol and cresol; lactams such as ε-caprolactamide, δ-valerolactamide, and γ-butyrolactam Compounds; oxime compounds such as formamide oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime; Methyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetylacetate, ethyl acetylacetate, acetylacetone, butylsulfide Alcohol, lauryl mercaptan, acetaniline, acetic acid amide, succinimide, maleimide, imidazole, 2-methylimidazole, urea, thiourea, ethylurea, Diphenylaniline, aniline, carbazole, ethylenimine, polyethylenimine, 1H-pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, etc. Among them, preferred is a blocking agent capable of dissociation and generation of isocyanate groups by heating in the range of 70 to 200°C, more preferably a blocking agent capable of dissociation and generation of isocyanate groups by heating in the range of 110 to 180°C. Blocking agent for cyanate groups. Specifically, phenolic compounds, lactam compounds, and oxime compounds are preferred, and phenolic compounds are particularly preferred because the capping agent becomes a reducing compound when detached by heating.
作為上述封端異氰酸酯之製造方法，例如可例舉：將預先製造之上述異氰酸酯化合物與上述封端劑進行混合並使其反應之方法；與用於製造上述異氰酸酯化合物之原料一起混合上述封端劑並使其反應之方法等。As a method for producing the above-mentioned blocked isocyanate, for example, a method of mixing and reacting the above-mentioned isocyanate compound and the above-mentioned blocking agent prepared in advance; mixing the above-mentioned blocking agent with the raw materials for producing the above-mentioned isocyanate compound And the method of making it react, etc.
更具體而言，上述封端異氰酸酯可藉由以下方式而製造：使上述聚異氰酸酯化合物與具有羥基或胺基之化合物反應，藉此製造末端具有異氰酸基之異氰酸酯化合物，繼而，將上述異氰酸酯化合物與上述封端劑進行混合並使其反應。More specifically, the above-mentioned blocked isocyanate can be produced by reacting the above-mentioned polyisocyanate compound with a compound having a hydroxyl group or an amino group to produce an isocyanate compound having an isocyanate group at the end, and then, the above-mentioned isocyanate The compound is mixed with the above capping agent and allowed to react.
藉由上述方法所獲得之封端異氰酸酯在形成上述底塗層（B）之樹脂中之含有比率較佳為50～100質量%之範圍，更佳為70～100質量%之範圍。The content rate of the blocked isocyanate obtained by the above method in the resin forming the undercoat layer (B) is preferably in the range of 50 to 100% by mass, more preferably in the range of 70 to 100% by mass.
作為上述三聚氰胺樹脂，例如可例舉：對三聚氰胺1莫耳加成1～6莫耳之甲醛而獲得之單或聚羥甲基三聚氰胺；三甲氧基羥甲基三聚氰胺、三丁氧基羥甲基三聚氰胺、六甲氧基羥甲基三聚氰胺等（聚）羥甲基三聚氰胺之醚化物（醚化度為任意）；脲-三聚氰胺-甲醛-甲醇縮合物等。Examples of the above-mentioned melamine resin include: mono- or polymethylol melamine obtained by adding 1 to 6 mol of formaldehyde to 1 mol of melamine; trimethoxymethylol melamine, tributoxymethylol melamine, Melamine, hexamethoxymethylolmelamine and other (poly)methylolmelamine ether compounds (the degree of etherification is optional); urea-melamine-formaldehyde-methanol condensates, etc.
又，除了如上所述使用藉由加熱而生成還原性化合物之樹脂之方法以外，亦可例舉向樹脂中添加還原性化合物之方法。於該情形時，作為所添加之還原性化合物，例如可例舉：酚系抗氧化劑、芳香族胺系抗氧化劑、硫系抗氧化劑、磷酸系抗氧化劑、維生素C、維生素E、乙二胺四乙酸鈉、亞硫酸鹽、次磷酸、次磷酸鹽、肼、甲醛、硼氫化鈉、二甲胺硼烷、苯酚等。Moreover, other than the method of using the resin which produces|generates a reducing compound by heating as mentioned above, the method of adding a reducing compound to resin is also mentioned. In this case, as the reducing compound to be added, for example, phenolic antioxidants, aromatic amine antioxidants, sulfur antioxidants, phosphoric acid antioxidants, vitamin C, vitamin E, ethylenediaminetetra Sodium acetate, sulfite, hypophosphorous acid, hypophosphite, hydrazine, formaldehyde, sodium borohydride, dimethylamine borane, phenol, etc.
本發明中，向樹脂中添加還原性化合物之方法可能因最終殘留低分子量成分或離子性化合物而導致電特性降低，因此更佳為使用藉由加熱而生成還原性化合物之樹脂之方法。In the present invention, the method of adding a reducing compound to the resin may lower the electrical characteristics due to residual low-molecular-weight components or ionic compounds. Therefore, it is more preferable to use a resin that generates a reducing compound by heating.
又，作為形成上述底塗層（B）之較佳之樹脂，可例舉含有具有胺基三
作為上述具有胺基三
關於上述具有胺基三
作為上述具有胺基三
上述胺基三
上述胺基三
作為上述酚結構，例如可例舉：苯酚殘基、甲酚殘基、丁基苯酚殘基、雙酚A殘基、苯基苯酚殘基、萘酚殘基、間苯二酚殘基等。又，此處之殘基意指鍵結於芳香環之碳之氫原子脫去至少1個而成之結構。例如若為苯酚，則意指羥苯基。As said phenolic structure, a phenol residue, a cresol residue, a butylphenol residue, a bisphenol A residue, a phenylphenol residue, a naphthol residue, a resorcinol residue, etc. are mentioned, for example. In addition, the residue here means a structure in which at least one hydrogen atom bonded to carbon of an aromatic ring is removed. For example, when it is phenol, it means a hydroxyphenyl group.
作為上述三
上述酚結構及上述三
又，自能夠進一步提高密接性之方面而言，上述胺基三
上述胺基三
又，於使用胺基三
作為上述環氧樹脂，可例舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、醇醚型環氧樹脂、四溴雙酚A型環氧樹脂、萘型環氧樹脂、具有源自9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物衍生物之結構之含磷環氧化合物、具有源自二環戊二烯衍生物之結構之環氧樹脂、環氧化大豆油等油脂之環氧化物等。該等環氧樹脂可使用一種，亦可併用兩種以上。Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, cresol novolac epoxy resin, phenol novolak epoxy resin, Bisphenol A novolak type epoxy resin, alcohol ether type epoxy resin, tetrabromobisphenol A type epoxy resin, naphthalene type epoxy resin, with 9,10-dihydro-9-oxa-10- Phosphorus-containing epoxy compounds with structures derived from phosphaphenanthrene-10-oxide derivatives, epoxy resins with structures derived from dicyclopentadiene derivatives, epoxides of epoxidized soybean oil and other oils, etc. These epoxy resins may be used alone or in combination of two or more.
上述環氧樹脂中，自能夠進一步提高密接性之方面而言，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、聯苯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂，尤佳為雙酚A型環氧樹脂。Among the above-mentioned epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and cresol novolak-type epoxy resins are preferable in terms of further improving the adhesiveness. Resin, phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin, especially bisphenol A type epoxy resin.
又，自能夠進一步提高密接性之方面而言，上述環氧樹脂之環氧當量較佳為100 g/當量以上300 g/當量以下，更佳為120 g/當量以上250 g/當量以下，進而較佳為150 g/當量以上200 g/當量以下。Also, from the viewpoint of further improving the adhesiveness, the epoxy equivalent of the above-mentioned epoxy resin is preferably from 100 g/equivalent to 300 g/equivalent, more preferably from 120 g/equivalent to 250 g/equivalent, and further Preferably, it is 150 g/equivalent or more and 200 g/equivalent or less.
於上述底塗層（B）為含有胺基三
於形成含有胺基三
進而，在用於形成上述含有胺基三
用於形成上述底塗層（B）之底塗劑就塗布性、成膜性之觀點而言，較佳為於底塗劑中含有1～70質量%之上述樹脂，更佳為含有1～20質量%。The primer used to form the primer layer (B) preferably contains 1 to 70% by mass of the above-mentioned resin in the primer from the viewpoint of coatability and film-forming properties, more preferably 1 to 20% by mass.
又，作為可用於上述底塗劑中之溶劑，可例舉各種有機溶劑、水性介質。作為上述有機溶劑，例如可例舉甲苯、乙酸乙酯、甲基乙基酮、環己酮等，作為上述水性介質，可例舉水、與水混合之有機溶劑、及其等之混合物。Moreover, various organic solvents and aqueous media are mentioned as a solvent which can be used for the said primer. Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, and cyclohexanone, and examples of the aqueous medium include water, an organic solvent mixed with water, and mixtures thereof.
作為上述與水混合之有機溶劑，例如可例舉：甲醇、乙醇、正丙醇、異丙醇、乙基卡必醇、乙基賽珞蘇、丁基賽珞蘇等醇溶劑；丙酮、甲基乙基酮等酮溶劑；乙二醇、二乙二醇、丙二醇等伸烷基二醇溶劑；聚乙二醇、聚丙二醇、聚四亞甲基二醇等聚伸烷基二醇溶劑；N-甲基-2-吡咯啶酮等內醯胺溶劑等。As the above-mentioned organic solvent mixed with water, for example, alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosulfur, and butyl cellosulfate; Ketone solvents such as ethyl ethyl ketone; alkylene glycol solvents such as ethylene glycol, diethylene glycol, and propylene glycol; polyalkylene glycol solvents such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; Lactamic solvents such as N-methyl-2-pyrrolidone, etc.
又，形成上述底塗層（B）之樹脂可視需要具有例如烷氧基矽基、矽醇基、羥基、胺基等有助於交聯反應之官能基。關於利用該等官能基而形成之交聯結構，可於後續步驟之形成銀粒子層（M1）之步驟前已形成交聯結構，又，亦可於形成銀粒子層（M1）之步驟後形成交聯結構。於形成銀粒子層（M1）之步驟後形成交聯結構時，可於形成上述導電電路層（CM1）前在上述底塗層（B）形成交聯結構，亦可於形成上述導電電路層（CM1）後例如藉由熟化而在上述底塗層（B）形成交聯結構。Moreover, the resin which forms the said primer layer (B) may have the functional group which contributes to a crosslinking reaction, such as an alkoxysilyl group, a silanol group, a hydroxyl group, an amino group, etc. as needed. Regarding the crosslinked structure formed by using these functional groups, the crosslinked structure may be formed before the step of forming the silver particle layer (M1) in the subsequent step, and may be formed after the step of forming the silver particle layer (M1) Cross-linked structure. When the cross-linked structure is formed after the step of forming the silver particle layer (M1), the cross-linked structure can be formed on the above-mentioned undercoat layer (B) before the formation of the above-mentioned conductive circuit layer (CM1), or it can be formed after the formation of the above-mentioned conductive circuit layer ( After CM1), a cross-linked structure is formed in the above-mentioned undercoat layer (B) by aging, for example.
於上述底塗層（B）中，亦可視需要適當地添加以交聯劑為代表之pH值調節劑、皮膜形成助劑、調平劑、增黏劑、撥水劑、消泡劑等公知者而使用。In the above primer layer (B), well-known pH adjusters represented by cross-linking agents, film forming aids, leveling agents, tackifiers, water repellents, defoamers, etc. may also be appropriately added as needed. who use it.
作為上述交聯劑，例如可例舉金屬螯合化合物、聚胺化合物、氮環丙烷化合物、金屬鹽化合物、異氰酸酯化合物等，可例舉在25～100℃左右之相對較低之溫度進行反應而形成交聯結構之熱交聯劑、三聚氰胺系化合物、環氧系化合物、
上述交聯劑之使用量根據種類而有所不同，但就提導電電路層（CM1）在基材上之密接性之觀點而言，相對於上述底塗劑中所含之樹脂之合計100質量份，較佳為0.01～60質量份之範圍，更佳為0.1～10質量份之範圍，進而較佳為0.1～5質量份之範圍。The amount of the above-mentioned crosslinking agent varies depending on the type, but from the viewpoint of improving the adhesion of the conductive circuit layer (CM1) to the base material, it is 100% by mass relative to the total resin contained in the above-mentioned primer. Parts, preferably in the range of 0.01 to 60 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, still more preferably in the range of 0.1 to 5 parts by mass.
於使用上述交聯劑之情形時，可於後續步驟之形成銀粒子層（M1）之步驟前已形成交聯結構，又，亦可於形成銀粒子層（M1）之步驟後形成交聯結構。於形成銀粒子層（M1）之步驟後形成交聯結構之情形時，可於形成上述導電電路層（CM1）前在上述底塗層（B）形成交聯結構，亦可於形成上述導電電路層（CM1）後例如藉由熟化而在上述底塗層（B）形成交聯結構。When the above-mentioned crosslinking agent is used, the crosslinked structure can be formed before the step of forming the silver particle layer (M1) in the subsequent step, and the crosslinked structure can also be formed after the step of forming the silver particle layer (M1) . When the cross-linked structure is formed after the step of forming the silver particle layer (M1), the cross-linked structure may be formed on the above-mentioned undercoat layer (B) before forming the above-mentioned conductive circuit layer (CM1), or may be formed after forming the above-mentioned conductive circuit. After the layer (CM1), for example, by aging, a crosslinked structure is formed in the above-mentioned undercoat layer (B).
於本發明中，在上述底塗層（B）上形成上述銀粒子層（M1）之方法與在絕緣層（A）上形成上述銀粒子層（M1）之方法相同。In this invention, the method of forming the said silver particle layer (M1) on the said primer layer (B) is the same as the method of forming the said silver particle layer (M1) on the insulating layer (A).
又，關於上述底塗層（B），與上述絕緣層（A）同樣地可在塗布銀粒子分散液前進行表面處理，以提高上述銀粒子分散液之塗布性，或提高導電電路層（CM1）對基材之密接性。Also, regarding the above-mentioned undercoat layer (B), similarly to the above-mentioned insulating layer (A), surface treatment can be carried out before coating the silver particle dispersion liquid, to improve the coatability of the above-mentioned silver particle dispersion liquid, or to improve the conductive circuit layer (CM1 ) Adhesion to the base material.
本發明之半加成工法用積層體係上述銀粒子層（M1）上積層有銅層（M2）者。The lamination system for the semi-additive process of the present invention is one in which the copper layer (M2) is laminated on the silver particle layer (M1).
上述銅層（M2）係藉由積層於上述銀粒子層（M1）上，而於下述印刷配線板之製造方法中之蝕刻步驟中保護導電性銀粒子層（M1）者，該蝕刻步驟用於將吸附於具有與內層印刷配線基材之導體電路層（CM2）連接之連接結構且形成於絕緣層（A）之孔之內壁表面以外之鈀、導電性聚合物、碳加以去除者。The above-mentioned copper layer (M2) is laminated on the above-mentioned silver particle layer (M1) to protect the conductive silver particle layer (M1) in the etching step in the manufacturing method of the printed wiring board described below. To remove palladium, conductive polymer, and carbon adsorbed on other than the inner wall surface of the hole of the insulating layer (A) having a connection structure connected to the conductor circuit layer (CM2) of the inner printed wiring substrate .
作為上述銅層（M2）之層厚，自於下述印刷配線板之製造方法中之對銅層（M2）進行蝕刻而使導電性銀粒子層（M1）露出之步驟中，不使銀粒子層（M1）受損而效率良好地使其露出之方面而言，上述銅層（M2）之層厚較佳為0.1 μm～2 μm，更佳為0.5 μm～1.5 μm。As the layer thickness of the above-mentioned copper layer (M2), in the step of etching the copper layer (M2) to expose the conductive silver particle layer (M1) in the following method of manufacturing a printed wiring board, no silver particles The thickness of the copper layer (M2) is preferably from 0.1 μm to 2 μm, more preferably from 0.5 μm to 1.5 μm, in order to efficiently expose the layer (M1) due to damage.
本發明之半加成工法用積層體中，作為在上述導電性銀粒子層（M1）上積層並形成上述銅層（M2）之方法，可藉由在上述導電性銀粒子層（M1）上進行乾式或濕式鍍銅法而形成。In the laminated body for the semi-additive process of the present invention, as a method of laminating the above-mentioned conductive silver particle layer (M1) to form the above-mentioned copper layer (M2), it is possible to form the above-mentioned conductive silver particle layer (M1) by Formed by dry or wet copper plating.
作為上述乾式鍍銅法，可例舉真空蒸鍍、離子鍍覆、濺鍍等方法。又，作為藉由濕式鍍銅法進行之處理，可列舉：以上述銀粒子層（M1）作為鍍覆觸媒之無電解鍍銅、或電鍍銅、無電解鍍銅與電鍍銅之組合。若使用電鍍，則可使鍍覆析出速度變大，因此製造效率變高，故具有優勢。As said dry copper plating method, methods, such as vacuum vapor deposition, ion plating, and sputtering, are mentioned. Moreover, as a process by the wet copper plating method, the electroless copper plating which used the said silver particle layer (M1) as a plating catalyst, or electroless copper plating, and the combination of electroless copper plating and electrolytic copper plating are mentioned. If electroplating is used, since the deposition rate of plating can be increased, the production efficiency can be increased, which is advantageous.
作為用於在上述銀粒子層（M1）上形成銅層（M2）之鍍銅法，並無特別限制，可藉由作為乾式鍍覆法之真空蒸鍍法、離子鍍覆法、濺鍍法來形成，亦可藉由作為濕式鍍覆法之無電解鍍銅法、電鍍銅法、無電解鍍銅與電鍍銅之組合來形成，又，亦可將乾式鍍覆法與濕式鍍覆法進行組合來形成。所有情形均可較佳地使用公知慣用之鍍銅法。The copper plating method for forming the copper layer (M2) on the above-mentioned silver particle layer (M1) is not particularly limited, and vacuum evaporation, ion plating, and sputtering can be used as dry plating methods. It can also be formed by the combination of electroless copper plating method, electrolytic copper plating method, electroless copper plating and electroplating copper plating method as wet plating method, and dry plating method and wet plating method can also be combined. The method is combined to form. In all cases, known and customary copper plating methods can preferably be used.
於上述絕緣層（A）形成於基材之兩平面，上述鍍銅較佳為於兩表面之銀粒子層（A）上形成相同厚度之銅層（M2）。When the insulating layer (A) is formed on both surfaces of the substrate, the copper plating is preferably to form a copper layer (M2) of the same thickness on the silver particle layer (A) on both surfaces.
於藉由上述鍍銅法來形成銅層（M2）之步驟中，可視需要對上述銀粒子層（M1）表面進行表面處理。作為該表面處理，在上述銀粒子層（M1）之表面或所形成之抗蝕劑圖案不受損之條件下，可例舉：利用酸性或鹼性清洗液進行之清洗處理、電暈處理、電漿處理、UV處理、氣相臭氧處理、液相臭氧處理、利用表面處理劑進行之處理等。該等表面處理可用一種方法進行，亦可併用兩種以上之方法。In the step of forming the copper layer (M2) by the above-mentioned copper plating method, the surface of the above-mentioned silver particle layer (M1) may be subjected to surface treatment as required. As the surface treatment, under the condition that the surface of the above-mentioned silver particle layer (M1) or the formed resist pattern is not damaged, cleaning treatment with an acidic or alkaline cleaning solution, corona treatment, Plasma treatment, UV treatment, gas-phase ozone treatment, liquid-phase ozone treatment, treatment with surface treatment agents, etc. Such surface treatment may be performed by one method, or two or more methods may be used in combination.
使用本發明之半加成工法用積層體的多層印刷配線板之製造方法之步驟1係以下步驟：於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上依序積層有絕緣層（A）、銀粒子層（M1）及銅層（M2）且上述銅層（M2）之層厚為0.1 μm～2 μm之半加成工法用積層體、或在絕緣層（A）與銀粒子層（M1）之間進而積層有底塗層（B）之半加成工法用積層體，形成自絕緣層（A）達至導體電路層（CM2）之孔。Step 1 of the manufacturing method of the multilayer printed wiring board using the semi-additive method of the present invention is the following steps: on the inner layer printed wiring substrate on which the conductive circuit layer (CM2) is formed on the insulating material. Insulating layer (A), silver particle layer (M1) and copper layer (M2) are laminated, and the layer thickness of the above copper layer (M2) is 0.1 μm to 2 μm. The laminated body for the semi-additive process, or on the insulating layer ( A) A semi-additional laminate with a primer layer (B) between the silver particle layer (M1) and a layered body to form holes from the insulating layer (A) to the conductor circuit layer (CM2).
於步驟1中，作為在半加成工法用積層體形成到達上述導體電路層（CM2）之孔之方法，只要適當地選擇公知慣用之方法即可，例如可例舉：鑽孔器加工、雷射加工、藉由雷射加工進行之銅層之開孔與使用氧化劑、鹼性藥劑、酸性藥劑等進行之絕緣層之藥劑蝕刻的組合加工法、使用抗蝕劑進行之銅箔之孔圖案蝕刻與使用氧化劑、鹼性藥劑、酸性藥劑等進行之絕緣層之藥劑蝕刻的組合加工法等方法。In step 1, as a method of forming a hole reaching the above-mentioned conductor circuit layer (CM2) with a laminate in a semi-additive process, it is sufficient to select a known and commonly used method, for example: drill processing, lightning Laser processing, combination processing method of opening copper layer by laser processing and chemical etching of insulating layer using oxidizing agent, alkaline chemical, acidic chemical, etc., etching hole pattern of copper foil using resist Methods such as combined processing with chemical etching of the insulating layer using oxidizing agents, alkaline chemicals, acidic chemicals, etc.
該等孔加工方法中，為了形成用以與內層印刷配線基材上所形成之導體電路層（CM2）進行連接之非貫通孔，較佳為藉由雷射加工進行之孔加工方法。又，本發明之多層印刷配線板不僅具有與內層印刷配線基材上所形成之導體電路層（CM2）進行電性連接之構造，同時亦可具有經由連接基材兩面之貫通孔而將兩面進行電性連接之構造。連接兩面之貫通孔可與用以與導體電路層（CM2）連接之非貫通孔之形成一併於上述步驟1中形成即可。 上述開孔加工中所形成之孔之孔徑（直徑）較佳為0.01～1 mm之範圍，更佳為0.02～0.5 mm之範圍，進而較佳為0.03～0.1 mm之範圍。 Among these hole processing methods, in order to form non-through holes for connecting with the conductor circuit layer (CM2) formed on the inner layer printed wiring base material, a hole processing method by laser processing is preferable. In addition, the multilayer printed wiring board of the present invention not only has a structure for electrically connecting with the conductor circuit layer (CM2) formed on the inner layer printed wiring substrate, but also has a through hole connecting both sides of the substrate. Structure for electrical connection. The through hole connecting both sides can be formed together with the formation of the non-through hole for connecting with the conductor circuit layer (CM2) in the above-mentioned step 1. The hole diameter (diameter) of the hole formed in the above-mentioned drilling process is preferably in the range of 0.01 to 1 mm, more preferably in the range of 0.02 to 0.5 mm, and still more preferably in the range of 0.03 to 0.1 mm.
開孔加工時所產生之有機物或無機物之污物（膠渣，smear）可能導致在下述兩面電性連接及形成導電電路層（CM1）之鍍覆步驟中產生鍍覆析出性不良、或鍍覆密接性降低，有損鍍覆外觀，因此較佳為去除污物（除膠渣）。作為除膠渣之方法，例如可例舉：電漿處理、反濺鍍處理等乾式處理、利用過錳酸鉀等氧化劑水溶液進行之清洗處理、利用鹼或酸之水溶液進行之清洗處理、利用有機溶劑進行之清洗處理等濕式處理等。The organic or inorganic dirt (smear) generated during the drilling process may cause poor plating precipitation or plating in the following two-sided electrical connection and formation of the conductive circuit layer (CM1) plating step Adhesiveness is reduced and plating appearance is impaired, so it is better to remove dirt (smear removal). As the method of desmearing, for example, dry treatment such as plasma treatment and reverse sputtering treatment, cleaning treatment using an aqueous solution of an oxidant such as potassium permanganate, cleaning treatment using an aqueous solution of alkali or acid, cleaning treatment using an organic Wet treatment such as cleaning treatment with solvent, etc.
使用本發明之半加成工法用積層體的印刷配線板之製造方法之步驟2係以下步驟：於具有下述孔之積層體之表面上賦予鈀、導電性聚合物、碳中之任一種，使孔表面導電化，該孔經由上述步驟1而形成於絕緣層（A）且與內層印刷配線基材之導體電路層（CM2）連接。Step 2 of the method of manufacturing a printed wiring board using a laminate for a semi-additive process of the present invention is the following step: any one of palladium, a conductive polymer, and carbon is applied to the surface of a laminate having the following holes, The surface of the hole is made conductive, and the hole is formed in the insulating layer (A) through the above step 1 and is connected to the conductor circuit layer (CM2) of the inner printed wiring substrate.
作為使上述貫通孔表面導電化之方法，例如可參考於豐永 實，電路技術，vol.8, No.1（1993）, pp.47-59中記載為『直接鍍覆法』之方法而進行。As a method for making the surface of the above-mentioned through hole conductive, for example, the method described as "direct plating method" in Toyonaga Mito, Circuit Technology, vol.8, No.1 (1993), pp.47-59 can be referred to. conduct.
作為使上述與導體電路層（CM2）連接之孔表面導電化之方法，只要使用上述文獻中所記載之（1）鈀-錫膠體系、（2）無錫鈀系、（3）導電性聚合物系、（4）石墨系之四種中之任一種即可。As a method of making the surface of the hole connected to the conductor circuit layer (CM2) conductive, only the (1) palladium-tin glue system, (2) tin-free palladium system, (3) conductive polymer described in the above literature can be used. (4) Any one of the four types of graphite system.
使用鈀-錫膠體使上述與導體電路層（CM2）連接之孔表面導電化之方法係藉由以下方式而實施：對形成有孔之上述積層體表面進行清潔調整劑（cleaner-conditioner）處理後，使錫-鈀膠體吸附於表面，進行加速劑處理（accelerator treatment）而去除錫。又，亦可使用將鈀進而轉換為硫化鈀而提高導電性之方法。The method of using palladium-tin colloid to make the surface of the hole connected to the conductor circuit layer (CM2) conductive is implemented in the following manner: after cleaning the surface of the above-mentioned laminate with the hole formed thereon (cleaner-conditioner) treatment , the tin-palladium colloid is adsorbed on the surface, and the accelerator treatment is performed to remove tin. In addition, a method of improving conductivity by further converting palladium into palladium sulfide can also be used.
又，作為利用導電性聚合物使上述與導體電路層（CM2）連接之孔表面導電化之方法，可使用使吡咯衍生物之單體進行氧化聚合之方法。對形成有貫通孔之上述積層體表面進行調整劑處理後，利用過錳酸鹽水溶液進行處理，在形成於上述絕緣層（A）之貫通孔之表面形成MnO 2。基板表面浸漬於溶化有高沸點醇之單體水溶液後，再浸漬於稀硫酸水溶液中時，在經MnO 2被覆之表面進行聚合化而形成導電性聚合物，藉此進行導電化。 Also, as a method of making the surface of the hole connected to the conductive circuit layer (CM2) conductive with a conductive polymer, a method of oxidatively polymerizing a monomer of a pyrrole derivative can be used. After the conditioner treatment was performed on the surface of the above-mentioned laminate with the through-holes formed, MnO 2 was formed on the surface of the through-holes formed in the above-mentioned insulating layer (A) by treating with a permanganate aqueous solution. After immersing the surface of the substrate in an aqueous monomer solution in which a high-boiling-point alcohol is dissolved, and then immersing it in a dilute sulfuric acid aqueous solution, the MnO2 -coated surface is polymerized to form a conductive polymer, thereby conducting electrical conduction.
進而，作為利用石墨使上述與導體電路層（CM2）連接之孔表面導電化之方法，可藉由以下方式而進行：將上述形成有與導體電路層（CM2）連接之孔之半加成製程工法用基材之表面利用經懸浮之碳黑溶液進行處理，使碳吸附於基板整面。藉由對形成有與導體電路層（CM2）連接之孔之上述積層體表面進行調整劑處理，而使基材表面帶正電後，使帶負電荷之碳黑吸附於表面，從而可確保導電性。Furthermore, as a method of using graphite to make the surface of the hole connected to the conductive circuit layer (CM2) conductive, it can be carried out by the following method: the semi-additive process of forming the hole connected to the conductive circuit layer (CM2) The surface of the substrate used in the construction method is treated with a suspended carbon black solution, so that carbon is adsorbed on the entire surface of the substrate. By treating the surface of the above-mentioned laminate with holes connected to the conductor circuit layer (CM2) with a regulator, the surface of the substrate is positively charged, and negatively charged carbon black is adsorbed on the surface to ensure electrical conductivity. sex.
作為使與導體電路層（CM2）連接之孔表面導電化之方法，亦可使用上述使用鈀、導電性聚合物、碳之方法中之任一種，可利用市售之公知慣用之製程。例如於錫-鈀製程時，可使用作為CRIMSON製程而為人所知之方法，於石墨系時，例如可利用作為黑孔製程而為人所知之製程。該等方法中，就材料及製程成本之觀點而言，較佳為使用：利用碳進行導電化之方法。As a method of making the surface of the hole connected to the conductor circuit layer (CM2) conductive, any one of the above-mentioned methods using palladium, conductive polymer, and carbon can be used, and a commercially available known conventional process can be used. For example, in the tin-palladium process, a method known as the CRIMSON process can be used, and in the case of graphite, a process known as the black hole process can be used, for example. Among these methods, from the viewpoint of material and process costs, it is preferable to use a method of conducting electrical conduction using carbon.
於本發明中，如上所述，同時具有將基材之兩面加以連接之貫通孔之情形時，亦可使用上述使用鈀、導電性聚合物、碳之方法來使貫通孔導電化。貫通孔之導電化可與上述與導體電路層（CM2）連接之孔表面之導電化同時進行。In the present invention, as described above, when there are through holes connecting both surfaces of the substrate, the through holes can also be made conductive by using the above-mentioned method using palladium, a conductive polymer, and carbon. The conduction of the through hole can be carried out simultaneously with the conduction of the surface of the hole connected to the conductor circuit layer (CM2).
使用本發明之半加成工法用積層體的印刷配線板之製造方法之步驟3係以下步驟：對上述銅層（M2）進行蝕刻，使導電性銀粒子層（M1）露出。本步驟係使用以於後續步驟形成導電電路層（CM1）之鍍覆晶種層即導電性銀粒子層（M1）露出之步驟，並且本步驟具有將步驟2中用於使與導體電路層（CM2）連接之孔導電化之鈀、導電性聚合物、碳自鍍覆晶種上去除之目的。
於步驟3中，關於用於對積層於導電性銀粒子層（M1）上之0.1 μm～2 μm厚之銅層（M2）進行蝕刻去除之藥劑，只要能效率良好地對銅層（M2）進行蝕刻，不使下層之銀粒子層（M1）受損，便無特別限制，可使用公知慣用之銅之微蝕刻液、軟蝕刻液。作為銅層（M2）之蝕刻液，可使用過硫酸銨、過硫酸鈉、過硫酸鉀等過硫酸鹽之水溶液、或硫酸/過氧化氫水溶液而進行。In
關於過硫酸鹽之水溶液、或硫酸/過氧化氫水溶液之濃度，只要根據用於製造印刷配線板之上述半加成工法用積層體之銅層（M2）之層厚、製造裝置之設計等進行適當選擇即可，於所使用之製程中，較佳為以銅層之蝕刻速度小於2 μm/分鐘之方式進行設定，就效率良好地去除銅層（M2）、及防止作為底層之導電性銀粒子層（M1）受損之觀點而言，更佳為以成為0.1 μm/分鐘～1.5 μm/分鐘之蝕刻速度之方式進行設定。The concentration of the aqueous solution of persulfate or aqueous sulfuric acid/hydrogen peroxide should be determined according to the layer thickness of the copper layer (M2) of the laminate for the above-mentioned semi-additive process used to manufacture printed wiring boards, the design of the manufacturing equipment, etc. Appropriate selection is enough. In the process used, it is better to set the etching rate of the copper layer to be less than 2 μm/min, so as to remove the copper layer (M2) efficiently and prevent the conductive silver as the bottom layer. From the viewpoint of damage to the particle layer ( M1 ), it is more preferable to set so as to have an etching rate of 0.1 μm/min to 1.5 μm/min.
經由使用本發明之半加成工法用積層體的印刷配線板之製造方法之步驟3對上述銅層（M2）進行蝕刻而得之積層體，其經過乾燥步驟後，可用作以銀粒子層（M1）作為導電晶種之半加成工法用積層體。即，藉由使用本發明之半加成工法用積層體的印刷配線板之製造方法之步驟3對上述銅層（M2）進行蝕刻而得之積層體為以下半加成工法用積層體，該半加成工法用積層體之特徵在於為以下基材：
於積層於內層印刷配線基材上之絕緣層（A）之表面上具有導電性銀粒子層（M1），該內層印刷配線基材係於絕緣性材料上形成有導體電路層（CM2）者，
上述基材進而於絕緣層（A）具有與導體電路層（CM2）連接之孔，且該孔之表面經鈀、導電性聚合物、碳中之任一種而確保了導電性。
The laminate obtained by etching the above-mentioned copper layer (M2) in
於使用本發明之半加成工法用積層體的印刷配線板之製造方法之步驟4中，在經上述步驟3去除了上層之上述銅層（M2）之銀粒子層（M1）上形成電路圖案之圖案抗蝕劑。
於形成步驟4之圖案抗蝕劑之步驟中，對於上述銀粒子層（M1）之表面，可在形成抗蝕劑前進行利用酸性或鹼性清洗液進行之清洗處理、電暈處理、電漿處理、UV處理、氣相臭氧處理、液相臭氧處理、利用表面處理劑進行之處理等表面處理，用以提高與抗蝕劑層之密接性。該等表面處理可用一種方法進行，亦可併用兩種以上之方法。
In
作為上述利用表面處理劑進行之處理，例如可使用下述方法：日本特開平7-258870號公報中所記載之使用由***系化合物、矽烷偶合劑及有機酸所構成之防銹劑進行處理之方法；日本特開2000-286546號公報中所記載之使用有機酸、苯并***系防銹劑及矽烷偶合劑進行處理之方法；日本特開2002-363189號公報中所記載之使用下述結構之物質進行處理之方法，該結構係***或噻二唑等含氮雜環與三甲氧基矽基或三乙氧基矽基等矽基經由具有硫醚（硫化物）鍵等之有機基進行鍵結而成者；WO2013/186941號公報中所記載之使用具有三
於使用本發明之半加成工法用積層體在表面形成金屬圖案時，對於感光性抗蝕劑，通過光罩或使用直接曝光機利用活性光對圖案進行曝光。曝光量只要視需要進行適當設定即可。使用顯影液去除經由曝光而形成於感光性抗蝕劑之潛像，藉此形成圖案抗蝕劑。When forming a metal pattern on the surface of a laminate using the semi-additive process of the present invention, the photosensitive resist is exposed to active light through a photomask or using a direct exposure machine. The exposure amount may be appropriately set as necessary. A pattern resist is formed by removing the latent image formed on the photosensitive resist by exposure using a developing solution.
作為上述顯影液，可例舉0.3～2質量%之碳酸鈉、碳酸鉀等稀鹼水溶液。於上述稀鹼水溶液中，可添加界面活性劑、消泡劑、或為了促進顯影添加少量之有機溶劑等。又，將上述經曝光之基材浸漬於顯影液中，或利用噴霧器等將顯影液噴霧至抗蝕劑上，藉此進行顯影，藉由該顯影，可形成圖案形成部已被去除之圖案抗蝕劑。As said developing solution, 0.3-2 mass % of dilute alkaline aqueous solutions, such as sodium carbonate and potassium carbonate, are mentioned. In the above dilute alkaline aqueous solution, surfactants, defoamers, or a small amount of organic solvents can be added to promote development. In addition, development is carried out by immersing the above-mentioned exposed base material in a developing solution, or by spraying the developing solution onto the resist with a sprayer, etc., and by this development, a pattern resist in which the pattern forming portion has been removed can be formed. etchant.
於形成圖案抗蝕劑時，可進而使用基於電漿之除渣處理、或市售之抗蝕劑殘渣去除劑，來去除在硬化抗蝕劑與基板之交界部分所產生之翻邊部分或殘存於基板表面之抗蝕劑附著物等抗蝕劑殘渣。When forming a pattern resist, you can further use plasma-based desmear treatment or a commercially available resist residue remover to remove the burring portion or residual at the interface between the hardened resist and the substrate. Resist residues such as resist deposits on the substrate surface.
作為本發明中所使用之感光性抗蝕劑，可使用市售之抗蝕劑油墨、液體抗蝕劑、乾膜抗蝕劑，只要根據目標圖案之解析度、所使用之曝光機之種類、後續步驟之鍍覆處理中所使用之藥液之種類、pH值等進行適當選擇即可。As the photosensitive resist used in the present invention, commercially available resist inks, liquid resists, and dry film resists can be used, as long as it depends on the resolution of the target pattern, the type of exposure machine used, The type and pH value of the chemical solution used in the plating treatment in the subsequent steps may be appropriately selected.
作為市售之抗蝕劑油墨，例如可例舉：太陽油墨股份有限公司製造之「鍍覆抗蝕劑MA-830」、「蝕刻抗蝕劑X-87」；NAZDAR公司之蝕刻抗蝕劑、鍍覆抗蝕劑；互應化學工業股份有限公司製造之「蝕刻抗蝕劑 PLAS FINE PER」系列、「鍍覆抗蝕劑 PLAS FINE PPR」系列等。又，作為電沉積抗蝕劑，例如可例舉Dow Chemical Company公司之「Eagle系列」、「Pepper系列」等。進而，作為市售之乾膜，例如可例舉：日立化成股份有限公司製造之「Photec」系列；Nikko-Materials股份有限公司製造之「ALPHO」系列；旭化成股份有限公司製造之「Sunfort」系列、杜邦公司製造之「Riston」系列等。Examples of commercially available resist inks include "plating resist MA-830" and "etching resist X-87" manufactured by Sun Ink Co., Ltd.; Plating Resist: "Etching Resist PLAS FINE PER" series, "Plating Resist PLAS FINE PPR" series, etc. manufactured by Huying Chemical Industry Co., Ltd. Moreover, as an electrodeposition resist, Dow Chemical Company's "Eagle series", "Pepper series", etc. are mentioned, for example. Furthermore, as a commercially available dry film, for example, "Photec" series manufactured by Hitachi Chemical Co., Ltd.; "ALPHO" series manufactured by Nikko-Materials Co., Ltd.; "Sunfort" series manufactured by Asahi Kasei Co., Ltd., "Riston" series manufactured by DuPont, etc.
為了效率良好地製造印刷配線板，使用乾膜抗蝕劑較為簡便，尤其於形成微細電路之情形時，只要使用半加成工法用乾膜即可。作為用於該目的之市售之乾膜，例如可使用：Nikko-Materials股份有限公司製造之「ALFO LDF500」、「NIT2700」、旭化成股份有限公司製造之「Sunfort UFG-258」、日立化成股份有限公司製造之「RD系列（RD-2015、1225）」、「RY系列（RY-5319、5325）」、杜邦公司製造之「PlateMaster系列（PM200、300）」等。In order to efficiently manufacture printed wiring boards, it is easier to use a dry film resist, especially when forming a fine circuit, it is only necessary to use a dry film for a semi-additive process. As a commercially available dry film for this purpose, for example, "ALFO LDF500" and "NIT2700" manufactured by Nikko-Materials Co., Ltd., "Sunfort UFG-258" manufactured by Asahi Kasei Co., Ltd., Hitachi Chemical Co., Ltd. "RD series (RD-2015, 1225)" and "RY series (RY-5319, 5325)" manufactured by the company, "PlateMaster series (PM200, 300)" manufactured by DuPont, etc.
於本發明之印刷配線板之製造方法之步驟5中，將上述導電性銀粒子層（M1）用作電鍍銅之陰極電極，於如上所述藉由顯影而露出之上述銀粒子層（M1）上進行基於電鍍銅法之處理，藉此可藉由鍍銅而將用以與導體電路層（CM2）連接之非貫通孔加以連接，同時可形成電路圖案導電電路層（CM1）。In
亦可於藉由上述電鍍銅法來形成導電電路層（CM1）前，視需要對上述銀粒子層（M1）表面進行表面處理。作為該表面處理，於上述銀粒子層（M1）之表面或所形成之抗蝕劑圖案不受損之條件下，可例舉：利用酸性或鹼性清洗液進行之清洗處理、電暈處理、電漿處理、UV處理、氣相臭氧處理、液相臭氧處理、利用表面處理劑進行之處理等。該等表面處理可用一種方法進行，亦可併用兩種以上之方法。Before forming the conductive circuit layer ( CM1 ) by the above-mentioned copper electroplating method, surface treatment may be performed on the surface of the above-mentioned silver particle layer ( M1 ) as needed. As the surface treatment, under the condition that the surface of the above-mentioned silver particle layer (M1) or the formed resist pattern is not damaged, cleaning treatment with an acidic or alkaline cleaning solution, corona treatment, Plasma treatment, UV treatment, gas-phase ozone treatment, liquid-phase ozone treatment, treatment with surface treatment agents, etc. Such surface treatment may be performed by one method, or two or more methods may be used in combination.
於使用本發明之半加成工法用積層體在絕緣層上形成電路圖案導電電路層（CM1）時，可於鍍覆後進行退火，以緩和鍍膜之應力或提高密接力。退火可於下述蝕刻步驟前進行，亦可於蝕刻步驟後進行，亦可於蝕刻前後進行。When the semi-additive method of the present invention is used to form the circuit pattern conductive circuit layer (CM1) on the insulating layer, it can be annealed after plating to ease the stress of the plating film or improve the adhesion. Annealing can be performed before the etching step described below, after the etching step, or before or after the etching step.
退火之溫度只要根據所使用之基材之耐熱性或使用目的，在40～300℃之溫度範圍進行適當選擇即可，但較佳為40～250℃之範圍，自抑制鍍膜之氧化劣化之目的考慮，更佳為40～200℃之範圍。又，於處於40～200℃之溫度範圍時，退火之時間較佳為10分鐘～10天，若在超過200℃之溫度進行退火，則較佳為5分鐘～10小時左右。又，對鍍膜進行退火時，亦可適當地對鍍膜表面賦予防銹劑。The annealing temperature can be properly selected in the temperature range of 40-300°C according to the heat resistance of the substrate used or the purpose of use, but it is preferably in the range of 40-250°C, from the purpose of inhibiting the oxidation degradation of the coating In consideration, the range of 40 to 200°C is more preferable. In addition, when the temperature ranges from 40 to 200°C, the annealing time is preferably 10 minutes to 10 days, and if the annealing is performed at a temperature exceeding 200°C, it is preferably about 5 minutes to 10 hours. In addition, when annealing the plated film, an antirust agent may be appropriately applied to the plated film surface.
於本發明之印刷配線板之製造方法之步驟6中，當於上述步驟5中藉由鍍覆而形成導電電路層（CM1）後，將使用上述感光性抗蝕劑所形成之圖案抗蝕劑剝離，利用蝕刻液去除非導電電路圖案形成部之銀粒子層（M1）。關於圖案抗蝕劑之剝離，只要在所使用之感光性抗蝕劑之目錄、說明書等中所記載之建議條件下進行即可。又，作為剝離圖案抗蝕劑時所使用之抗蝕劑剝離液，可使用市售之抗蝕劑剝離液、或設定為45～60℃之氫氧化鈉或氫氧化鉀之1.5～3質量%水溶液。抗蝕劑之剝離可藉由以下方式進行：將形成有上述電路圖案導電電路層（CM1）之基材浸漬於剝離液中；或利用噴霧器等噴霧剝離液。In
又，去除非導電電路圖案形成部之銀粒子層（M1）時所使用之蝕刻液較佳為僅對上述銀粒子層（M1）選擇性地進行蝕刻，不對形成上述導電電路層（CM1）之銅進行蝕刻者。作為此種蝕刻液，可例舉羧酸與過氧化氫之混合物。In addition, it is preferable that the etchant used for removing the silver particle layer (M1) of the non-conductive circuit pattern formation part selectively etches only the above-mentioned silver particle layer (M1) and does not etch the above-mentioned conductive circuit layer (CM1). Copper etcher. As such an etchant, a mixture of carboxylic acid and hydrogen peroxide may, for example, be mentioned.
作為上述羧酸，例如可例舉：乙酸、甲酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、棕櫚酸、珠光子酸、硬脂酸、油酸、亞麻油酸、次亞麻油酸、花生油酸、二十碳五烯酸、二十二碳六烯酸、草酸、丙二酸、琥珀酸、苯甲酸、水楊酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、沒食子酸、苯六甲酸、桂皮酸、丙酮酸、乳酸、蘋果酸、檸檬酸、富馬酸、馬來酸、烏頭酸、戊二酸、己二酸、胺基酸等。該等羧酸可使用一種，亦可併用兩種以上。該等羧酸中，自蝕刻液之製造、使用較為容易之方面考慮，較佳為主要使用乙酸。Examples of the above-mentioned carboxylic acids include acetic acid, formic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, and nacreic acid. , stearic acid, oleic acid, linolenic acid, sublinolenic acid, arachidic acid, eicosapentaenoic acid, docosahexaenoic acid, oxalic acid, malonic acid, succinic acid, benzoic acid, salicylic acid , phthalic acid, isophthalic acid, terephthalic acid, gallic acid, mellitic acid, cinnamic acid, pyruvic acid, lactic acid, malic acid, citric acid, fumaric acid, maleic acid, aconitic acid, Glutaric acid, adipic acid, amino acids, etc. These carboxylic acids may be used alone or in combination of two or more. Among these carboxylic acids, it is preferable to mainly use acetic acid in terms of ease of production and use of the etching solution.
認為若使用羧酸與過氧化氫之混合物作為蝕刻液，則過氧化氫與羧酸進行反應，藉此生成過氧羧酸（peroxycarboxylic acid）。推測所生成之過氧羧酸係抑制構成上述導電電路層（CM1）之銅之溶解，並同時優先溶解構成上述銀粒子層（M1）之銀者。It is considered that when a mixture of carboxylic acid and hydrogen peroxide is used as an etching solution, hydrogen peroxide and carboxylic acid react to generate peroxycarboxylic acid. It is speculated that the generated peroxycarboxylic acid suppresses the dissolution of copper constituting the above-mentioned conductive circuit layer (CM1), and at the same time preferentially dissolves the silver constituting the above-mentioned silver particle layer (M1).
作為上述羧酸與過氧化氫之混合物之混合比率，自能夠抑制銅導電電路層（CM1）之溶解之方面而言，相對於羧酸1莫耳，過氧化氫較佳為2～100莫耳之範圍，過氧化氫更佳為2～50莫耳之範圍。As the mixing ratio of the mixture of the above-mentioned carboxylic acid and hydrogen peroxide, hydrogen peroxide is preferably 2 to 100 moles relative to 1 mole of the carboxylic acid from the viewpoint of being able to suppress the dissolution of the copper conductive circuit layer (CM1). The range of hydrogen peroxide is more preferably in the range of 2 to 50 moles.
上述羧酸與過氧化氫之混合物較佳為經水稀釋所得之水溶液。又，關於上述水溶液中之上述羧酸與過氧化氫之混合物之含有比率，自能夠抑制蝕刻液之溫度上升之影響之方面而言，較佳為2～65質量%之範圍，更佳為2～30質量%之範圍。The above-mentioned mixture of carboxylic acid and hydrogen peroxide is preferably an aqueous solution diluted with water. Moreover, the content ratio of the mixture of the above-mentioned carboxylic acid and hydrogen peroxide in the above-mentioned aqueous solution is preferably in the range of 2 to 65% by mass, more preferably 2 ~30% by mass.
作為上述用於稀釋之水，較佳為使用離子交換水、純水、超純水等離子性物質或去除了雜質之水。As the water used for dilution, it is preferable to use ion-exchanged water, pure water, ultrapure water, or other ionic substances, or water from which impurities have been removed.
於上述蝕刻液中，可進而添加用於保護上述銅導電電路層（CM1）而抑制溶解之保護劑。作為保護劑，較佳為使用唑系化合物。A protective agent for protecting the above-mentioned copper conductive circuit layer (CM1) and suppressing dissolution may be further added to the above-mentioned etching solution. As a protective agent, it is preferable to use an azole compound.
作為上述唑系化合物，例如可例舉：咪唑、吡唑、***、四唑、
作為上述唑系化合物之具體例，例如可例舉：2-甲基苯并咪唑、胺基***、1,2,3-苯并***、4-胺基苯并***、1-雙胺基甲基苯并***、胺基四唑、苯基四唑、2-苯基噻唑、苯并噻唑等。該等唑系化合物可使用一種，亦可併用兩種以上。Specific examples of the aforementioned azole compounds include, for example, 2-methylbenzimidazole, aminotriazole, 1,2,3-benzotriazole, 4-aminobenzotriazole, 1-bis Aminomethylbenzotriazole, aminotetrazole, phenyltetrazole, 2-phenylthiazole, benzothiazole and the like. One of these azole-based compounds may be used alone, or two or more of them may be used in combination.
上述唑系化合物在蝕刻液中之濃度較佳為0.001～2質量%之範圍，更佳為0.01～0.2質量%之範圍。The concentration of the azole compound in the etching solution is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.01 to 0.2% by mass.
又，於上述蝕刻液中，自能夠抑制上述銅導電電路層（CM1）之溶解之方面而言，較佳為添加聚伸烷基二醇作為保護劑。Moreover, it is preferable to add polyalkylene glycol as a protective agent to the said etchant from the point which can suppress the dissolution of the said copper conductive circuit layer (CM1).
作為上述聚伸烷基二醇，例如可例舉聚乙二醇、聚丙二醇、聚氧乙烯聚氧丙烯嵌段共聚物等水溶性聚合物等。其中，較佳為聚乙二醇。又，作為聚伸烷基二醇之數量平均分子量，較佳為200～20,000之範圍。As said polyalkylene glycol, water-soluble polymers, such as polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene block copolymer, etc. are mentioned, for example. Among them, polyethylene glycol is preferred. In addition, the number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 20,000.
上述聚伸烷基二醇在蝕刻液中之濃度較佳為0.001～2質量%之範圍，更佳為0.01～1質量%之範圍。The concentration of the polyalkylene glycol in the etching solution is preferably in the range of 0.001 to 2% by mass, more preferably in the range of 0.01 to 1% by mass.
於上述蝕刻液中，可視需要摻合有機酸之鈉鹽、鉀鹽、銨鹽等添加劑，以抑制pH值之變動。Additives such as sodium salts, potassium salts, and ammonium salts of organic acids may be added to the above etching solution to suppress changes in pH.
於本發明之半加成工法用積層體中，非圖案形成部之銀粒子層（M1）之去除可藉由以下方式進行：於形成上述導電電路層（CM1）後，將使用上述感光性抗蝕劑所形成之圖案抗蝕劑剝離，將剝離後之基材浸漬於上述蝕刻液中；或者利用噴霧器等對上述基材上噴霧蝕刻液。In the laminated body for the semi-additive process of the present invention, the removal of the silver particle layer (M1) of the non-pattern formation part can be carried out in the following manner: after the above-mentioned conductive circuit layer (CM1) is formed, the above-mentioned photosensitive resist The pattern resist formed by the etchant is stripped, and the stripped substrate is immersed in the above-mentioned etching solution; or the etching solution is sprayed on the above-mentioned substrate with a sprayer or the like.
於使用蝕刻裝置來去除非圖案形成部之銀粒子層（M1）之情形時，例如可將上述蝕刻液之所有成分以成為特定組成之方式進行製備後供給至蝕刻裝置；亦可將上述蝕刻液之各成分分別供給至蝕刻裝置，於裝置內混合上述各成分，以成為特定組成之方式進行製備。When using an etching device to remove the silver particle layer (M1) of the non-pattern formation part, for example, all the components of the above etching solution may be prepared in a specific composition and then supplied to the etching device; Each component is supplied to an etching device, and the above-mentioned components are mixed in the device to prepare a specific composition.
上述蝕刻液較佳為於10～35℃之溫度範圍使用，尤其於使用含有過氧化氫之蝕刻液時，自能夠抑制過氧化氫之分解之方面而言，較佳為於30℃以下之溫度範圍使用。The above etching solution is preferably used at a temperature range of 10 to 35°C, especially when using an etching solution containing hydrogen peroxide, it is preferably at a temperature below 30°C from the aspect of being able to suppress the decomposition of hydrogen peroxide range of use.
利用上述蝕刻液對上述銀粒子層（M1）進行去除處理後，為了防止溶解於蝕刻液中之銀成分附著、殘留於印刷配線板上，亦可除水洗以外進而進行清洗操作。於清洗操作中，較佳為使用雖然會溶解氧化銀、硫化銀、氯化銀，但幾乎不溶解銀之清洗溶液。具體而言，較佳為使用含有硫代硫酸鹽或參(3-羥基烷基)膦之水溶液、或者含有巰基羧酸或其鹽之水溶液作為清洗藥液。After removing the silver particle layer (M1) with the etching solution, in order to prevent the silver component dissolved in the etching solution from adhering to and remaining on the printed wiring board, cleaning may be performed in addition to washing with water. In the cleaning operation, it is preferable to use a cleaning solution that dissolves silver oxide, silver sulfide, and silver chloride but hardly dissolves silver. Specifically, it is preferable to use an aqueous solution containing thiosulfate or ginseng(3-hydroxyalkyl)phosphine, or an aqueous solution containing mercaptocarboxylic acid or its salt as the cleaning solution.
作為上述硫代硫酸鹽，例如可例舉：硫代硫酸銨、硫代硫酸鈉、硫代硫酸鉀等。又，作為上述參(3-羥基烷基)膦，例如可例舉：參(3-羥基甲基)膦、參(3-羥基乙基)膦、參(3-羥基丙基)膦等。該等硫代硫酸鹽或參(3-羥基烷基)膦可分別使用一種，亦可併用兩種以上。As said thiosulfate, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate etc. are mentioned, for example. Moreover, as said para(3-hydroxyalkyl)phosphine, a para(3-hydroxymethyl)phosphine, a paraffin(3-hydroxyethyl)phosphine, a paraffin(3-hydroxypropyl)phosphine etc. are mentioned, for example. These thiosulfate or ginseng (3-hydroxyalkyl) phosphine may be used individually by 1 type, and may use 2 or more types together.
作為使用含有硫代硫酸鹽之水溶液時之濃度，只要根據步驟時間、所使用之清洗裝置之特性等進行適當設定即可，但較佳為0.1～40質量%之範圍，就清洗效率或連續使用時之藥液之穩定性之觀點而言，更佳為1～30質量%之範圍。As the concentration when using an aqueous solution containing thiosulfate, it only needs to be appropriately set according to the step time and the characteristics of the cleaning device used, but it is preferably in the range of 0.1 to 40% by mass. In terms of cleaning efficiency or continuous use From the viewpoint of the stability of the chemical solution at the time, it is more preferably in the range of 1 to 30% by mass.
又，作為使用含有上述參(3-羥基烷基)膦之水溶液時之濃度，只要根據步驟時間、所使用之清洗裝置之特性等進行適當設定即可，但較佳為0.1～50質量%之範圍，就清洗效率或連續使用時之藥液之穩定性之觀點而言，更佳為1～40質量%之範圍。Also, as the concentration when using the aqueous solution containing the above-mentioned ginseng(3-hydroxyalkyl)phosphine, it may be appropriately set according to the step time, the characteristics of the cleaning device used, etc., but it is preferably 0.1 to 50% by mass. The range is more preferably in the range of 1 to 40% by mass from the viewpoint of cleaning efficiency and stability of the chemical solution during continuous use.
作為上述巰基羧酸，例如可例舉：硫代乙醇酸、2-巰基丙酸、3-巰基丙酸、硫代蘋果酸、半胱胺酸、N-乙醯基半胱胺酸等。又，作為上述巰基羧酸之鹽，例如可例舉：鹼金屬鹽、銨鹽、胺鹽等。As said mercapto carboxylic acid, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, cysteine, N-acetylcysteine etc. are mentioned, for example. Moreover, as a salt of the said mercaptocarboxylic acid, an alkali metal salt, an ammonium salt, an amine salt, etc. are mentioned, for example.
作為使用巰基羧酸或其鹽之水溶液時之濃度，較佳為0.1～20質量%之範圍，就清洗效率或進行大量處理時之製程成本之觀點而言，更佳為0.5～15質量%之範圍。The concentration when using an aqueous solution of mercaptocarboxylic acid or its salt is preferably in the range of 0.1 to 20% by mass, and more preferably in the range of 0.5 to 15% by mass from the viewpoint of cleaning efficiency or process cost when a large amount of treatment is performed. scope.
作為進行上述清洗操作之方法，例如可例舉：將對上述非圖案形成部之銀粒子層（M1）進行蝕刻去除後所得之印刷配線板浸漬於上述清洗藥液中之方法、利用噴霧器等將清洗藥液噴霧至上述印刷配線板之方法等。關於清洗藥液之溫度，可於室溫（25℃）使用，但自能夠在不受室外氣溫影響之情況下穩定地進行清洗處理之方面而言，例如亦可將溫度設定為30℃而使用。As a method of performing the above-mentioned cleaning operation, for example, a method of immersing the printed wiring board obtained by etching and removing the silver particle layer (M1) of the above-mentioned non-pattern formation part in the above-mentioned cleaning chemical solution, using a sprayer, etc. to spray A method of spraying the cleaning solution onto the above-mentioned printed wiring board, etc. Regarding the temperature of the cleaning solution, it can be used at room temperature (25°C), but it can also be used at a temperature of 30°C, for example, in order to allow stable cleaning without being affected by the outdoor air temperature. .
又，利用蝕刻液去除上述非圖案形成部之銀粒子層（M1）之步驟與清洗操作可視需要反覆進行。Moreover, the process of removing the silver particle layer (M1) of the said non-pattern formation part by etchant, and a cleaning operation may be repeated as needed.
本發明之印刷配線板如上所述，於利用上述蝕刻液對非圖案形成部之銀粒子層（M1）進行去除處理後，可為了進一步提高非圖案形成部之絕緣性，而視需要進而進行清洗操作。於該清洗操作中，例如可使用將過錳酸鉀或過錳酸鈉溶解於氫氧化鉀或氫氧化鈉之水溶液中而獲得之鹼性過錳酸溶液。In the printed wiring board of the present invention, as described above, after removing the silver particle layer (M1) of the non-pattern forming part with the above-mentioned etchant, it may be further cleaned if necessary in order to further improve the insulation of the non-pattern forming part. operate. In this cleaning operation, for example, an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of potassium hydroxide or sodium hydroxide can be used.
關於使用上述鹼性過錳酸溶液之清洗，可例舉：向設定為20～60℃之鹼性過錳酸溶液中浸漬藉由上述方法所獲得之印刷配線板之方法、利用噴霧器等將鹼性過錳酸溶液噴霧至上述印刷配線板之方法等。上述印刷配線板可在清洗前進行使其與具有醇性羥基之水溶性有機溶劑接觸之處理，以使鹼性過錳酸溶液對基材表面之潤濕性變得良好，提高清洗效率。作為上述有機溶劑，可例舉：甲醇、乙醇、正丙醇、異丙醇等。該等有機溶劑可使用一種，亦可併用兩種以上。For cleaning using the above-mentioned alkaline permanganic acid solution, for example, a method of immersing the printed wiring board obtained by the above method in an alkaline permanganic acid solution set at 20 to 60°C, spraying the alkali with a sprayer, etc. The method of spraying permanganic acid solution to the above-mentioned printed wiring board, etc. The above-mentioned printed wiring board can be treated with a water-soluble organic solvent having an alcoholic hydroxyl group before cleaning, so that the wettability of the alkaline permanganic acid solution to the surface of the substrate becomes good, and the cleaning efficiency is improved. As said organic solvent, methanol, ethanol, n-propanol, isopropanol, etc. are mentioned. These organic solvents may be used alone or in combination of two or more.
上述鹼性過錳酸溶液之濃度只要視需要適當選擇即可，但較佳為向0.1～10質量%之氫氧化鉀或氫氧化鈉水溶液100質量份中溶解0.1～10質量份之過錳酸鉀或過錳酸鈉而獲得者，就清洗效率之觀點而言，更佳為向1～6質量%之氫氧化鉀或氫氧化鈉水溶液100質量份中溶解1～6質量份之過錳酸鉀或過錳酸鈉而獲得者。The concentration of the above-mentioned alkaline permanganic acid solution can be appropriately selected as needed, but it is preferable to dissolve 0.1 to 10 parts by mass of permanganic acid in 100 parts by mass of potassium hydroxide or sodium hydroxide aqueous solution of 0.1 to 10 mass % Potassium or sodium permanganate, from the viewpoint of cleaning efficiency, it is more preferable to dissolve 1 to 6 parts by mass of permanganate in 100 parts by mass of potassium hydroxide or sodium hydroxide aqueous solution of 1 to 6 mass % Those obtained from potassium or sodium permanganate.
於進行上述使用鹼性過錳酸溶液之清洗時，較佳為於鹼性過錳酸溶液之清洗後，使用具有中和、還原作用之液體對已清洗之上述印刷配線板進行處理。作為上述具有中和、還原作用之液體，例如可例舉0.5～15質量%之稀硫酸、或包含有機酸之水溶液。又，作為上述有機酸，例如可例舉：甲酸、乙酸、草酸、檸檬酸、抗壞血酸、甲硫胺酸等。When performing the cleaning with the alkaline permanganic acid solution, it is preferable to use a neutralizing and reducing liquid to treat the cleaned printed wiring board after the alkaline permanganic acid solution is cleaned. As the above-mentioned liquid having neutralization and reduction functions, for example, 0.5 to 15% by mass of dilute sulfuric acid or an aqueous solution containing an organic acid may be mentioned. Moreover, as said organic acid, formic acid, acetic acid, oxalic acid, citric acid, ascorbic acid, methionine etc. are mentioned, for example.
上述使用鹼性過錳酸溶液之清洗可於為了防止溶解於上述蝕刻液中之銀成分附著、殘留於印刷配線板上而進行之清洗後進行，亦可僅進行使用鹼性過錳酸溶液之清洗來代替為了防止溶解於上述蝕刻液中之銀成分附著、殘留於印刷配線板上而進行之清洗。The above-mentioned cleaning using alkaline permanganic acid solution may be performed after cleaning to prevent the silver components dissolved in the above-mentioned etching solution from adhering to and remaining on the printed wiring board, or only using alkaline permanganic acid solution may be performed. Cleaning is performed instead of cleaning to prevent the silver component dissolved in the above etching solution from adhering to and remaining on the printed wiring board.
又，對於使用本發明之印刷配線板用積層體所獲得之印刷配線板，可適當地視需要實施鎳/金鍍覆、鎳/鈀/金鍍覆、鈀/金鍍覆作為在電路圖案上積層覆蓋膜、形成阻焊層、及電路圖案之最終表面處理之手段。Also, for a printed wiring board obtained by using the laminate for a printed wiring board of the present invention, nickel/gold plating, nickel/palladium/gold plating, and palladium/gold plating can be appropriately performed as required on the circuit pattern. The final surface treatment means of laminating cover film, forming solder resist layer, and circuit pattern.
藉由以上所述之本發明之半加成工法用積層體，可不使用真空裝置，而製造於各種平滑基材上之密接性較高、設計再現性良好，且具有良好之矩形截面形狀之表面平滑的電路圖案之經兩面連接之多層印刷基配線板。因此，藉由使用本發明之半加成工法用積層體，能夠以低成本良好地提供各種形狀、高密度尺寸、高性能之印刷配線板用基板、印刷配線板，於印刷配線板領域中之產業上具有高利用性。又，藉由使用積層體，不僅可製造印刷配線板，亦可製造於平面狀基材表面具有經圖案化之金屬層之各種構件、例如連接器、電磁波屏蔽、RFID等天線、膜電容器等。 [實施例] By virtue of the laminated body for the semi-additive process of the present invention described above, it can be manufactured on various smooth substrates without using a vacuum device, with high adhesion, good design reproducibility, and a surface with a good rectangular cross-sectional shape Multilayer printed wiring board with smooth circuit pattern connected on both sides. Therefore, by using the laminate for the semi-additive process of the present invention, it is possible to provide substrates for printed wiring boards of various shapes, high-density dimensions, and high performance at low cost, and printed wiring boards, which are used in the field of printed wiring boards. It has high applicability in industry. In addition, by using a laminate, not only printed wiring boards but also various components having a patterned metal layer on the surface of a planar substrate, such as connectors, electromagnetic wave shields, antennas such as RFID, and film capacitors, can be manufactured. [Example]
以下，使用實施例及比較例來更詳細地說明本發明。於以下之實施例及比較例中，「份」及「%」均為質量基準。Hereinafter, the present invention will be described in more detail using examples and comparative examples. In the following examples and comparative examples, "parts" and "%" are based on mass.
[製造例1：底塗劑（B-1）之製造] 於具備溫度計、氮導入管、攪拌器之經氮置換之容器中，使聚酯多元醇（使1,4-環己烷二甲醇、新戊二醇及己二酸進行反應而獲得之聚酯多元醇）100質量份、2,2-二羥甲基丙酸17.6質量份、1,4-環己烷二甲醇21.7質量份及二環己基甲烷-4,4’-二異氰酸酯106.2質量份在甲基乙基酮178質量份之混合溶劑中進行反應，藉此獲得末端具有異氰酸基之胺酯預聚物溶液。 [Manufacturing example 1: Manufacture of primer (B-1)] Polyester polyol (polyester obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol and adipic acid) Polyol) 100 parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol and 106.2 parts by mass of dicyclohexylmethane-4,4'-diisocyanate in The reaction was carried out in a mixed solvent of 178 parts by mass of methyl ethyl ketone, thereby obtaining a solution of an urethane prepolymer having an isocyanate group at the end.
繼而，向上述胺酯預聚物溶液中加入三乙胺13.3質量份，中和上述胺酯預聚物所具有之羧基，進而加入水380質量份並充分地攪拌，藉此獲得胺酯預聚物之水性分散液。Next, 13.3 parts by mass of triethylamine was added to the above-mentioned urethane prepolymer solution to neutralize the carboxyl groups of the above-mentioned urethane prepolymer, and then 380 parts by mass of water was added and fully stirred to obtain the urethane prepolymer solution. Aqueous dispersion of substances.
向上述所獲得之胺酯預聚物之水性分散液中加入25質量%乙二胺水溶液8.8質量份並進行攪拌，藉此使胺酯預聚物鏈伸長。進而進行熟化、脫溶劑，藉此獲得胺酯樹脂之水性分散液（不揮發分30質量%）。上述胺酯樹脂之重量平均分子量為53,000。To the aqueous dispersion of the urethane prepolymer obtained above, 8.8 parts by mass of a 25% by mass aqueous solution of ethylenediamine was added and stirred to extend the chain of the urethane prepolymer. Furthermore, aging and solvent removal were performed to obtain an aqueous dispersion of urethane resin (30% by mass of non-volatile matter). The weight average molecular weight of the above-mentioned urethane resin is 53,000.
繼而，向具備攪拌機、回流冷凝管、氮導入管、溫度計、單體混合物滴加用滴液漏斗、聚合觸媒滴加用滴液漏斗之反應容器中加入去離子水140質量份、上述所獲得之胺酯樹脂之水分散液100質量份，吹入氮並同時升溫至80℃。其後，進行攪拌，並同時在將反應容器內溫度保持在80℃之狀態下，自分開之滴液漏斗歷時120分鐘滴加由甲基丙烯酸甲酯60質量份、丙烯酸正丁酯30質量份及N-正丁氧基甲基丙烯醯胺10質量份所構成之單體混合物、以及0.5質量%過硫酸銨水溶液20質量份。Then, add 140 parts by mass of deionized water, the above obtained 100 parts by mass of the aqueous dispersion of the urethane resin was blown in nitrogen while simultaneously raising the temperature to 80°C. Thereafter, while stirring, 60 parts by mass of methyl methacrylate and 30 parts by mass of n-butyl acrylate were added dropwise from a separate dropping funnel over 120 minutes while keeping the temperature in the reaction vessel at 80°C. and a monomer mixture composed of 10 parts by mass of N-n-butoxymethacrylamide, and 20 parts by mass of a 0.5 mass % ammonium persulfate aqueous solution.
滴加結束後，在當前溫度進而攪拌60分鐘，其後，將反應容器內之溫度冷卻至40℃，以不揮發分成為20質量%之方式利用去離子水進行稀釋後，利用200目濾布進行過濾，藉此獲得以上述胺酯樹脂作為殼層且以將甲基丙烯酸甲酯等作為原料之丙烯酸樹脂作為核層之核-殼型複合樹脂即底塗層用樹脂組成物之水分散液。繼而，以異丙醇與水之質量比率成為7/3且不揮發分成為2質量%之方式，向該水分散液中加入異丙醇及去離子水並進行混合，從而獲得底塗劑（B-1）。After the dropwise addition, stir at the current temperature for 60 minutes, then cool the temperature in the reaction vessel to 40°C, dilute with deionized water so that the non-volatile matter becomes 20% by mass, and then use a 200-mesh filter cloth Filtration is performed to obtain an aqueous dispersion of a core-shell type composite resin, which is a resin composition for an undercoat layer, in which the above-mentioned urethane resin is used as a shell layer and an acrylic resin made of methyl methacrylate or the like is used as a core layer. . Then, in the mode that the mass ratio of isopropanol and water becomes 7/3 and the non-volatile matter becomes 2% by mass, isopropanol and deionized water are added to the aqueous dispersion and mixed to obtain a primer ( B-1).
[製造例2：底塗劑（B-2）之製造] 向具備回流冷卻器、溫度計、攪拌機之反應燒瓶中加入包含37質量%甲醛及7質量%甲醇之福馬林600質量份、以及水200質量份及甲醇350質量份。繼而，向該水溶液中加入25質量%氫氧化鈉水溶液，並調節至pH10後，加入三聚氰胺310質量份，將液溫升溫至85℃，進行1小時之羥甲基化反應。 [Manufacturing example 2: Manufacture of primer (B-2)] 600 parts by mass of formalin containing 37% by mass of formaldehyde and 7% by mass of methanol, 200 parts by mass of water, and 350 parts by mass of methanol were added to a reaction flask equipped with a reflux cooler, a thermometer, and a stirrer. Then, 25 mass % sodium hydroxide aqueous solution was added to this aqueous solution, and after adjusting to pH 10, 310 mass parts of melamines were added, and liquid temperature was raised to 85 degreeC, and the methylolation reaction was performed for 1 hour.
其後，加入甲酸並調節至pH7後，冷卻至60℃，使其進行醚化反應（二級反應）。於白濁溫度40℃加入25質量%氫氧化鈉水溶液並調節至pH9，停止醚化反應（反應時間：1小時）。於溫度50℃之減壓下去除殘存之甲醇（脫甲醇時間：4小時），而獲得不揮發分80質量%之包含三聚氰胺樹脂之底塗劑用樹脂組成物。繼而，向該樹脂組成物中加入甲基乙基酮進行稀釋混合，藉此獲得不揮發分2質量%之底塗劑（B-2）。Then, after adding formic acid and adjusting to
[製造例3：底塗劑（B-3）之製造] 向具備溫度計、氮導入管、攪拌器且經氮置換之反應容器中，加入2,2-二羥甲基丙酸9.2質量份、聚亞甲基聚苯基聚異氰酸酯（Tosoh股份有限公司製造之「Millionate MR-200」）57.4質量份及甲基乙基酮233質量份，於70℃使之反應6小時而獲得異氰酸酯化合物。繼而，向反應容器內供給苯酚26.4質量份作為封端劑，於70℃使之反應6小時。其後，冷卻至40℃而獲得封端異氰酸酯之溶液。 [Manufacturing example 3: Manufacture of primer (B-3)] Add 9.2 parts by mass of 2,2-dimethylolpropionic acid, polymethylene polyphenyl polyisocyanate (manufactured by Tosoh Co., Ltd. "Millionate MR-200") 57.4 parts by mass and 233 parts by mass of methyl ethyl ketone were reacted at 70° C. for 6 hours to obtain an isocyanate compound. Next, 26.4 parts by mass of phenol was supplied as a terminal blocking agent into the reaction container, and it was made to react at 70 degreeC for 6 hours. Thereafter, it was cooled to 40° C. to obtain a solution of blocked isocyanate.
繼而，向上述所獲得之封端異氰酸酯之溶液中，於40℃加入三乙胺7質量份，中和上述封端異氰酸酯所具有之羧基，加入水並充分地攪拌後，蒸餾去除甲基乙基酮而獲得不揮發分20質量%之含有封端異氰酸酯及水之底塗層用樹脂組成物。繼而，向該樹脂組成物中加入甲基乙基酮進行稀釋混合，藉此獲得不揮發分2質量%之底塗劑（B-3）。Next, 7 parts by mass of triethylamine was added to the solution of the above-obtained blocked isocyanate at 40°C to neutralize the carboxyl groups of the above-mentioned blocked isocyanate, and after adding water and stirring thoroughly, the methyl ethyl group was distilled off. A resin composition for an undercoat layer containing blocked isocyanate and water with 20% by mass of non-volatile matter obtained from ketone. Next, methyl ethyl ketone was added to this resin composition, and it diluted and mixed, and the primer (B-3) of 2 mass % of non-volatile matter was obtained.
[製造例4：底塗劑（B-4）之製造]
將酚醛清漆樹脂（DIC股份有限公司製造之「PHENOLITE TD-2131」，羥基當量104 g/當量）35質量份、環氧樹脂（DIC股份有限公司製造之「EPICLON 850-S」；雙酚A型環氧樹脂，環氧基當量188 g/當量）64質量份、及2,4-二胺基-6-乙烯基對稱三
[製造例5：底塗劑（B-5）之製造]
將酚醛清漆樹脂（DIC股份有限公司製造之「PHENOLITE TD-2131」，羥基當量104 g/當量）35質量份、環氧樹脂（DIC股份有限公司製造之「EPICLON 850-S」；雙酚A型環氧樹脂，環氧基當量188 g/當量）64質量份、及具有三
[製造例6：底塗劑（B-6）之製造]
向安裝有溫度計、冷凝管、分餾柱、攪拌器之燒瓶中加入苯酚750質量份、三聚氰胺75質量份、41.5質量%福馬林346質量份、及三乙胺1.5質量份，在注意放熱之同時升溫至100℃。在回流下以100℃使之反應2小時後，於常壓下去除水並同時歷時2小時升溫至180℃。繼而，於減壓下去除未反應之苯酚而獲得胺基三
[製造例7：底塗劑（B-7）之製造]
將製造例6中所獲得之胺基三
[製造例8：底塗劑（B-8）之製造]
將胺基三
[製造例9：底塗劑（B-9）之製造]
將胺基三
[製造例10：底塗劑（B-10）之製造]
將製造例7中所獲得之胺基三
[製造例11：底塗劑（B-11）之製造] 向具備攪拌機、回流冷凝管、氮導入管、溫度計、滴液漏斗之反應容器中加入去離子水350質量份、界面活性劑（花王股份有限公司製造之「Latemul E-118B」：有效成分25質量%）4質量份，吹入氮並同時升溫至70℃。 [Manufacture Example 11: Manufacture of Primer (B-11)] Add 350 parts by mass of deionized water and a surfactant ("Latemul E-118B" manufactured by Kao Co., Ltd.: 25 parts by mass of active ingredient %) 4 parts by mass, nitrogen was blown in while raising the temperature to 70°C.
於攪拌下向反應容器中添加以下所獲得之單體預乳液之一部分（5質量份），該單體預乳液係將由甲基丙烯酸甲酯47.0質量份、甲基丙烯酸環氧丙酯5.0質量份、丙烯酸正丁酯45.0質量份、甲基丙烯酸3.0質量份所構成之乙烯基單體混合物、界面活性劑（第一工業製藥股份有限公司製造之「Aqualon KH-1025」：有效成分25質量%）4質量份、及去離子水15質量份進行混合而獲得者，繼而添加過硫酸鉀0.1質量份，在將反應容器內溫度保持在70℃之狀態下使之聚合60分鐘。Add a part (5 parts by mass) of the following monomer pre-emulsion to the reaction vessel under stirring. The monomer pre-emulsion will be composed of 47.0 parts by mass of methyl methacrylate and 5.0 parts by mass of glycidyl methacrylate , a vinyl monomer mixture composed of 45.0 parts by mass of n-butyl acrylate and 3.0 parts by mass of methacrylic acid, and a surfactant ("Aqualon KH-1025" manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: active ingredient 25% by mass) What was obtained by mixing 4 parts by mass and 15 parts by mass of deionized water was then added with 0.1 part by mass of potassium persulfate, and polymerized for 60 minutes while keeping the temperature in the reaction vessel at 70°C.
繼而，在將反應容器內之溫度保持在70℃之狀態下，將剩餘之單體預乳液（114質量份）、及過硫酸鉀之水溶液（有效成分1.0質量%）30質量份分別使用不同之滴液漏斗歷時180分鐘進行滴加。滴加結束後，在當前溫度攪拌60分鐘。Then, with the temperature in the reaction container kept at 70°C, 30 parts by mass of the remaining monomer pre-emulsion (114 parts by mass) and an aqueous solution of potassium persulfate (1.0 mass % of active ingredient) were used in different The dropping funnel was added dropwise over 180 minutes. After the dropwise addition was completed, it was stirred at the current temperature for 60 minutes.
將上述反應容器內之溫度冷卻至40℃，繼而以不揮發分成為10.0質量%之方式使用去離子水後，利用200目濾布進行過濾，藉此獲得本發明中所使用之底塗層用樹脂組成物。繼而，向該樹脂組成物中加入水進行稀釋混合，藉此獲得不揮發分5質量%之底塗劑（B-11）。Cool the temperature in the reaction container to 40°C, then use deionized water so that the non-volatile content becomes 10.0% by mass, and then filter with a 200-mesh filter cloth to obtain the undercoat layer used in the present invention. Resin composition. Next, water was added to this resin composition, it diluted and mixed, and the primer (B-11) of 5 mass % of non-volatile matter was obtained.
[製備例1：銀粒子分散液之製備] 使用對聚伸乙基亞胺加成聚氧乙烯而成之化合物作為分散劑，使平均粒徑30 nm之銀粒子分散於乙二醇45質量份及離子交換水55質量份之混合溶劑中，藉此製備含有銀粒子及分散劑之分散體。繼而，向所獲得之分散體中添加離子交換水、乙醇及界面活性劑，從而製備5質量%之銀粒子分散液。 [Preparation Example 1: Preparation of Silver Particle Dispersion] Using a compound obtained by adding polyoxyethylene to polyethyleneimine as a dispersant, disperse silver particles with an average particle diameter of 30 nm in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water, A dispersion containing silver particles and a dispersant is thus prepared. Next, ion-exchanged water, ethanol, and a surfactant were added to the obtained dispersion to prepare a 5% by mass silver particle dispersion.
[製備例2：銅蝕刻液之製備] 於離子交換水中，以硫酸37.5 g/L、及過氧化氫13.5 g/L之比率進行混合而製備銅蝕刻液。 [Preparation Example 2: Preparation of Copper Etching Solution] A copper etching solution was prepared by mixing sulfuric acid 37.5 g/L and hydrogen peroxide 13.5 g/L in ion-exchanged water.
[製備例3：銀用蝕刻液之製備] 向水47.4質量份中加入乙酸2.6質量份，進而加入35質量%過氧化氫溶液50質量份而製備銀用蝕刻液（1）。該銀用蝕刻液（1）之過氧化氫與羧酸之莫耳比（過氧化氫/羧酸）為13.6，銀用蝕刻液（1）中之過氧化氫及羧酸之混合物之含有比率為22.4質量%。 [Preparation Example 3: Preparation of Silver Etching Solution] 2.6 mass parts of acetic acid were added to 47.4 mass parts of water, and 50 mass parts of 35 mass % hydrogen peroxide solutions were further added, and the etchant (1) for silver was prepared. The molar ratio of hydrogen peroxide and carboxylic acid (hydrogen peroxide/carboxylic acid) in the silver etching solution (1) is 13.6, and the content ratio of the mixture of hydrogen peroxide and carboxylic acid in the silver etching solution (1) It is 22.4% by mass.
[製備例4：導電性聚合物分散液之製備] 基於專利文獻（日本特開2003-231991），合成出摻雜有硫酸根離子之聚吡咯/聚乙烯吡咯啶酮(PPy/PVP（SO 4 2-）)膠體。使用硫酸鈉作為摻雜劑，使用過硫酸銨作為氧化劑，使用聚乙烯吡咯啶酮作為界面活性劑。使用吡咯作為單體。 將0.85 g之PVP（聚乙烯吡咯啶酮，和光純藥公司製造，特級）溶解於溫度40℃之熱水500 ml中，向所獲得之溶液中加入過硫酸銨7.0 g作為氧化劑，加入硫酸鈉32.2 g作為摻雜劑，進而加入水而獲得總量1 L之水溶液。向所獲得之水溶液中加入5 mL之吡咯（東京化成（股）製造，特級），於室溫攪拌約12小時而進行化學氧化聚合，從而獲得聚合反應混合物。藉由對其進行離心分離，而獲得黑色之堆積物。將所獲得之堆積物用水清洗數次，使其再次分散於50 ml之水中而獲得10 g/L之(PPy/PVP（SO 4 2-）)水性膠體液。 [Preparation Example 4: Preparation of Conductive Polymer Dispersion] Based on the patent literature (Japanese Patent Laid-Open No. 2003-231991), polypyrrole/polyvinylpyrrolidone (PPy/PVP (SO 4 2- )) Colloids. Sodium sulfate is used as a dopant, ammonium persulfate is used as an oxidizing agent, and polyvinylpyrrolidone is used as a surfactant. Pyrrole was used as the monomer. Dissolve 0.85 g of PVP (polyvinylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., special grade) in 500 ml of hot water at a temperature of 40°C, add 7.0 g of ammonium persulfate as an oxidizing agent to the obtained solution, and add sodium sulfate 32.2 g was used as a dopant, and water was added to obtain a total of 1 L of aqueous solution. To the obtained aqueous solution, 5 mL of pyrrole (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) was added, and stirred at room temperature for about 12 hours to carry out chemical oxidation polymerization to obtain a polymerization reaction mixture. By centrifuging it, a black deposit was obtained. The obtained accumulation was washed several times with water, and dispersed again in 50 ml of water to obtain a 10 g/L (PPy/PVP(SO 4 2− )) hydrocolloid.
[製作例1] 使用兩面層壓有12 μm厚之銅箔之玻璃環氧基材（Panasonic股份有限公司製造之「多層基板材料R-1766」；厚度0.8 mm），藉由減成法製作在基材之兩表面具有L/S＝100/100 μm之梳狀電極且在末端具有5 mm見方之墊的銅電路圖案（圖5）。 [Production example 1] Using a glass epoxy substrate with 12 μm thick copper foil laminated on both sides ("Multilayer substrate material R-1766" manufactured by Panasonic Co., Ltd.; thickness 0.8 mm), fabricated on both surfaces of the substrate by the subtractive method Copper circuit pattern with comb electrodes of L/S = 100/100 μm with 5 mm square pads at the ends (Fig. 5).
（半加成工法用積層體之製造） （實施例1） 於製作例1中所製作之具有梳狀電極及墊圖案之玻璃環氧基材之兩面重疊預浸體（絕緣層（A）），進而於搭載有聚醯亞胺膜（宇部興產股份有限公司製造之「Upilex 50S」）之狀態下進行熱壓接（170℃、60分鐘），剝離聚醯亞胺膜，藉此製作在具有導體電路層（CM2）之玻璃環氧基材（絕緣性材料）上層壓有已硬化之預浸體（絕緣層（A））之基板。 (manufacture of laminates for semi-additive process) (Example 1) The prepreg (insulating layer (A)) laminated on both sides of the glass epoxy substrate with comb-shaped electrodes and pad patterns produced in Production Example 1, and then mounted on a polyimide film (Ube Industries, Ltd. "Upilex 50S" manufactured by the company) was bonded by thermocompression (170°C, 60 minutes), and the polyimide film was peeled off to produce a glass epoxy substrate (insulating property) with a conductor circuit layer (CM2). material) is laminated with a hardened prepreg (insulating layer (A)) on the substrate.
於上述玻璃環氧基材上之已硬化之預浸體（絕緣層（A）；預浸體（Panasonic股份有限公司製造之「R-1661」，厚度100 μm））之表面，使用桌上型小型塗布機（RK Print Coat Instruments公司製造之「K Printing Proofer」），將製備例1中所獲得之銀粒子分散體以乾燥後之銀粒子層（M1）成為0.5 g/m
2之方式進行塗布。繼而，使用熱風乾燥機以160℃乾燥5分鐘。進而，將膜翻面，以與上述相同之方式，將製備例1中所獲得之銀粒子分散體以銀粒子層（M1）成為0.5 g/m
2之方式進行塗布，使用熱風乾燥機以160℃乾燥5分鐘，藉此於已硬化之兩表面之預浸體（絕緣層（A））上形成銀粒子層（M1）。將藉此獲得之膜基材於250℃焙燒5分鐘，利用測試機確認到銀粒子層之導通。
On the surface of the hardened prepreg (insulation layer (A); prepreg ("R-1661" manufactured by Panasonic Co., Ltd.,
將上述所獲得之兩表面具有導電性銀粒子層之玻璃環氧基板，於無電解鍍銅液（羅門哈斯電子材料股份有限公司製造之「Circuposit 6550」）中在35℃浸漬10分鐘，於兩表面形成無電解鍍銅膜（M2；厚度0.2 μm），而製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及0.2 μm厚之銅層（M2）的半加成工法用積層體。The above-obtained glass epoxy substrate with conductive silver particle layers on both surfaces was immersed in an electroless copper plating solution ("Circuposit 6550" manufactured by Rohm and Haas Electronic Materials Co., Ltd.) at 35°C for 10 minutes. The electroless copper plating film (M2; thickness 0.2 μm) is formed on both surfaces, and the surface of the insulating layer (A) laminated on the inner printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material A layered body for semi-additive processing with a conductive silver particle layer (M1) and a 0.2 μm thick copper layer (M2) layered on top of it in sequence.
（實施例2） 除了將在無電解鍍銅液中之浸漬時間自10分鐘變更為25分鐘以外，以與實施例1相同之方式在銀粒子層（M1）上形成0.5 μm厚之無電解鍍銅膜，藉此製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上，依序積層有導電性銀粒子層（M1）及0.5 μm之銅層（M2）的半加成工法用積層體。 (Example 2) Except that the immersion time in the electroless copper plating solution was changed from 10 minutes to 25 minutes, a 0.5 μm thick electroless copper plating film was formed on the silver particle layer (M1) in the same manner as in Example 1, thereby Produced on the surface of the insulating layer (A) laminated on the inner printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, a conductive silver particle layer (M1) and a 0.5 μm The semi-additive method of the copper layer (M2) is used for laminates.
（實施例3） 將實施例1中所製作之在玻璃環氧基材上之已硬化之兩面之預浸體（絕緣層（A））表面上形成有導電性銀粒子層（M1）及0.2 μm厚之銅層的積層體固定於銅製之框，將無電解鍍銅層設置於陰極，將含磷銅作為陽極，使用含有硫酸銅之電鍍液（硫酸銅60 g/L、硫酸190 g/L、氯離子50 mg/L、添加劑「羅門哈斯電子材料股份有限公司製造之Copper Gleam ST-901」），以2 A/dm 2之電流密度進行4分鐘電鍍，藉此製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及2 μm之銅層（M2）的半加成工法用積層體。 (Example 3) A conductive silver particle layer (M1) and 0.2 The laminate of the μm-thick copper layer is fixed on a copper frame, the electroless copper plating layer is placed on the cathode, and the phosphorus-containing copper is used as the anode, and the electroplating solution containing copper sulfate (copper sulfate 60 g/L, sulfuric acid 190 g/ L, chloride ion 50 mg/L, additive "Copper Gleam ST-901 manufactured by Rohm and Haas Electronic Materials Co., Ltd."), electroplating at a current density of 2 A/dm 2 for 4 minutes, thereby making insulative A conductive circuit layer (CM2) is formed on the material, and a conductive silver particle layer (M1) and a 2 μm copper layer (M2) are sequentially laminated on the surface of the insulating layer (A) laminated on the inner printed wiring substrate. The semi-additive method uses laminates.
（實施例4） 除了將乾燥後之銀粒子層自0.5 g/m 2變更為0.8 g/m 2以外，以與實施例1相同之方式於玻璃環氧基材上之已硬化之兩面之預浸體（絕緣層（A））表面上形成導電性銀粒子層（M1），於250℃焙燒5分鐘，利用測試機確認到銀粒子層之導通。對於藉此所獲得之兩表面具有導電性銀粒子層之基材，將銀粒子層之表面設置於陰極，將含磷銅作為陽極，使用含有硫酸銅之電鍍液（硫酸銅60 g/L、硫酸190 g/L、氯離子50 mg/L、添加劑「羅門哈斯電子材料股份有限公司製造之Copper Gleam ST-901」），以2 A/dm 2之電流密度進行4.5分鐘電鍍，藉此製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及2 μm之銅層（M2）的半加成工法用積層體。 (Example 4) Except changing the silver particle layer after drying from 0.5 g/m 2 to 0.8 g/m 2 , in the same manner as in Example 1, the pre-treatment on both sides of the hardened glass epoxy substrate was carried out. A conductive silver particle layer (M1) was formed on the surface of the immersion body (insulating layer (A)), and it was baked at 250°C for 5 minutes, and the conduction of the silver particle layer was confirmed by a testing machine. For the base material with the conductive silver particle layer on both surfaces thus obtained, the surface of the silver particle layer is arranged on the cathode, and phosphorus-containing copper is used as the anode, and an electroplating solution containing copper sulfate (copper sulfate 60 g/L, Sulfuric acid 190 g/L, chloride ion 50 mg/L, additive "Copper Gleam ST-901 manufactured by Rohm and Haas Electronic Materials Co., Ltd."), electroplating at a current density of 2 A/dm 2 for 4.5 minutes, thereby producing Conductive silver particle layer (M1) and 2 μm copper are sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material Laminates are used for the semi-additive process of the layer (M2).
（實施例5） 以與實施例1相同之方式，於製作例1中所製作之具有梳狀電極及墊圖案之玻璃環氧基材之兩面重疊預浸體（絕緣層（A）），進而於搭載有聚醯亞胺膜（宇部興產股份有限公司製造之「Upilex 50S」）之狀態下進行熱壓接（170℃、60分鐘），剝離聚醯亞胺膜，藉此製作於具有導體電路層（CM2）之玻璃環氧基材（絕緣性材料）上層壓有已硬化之預浸體（絕緣層（A））的基板。 (Example 5) In the same manner as in Example 1, the prepreg (insulating layer (A)) was laminated on both sides of the glass epoxy substrate with comb electrodes and pad patterns produced in Production Example 1, and the polyamide In the state of the imide film ("Upilex 50S" manufactured by Ube Industries Co., Ltd.), thermocompression bonding (170°C, 60 minutes) was performed, and the polyimide film was peeled off to fabricate a circuit layer with a conductor (CM2) A substrate in which a hardened prepreg (insulating layer (A)) is laminated on a glass epoxy substrate (insulating material).
於上述玻璃環氧基材上之已硬化之預浸體（絕緣層（A））之表面，使用桌上型小型塗布機（RK Print Coat Instruments公司製造之「K Printing Proofer」），將製造例1中所獲得之底塗劑（B-1）以乾燥後之厚度成為120 nm之方式進行塗布，繼而使用熱風乾燥機以80℃乾燥5分鐘。進而，將基材翻面，以與上述相同之方式將製造例1中所獲得之底塗劑（B-1）以乾燥後之厚度成為120 nm之方式進行塗布，使用熱風乾燥機以80℃乾燥5分鐘，藉此於已硬化之兩表面之預浸體（絕緣層（A））上形成底塗層。On the surface of the hardened prepreg (insulating layer (A)) on the above-mentioned glass epoxy base material, using a desktop small coater ("K Printing Proofer" manufactured by RK Print Coat Instruments Co., Ltd.), the production example The primer (B-1) obtained in 1 was applied so that the thickness after drying would be 120 nm, and then dried at 80° C. for 5 minutes using a hot air dryer. Furthermore, the substrate was turned over, and the primer (B-1) obtained in Production Example 1 was applied in the same manner as above so that the thickness after drying became 120 nm, and it was heated at 80°C using a hot air dryer. Drying was carried out for 5 minutes, whereby an undercoat layer was formed on the prepreg (insulating layer (A)) on both surfaces of the hardened surface.
使用上述所獲得之在已硬化之兩表面之預浸體（絕緣層（A））上形成有底塗層之基材，除此以外，以與實施例2相同之方式於導電性銀粒子層（M1）上形成0.5 μm厚之無電解鍍銅膜，藉此製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有底塗層（B）、導電性銀粒子層（M1）及0.5 μm之銅層（M2）的半加成工法用積層體。Using the substrate obtained above on which the undercoat layer was formed on the hardened prepreg (insulating layer (A)) on both surfaces, the conductive silver particle layer was formed in the same manner as in Example 2. A 0.5 μm thick electroless copper plating film is formed on (M1), thereby making the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material It is a laminate for semi-additive process, in which a primer layer (B), a conductive silver particle layer (M1) and a 0.5 μm copper layer (M2) are sequentially laminated.
（實施例6） 於實施例5中，將銀粒子層自0.5 g/m 2變更為0.8 g/m 2，以與實施例4相同之方式進行電鍍銅處理，藉此製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有底塗層（B）、導電性銀粒子層（M1）及0.5 μm之銅層（M2）的半加成工法用積層體。 (Example 6) In Example 5, the silver particle layer was changed from 0.5 g/m 2 to 0.8 g/m 2 , and copper electroplating was performed in the same manner as in Example 4, thereby producing A conductive circuit layer (CM2) is formed on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate, and a primer layer (B), a conductive silver particle layer (M1) and a 0.5 μm The semi-additive method of the copper layer (M2) is used for laminates.
（實施例7～16） 將用於底塗層（B）之底塗劑之種類及其乾燥條件、銀粒子層（M1）之銀量變更為如表1或2所示，除此以外，以與實施例6相同之方式製作於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有底塗層（B）、導電性銀粒子層（M1）及銅層（M2）之半加成工法用積層體。 (Embodiments 7-16) The type and drying condition of the primer used for the primer layer (B) and the amount of silver in the silver particle layer (M1) were changed as shown in Table 1 or 2. In addition, the same method as in Example 6 was used. Manufactured on the surface of the insulating layer (A) laminated on the inner printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, the undercoat layer (B) and the conductive silver particles are sequentially laminated. Layer (M1) and copper layer (M2) semi-additive method of laminated body.
（實施例17） 使用實施例2中所製作之於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及0.5 μm之銅層（M2）的積層體，於內層導體電路層（CM2）之墊位置，使用雷射形成與內層之導體電路層（CM2）連接之70 μm直徑之導孔。 對藉此所獲得之附有與內層導體電路層（CM2）連接之導孔之基材實施MacDermid公司之黑孔製程（調整（conditioning）-碳吸附處理-蝕刻），使碳附著於導孔之表面，對於附著有碳之銅層（M2），使用製備例2中所製作之硫酸/過氧化氫水溶液進行蝕刻處理而將其去除，藉此使絕緣層（A）上之導電性銀粒子層（M1）露出。藉此獲得於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上具有導電性銀粒子層（M1），進而具有自絕緣層（A）達至導體電路層（CM2）之導孔，且導孔之表面由碳確保了導電性之半加成工法用積層體。 （實施例18） 除了使用實施例6中所製作之積層體代替實施例2中所製作之積層體以外，以與實施例17相同之方式，獲得於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上具有導電性銀粒子層（M1），進而具有自絕緣層（A）達至導體電路層（CM2）之導孔，且導孔之表面由碳確保了導電性之半加成工法用積層體。 (Example 17) Conductive silver particle layers are sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material produced in Example 2. (M1) and a 0.5 μm copper layer (M2) laminate, use laser to form a 70 μm diameter guide connected to the inner conductor circuit layer (CM2) at the pad position of the inner conductor circuit layer (CM2) hole. The black hole process (conditioning-carbon adsorption treatment-etching) of MacDermid Company is implemented on the substrate obtained by this method with the guide hole connected to the inner conductor circuit layer (CM2), so that carbon is attached to the guide hole On the surface, for the copper layer (M2) with carbon attached, use the sulfuric acid/hydrogen peroxide aqueous solution prepared in Preparation Example 2 to perform etching treatment to remove it, so that the conductive silver particles on the insulating layer (A) Layer (M1) is exposed. In this way, a conductive silver particle layer (M1) is obtained on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, thereby having self-insulating properties. The layer (A) reaches the lead hole of the conductor circuit layer (CM2), and the surface of the lead hole is made of carbon to ensure the conductivity of the laminated body for the semi-additive method. (Example 18) In the same manner as in Example 17, except that the laminate produced in Example 6 was used instead of the laminate produced in Example 2, an inner layer in which a conductor circuit layer (CM2) was formed on an insulating material was obtained. The surface of the insulating layer (A) laminated on the printed wiring substrate has a conductive silver particle layer (M1), and then has a guide hole from the insulating layer (A) to the conductor circuit layer (CM2), and the guide hole A layered body for the semi-additive method whose surface is secured with carbon.
（實施例19） 除了使用實施例11中所製作之積層體代替實施例2中所製作之積層體以外，以與實施例17相同之方式，獲得於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上具有導電性銀粒子層（M1），進而具有自絕緣層（A）達至導體電路層（CM2）之導孔，且導孔之表面由碳確保了導電性之半加成工法用積層體。 (Example 19) In the same manner as in Example 17, except that the laminate produced in Example 11 was used instead of the laminate produced in Example 2, an inner layer in which a conductor circuit layer (CM2) was formed on an insulating material was obtained. The surface of the insulating layer (A) laminated on the printed wiring substrate has a conductive silver particle layer (M1), and then has a guide hole from the insulating layer (A) to the conductor circuit layer (CM2), and the guide hole A layered body for the semi-additive method whose surface is secured with carbon.
（實施例20） 以與實施例19相同之方式，使用於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上依序積層有導電性銀粒子層（M1）及0.5 μm之銅層（M2）之積層體，於內層導體電路層（CM2）之墊位置，使用雷射形成與內層之導體電路層（CM2）連接之70 μm直徑之導孔。 (Example 20) In the same manner as in Example 19, conductive silver was sequentially laminated on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate on which the conductive circuit layer (CM2) was formed on the insulating material. The laminate of the particle layer (M1) and the 0.5 μm copper layer (M2) is formed at the pad position of the inner conductor circuit layer (CM2) using a laser to form a 70 μm diameter connected to the inner conductor circuit layer (CM2) The guide hole.
對於藉此所獲得之附有與內層導體電路層（CM2）連接之導孔之基材，將其於包含氯化鈀1 g/l、鹽酸1 ml/l及二甲基硫脲1 g/l之觸媒液中在25℃浸漬3分鐘，以此代替對其實施黑孔製程。繼而，對基板進行水洗，利用包含二甲胺硼烷10 g/l及氫氧化鈉5 g/l之還原液在50℃處理2分鐘，而利用鈀使通孔之表面導電化，從而獲得於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上具有導電性銀粒子層（M1），進而具有自絕緣層（A）達至導體電路層（CM2）之導孔，且導孔之表面由鈀確保了導電性之半加成工法用積層體。For the substrate thus obtained with vias connected to the inner conductor circuit layer (CM2), it was mixed with palladium chloride 1 g/l, hydrochloric acid 1 ml/l and dimethylthiourea 1 g /l of catalyst solution at 25°C for 3 minutes instead of implementing the black hole process. Then, the substrate was washed with water, treated with a reducing solution containing 10 g/l of dimethylamine borane and 5 g/l of sodium hydroxide at 50° C. for 2 minutes, and the surface of the through hole was made conductive with palladium, thereby obtaining The conductive circuit layer (CM2) is formed on the insulating material, and the insulating layer (A) laminated on the inner layer printed wiring substrate has a conductive silver particle layer (M1) on the surface, and then has a self-insulating layer (A) The semi-additive method laminated body that reaches the guide hole of the conductor circuit layer (CM2), and the surface of the guide hole has ensured conductivity by palladium.
（實施例21） 於實施例20中，對於附有與內層導體電路層（CM2）連接之導孔之基材，將其於製備例4中所製作之(PPy/PVP（SO 4 2-）)水性膠體液中在室溫浸漬2分鐘，使膠體粒子附著於通孔表面，而利用導電性聚合物使通孔之表面導電化，以此代替利用鈀使其導電化。藉此獲得於在絕緣性材料上形成有導體電路層（CM2）之內層印刷配線基材上所積層之絕緣層（A）之表面上具有導電性銀粒子層（M1），進而具有自絕緣層（A）達至導體電路層（CM2）之導孔，且導孔之表面由導電性聚合物確保了導電性之半加成工法用積層體。 (Example 21) In Example 20, for the base material with the guide hole connected to the inner conductor circuit layer (CM2), the (PPy/PVP (SO 4 2- )) Immerse in the aqueous colloid solution at room temperature for 2 minutes to make the colloidal particles adhere to the surface of the through hole, and use the conductive polymer to make the surface of the through hole conductive instead of using palladium to make it conductive. In this way, a conductive silver particle layer (M1) is obtained on the surface of the insulating layer (A) laminated on the inner layer printed wiring substrate with the conductive circuit layer (CM2) formed on the insulating material, thereby having self-insulating properties. The layer (A) reaches the guide hole of the conductor circuit layer (CM2), and the surface of the guide hole is made of a conductive polymer to ensure the conductivity of the laminated body for the semi-addition method.
（印刷配線板之製造） （實施例22～26） 使用實施例17～21中所製作之半加成工法用積層體，於銀粒子層（M1）上，使用覆膜機以100℃壓接乾膜抗蝕劑（日立化成股份有限公司製造之「Photec RD-1225」；抗蝕劑膜厚25 μm），繼而使用直接曝光數位成像裝置（奧寶科技公司製造之「Nuvogo1000R」），如圖7所示在與內層導體電路（CM2）之墊部連接之導孔部，使200 μm直徑之焊盤（land）曝光，自焊盤使50 μm寬、5 cm長之導電電路層（CM1）之TEG圖案曝光。繼而，使用1質量%碳酸鈉水溶液進行顯影，藉此使上述TEG圖案之銀粒子層（M1）露出。 (Manufacturing of printed wiring boards) (Example 22-26) Using the laminates for the semi-additive process prepared in Examples 17 to 21, a dry film resist (manufactured by Hitachi Chemical Co., Ltd. "Hitachi Chemical Co., Ltd." Photec RD-1225"; resist film thickness 25 μm), and then use a direct exposure digital imaging device ("Nuvogo1000R" manufactured by Orbotech Corporation), as shown in Figure 7 on the pad with the inner layer conductor circuit (CM2) In the guide hole part connected to the bottom, expose the pad (land) with a diameter of 200 μm, and expose the TEG pattern of the conductive circuit layer (CM1) with a width of 50 μm and a length of 5 cm from the pad. Next, the silver particle layer (M1) of the said TEG pattern was exposed by image development using 1 mass % sodium carbonate aqueous solution.
繼而，將形成有圖案抗蝕劑之基材之銀粒子層（M1）表面設置於陰極，將含磷銅作為陽極，使用含有硫酸銅之電鍍液（硫酸銅60 g/L、硫酸190 g/L、氯離子50 mg/L、添加劑「羅門哈斯電子材料股份有限公司製造之Copper Gleam ST-901」），以2 A/dm 2之電流密度進行27分鐘電鍍，藉此於抗蝕劑已被去除之上述TEG圖案部，藉由電鍍銅而形成12 μm厚之導電電路層（CM1）。繼而，將該等基材浸漬於被設定為50℃之3質量%之氫氧化鈉水溶液中，藉此剝離圖案抗蝕劑。 Next, set the surface of the silver particle layer (M1) of the substrate with the pattern resist on the cathode, use phosphorus-containing copper as the anode, and use an electroplating solution containing copper sulfate (copper sulfate 60 g/L, sulfuric acid 190 g/L L, chloride ion 50 mg/L, additive "Copper Gleam ST-901 manufactured by Rohm and Haas Electronic Materials Co., Ltd."), electroplating was carried out for 27 minutes at a current density of 2 A/dm 2 . The removed TEG pattern part was formed by electroplating copper to form a 12 μm thick conductive circuit layer (CM1). Then, these base materials were immersed in the 3 mass % sodium hydroxide aqueous solution set to 50 degreeC, and the pattern resist was peeled off.
繼而，於製備例2中所獲得之銀用蝕刻液中，將上述所獲得之基材在25℃浸漬30秒鐘，藉此去除導電電路層圖案以外之銀粒子層（M1）而獲得印刷配線板。關於所製作之印刷配線板之導電電路層之截面形狀，分別為配線高度及配線寬度無減少，且呈現無底切之矩形形狀，為平滑表面之導電電路層（CM1）。Next, in the etching solution for silver obtained in Preparation Example 2, immerse the substrate obtained above at 25°C for 30 seconds, thereby removing the silver particle layer (M1) other than the conductive circuit layer pattern to obtain printed wiring plate. Regarding the cross-sectional shape of the conductive circuit layer of the produced printed wiring board, the height and width of the wiring are not reduced, and the rectangular shape without undercut is the conductive circuit layer (CM1) with a smooth surface.
（比較例1） 於實施例1中，在製作例1中所製作之玻璃環氧基材之兩面重疊上述預浸體及JX金屬公司製造之12 μm厚之壓延銅箔（BHY-82F-HA-V2），並進行熱壓接（170℃、60分鐘），以此代替在玻璃環氧基材上之已硬化之預浸體（絕緣層（A）；預浸體（Panasonic股份有限公司製造之「R-1661」，厚度100 μm））之表面形成銀粒子層，從而製作於具有導體電路層（CM2）之玻璃環氧基材（絕緣性材料）上積層有已硬化之預浸體（絕緣層（A））及銅箔之基板。使用製備例2中所製作之硫酸/過氧化氫系銅蝕刻液，將該基板之表層之銅箔蝕刻至3 μm後，以與實施例22～26相同之方式於銅箔之鍍覆底層上利用銅而形成12 μm厚之導電電路層。 (comparative example 1) In Example 1, the above-mentioned prepreg and rolled copper foil (BHY-82F-HA-V2) with a thickness of 12 μm (BHY-82F-HA-V2) manufactured by JX Metal Co. Carry out thermocompression bonding (170°C, 60 minutes) to replace the hardened prepreg (insulation layer (A) on the glass epoxy substrate; prepreg (Panasonic Co., Ltd. "R-1661 ", a thickness of 100 μm)) to form a silver particle layer on the surface, so that a hardened prepreg (insulating layer (A) ) and copper foil substrates. Using the sulfuric acid/hydrogen peroxide-based copper etchant prepared in Preparation Example 2, etch the copper foil on the surface layer of the substrate to 3 μm, and then coat the copper foil on the bottom layer of the copper foil in the same manner as in Examples 22-26. A 12 μm thick conductive circuit layer was formed using copper.
繼而，在浸漬於銅晶種之蝕刻中所使用之硫酸/過氧化氫系快速蝕刻液中而去除銅之晶種時，導電電路層受到蝕刻，膜厚變薄約3 μm，並且配線寬度亦減少約6 μm，且截面形狀無法保持矩形而變成「梯形」狀。又，銅之導電層表面因蝕刻而被粗化，平滑性降低。Then, when the copper seed crystal was removed by immersing it in the sulfuric acid/hydrogen peroxide-based rapid etching solution used for etching the copper seed crystal, the conductive circuit layer was etched, and the film thickness became thinner by about 3 μm, and the wiring width also became smaller. The reduction is about 6 μm, and the cross-sectional shape cannot be kept as a rectangle but becomes a "trapezoid" shape. Moreover, the surface of the conductive layer of copper is roughened by etching, and smoothness falls.
（比較例2） 於比較例1中，關於在具有導體電路層（CM2）之玻璃環氧基材（絕緣性材料）上積層有已硬化之預浸體（絕緣層（A））及銅箔之基板，不對該基板之表層之銅箔進行蝕刻而使用，於藉由使用氯化鐵蝕刻液之減成法而形成導電電路層時，電路層之截面形狀無法保持矩形而成為「梯形」，銅之導電層表面因蝕刻而被明顯粗化。 (comparative example 2) In Comparative Example 1, regarding the substrate in which the cured prepreg (insulating layer (A)) and copper foil were laminated on the glass epoxy substrate (insulating material) having the conductor circuit layer (CM2), the The copper foil on the surface of the substrate is used for etching. When the conductive circuit layer is formed by using the subtractive method of ferric chloride etching solution, the cross-sectional shape of the circuit layer cannot be kept as a rectangle and becomes a "trapezoid". The surface of the copper conductive layer Visibly roughened by etching.
[底切之有無及配線部之截面形狀之確認] 利用掃描式電子顯微鏡（日本電子股份有限公司製造之「JSM7800」）將上述所獲得之印刷配線板之梳狀電極部之剖面放大至500～10,000倍進行觀察，確認底切之有無及梳狀電極部之截面形狀。 [Confirmation of the presence or absence of undercut and the cross-sectional shape of the wiring part] Use a scanning electron microscope ("JSM7800" manufactured by JEOL Ltd.) to observe the cross-section of the comb-shaped electrode portion of the printed wiring board obtained above at a magnification of 500 to 10,000 times to confirm the presence or absence of undercuts and comb-shaped electrodes. Sectional shape of the part.
藉由利用雷射顯微鏡（基恩斯公司製造，VK-9710）對所製作之印刷配線板之配線表面進行觀察，而確認配線表面之表面粗糙度，將Rz為3 μm以下者評價為平滑（平滑性：〇），將Rz超過3 μm者評價為不平滑（平滑性：×）。又，於由用於形成配線之抗蝕劑所獲得之配線之設計寬度與所形成之配線之上表面寬度的差異為2 μm以下之情形時，評價為旁側蝕刻得到抑制，可保持矩形形狀（矩形性：〇），將差異超過2 μm者評價為未能保持矩形形狀（矩形性：×），將實施例、比較例、評價結果示於表1～表3。By observing the wiring surface of the produced printed wiring board with a laser microscope (manufactured by Keynes Corporation, VK-9710), the surface roughness of the wiring surface was confirmed, and the smoothness (smoothness) was evaluated when Rz was 3 μm or less. : 〇), Rz exceeding 3 μm was evaluated as not smooth (smoothness: ×). In addition, when the difference between the designed width of the wiring obtained from the resist used to form the wiring and the upper surface width of the formed wiring is 2 μm or less, it is evaluated that the side etching is suppressed and the rectangular shape can be maintained (rectangularity: 0), and those with a difference of more than 2 μm were evaluated as failing to maintain a rectangular shape (rectangularity: ×). Examples, comparative examples, and evaluation results are shown in Tables 1 to 3.
[表1]
[表2]
[表3]
1:絕緣性基材 2:銀粒子層（M1） 3:覆蓋層（銅層） 4:導體電路層（CM2） 5:盲孔 6:鈀、導電性聚合物、碳 7:圖案抗蝕劑 8:導電層（電鍍銅層） （a）:半加成工法用積層體（請求項1之構成） （b）步驟1:形成非貫通孔（盲通孔） （c）步驟2:使盲通孔導電化 （d）步驟3:使導電性銀粒子層露出 （e）步驟4:形成圖案抗蝕劑形成 （f）步驟5:藉由電鍍銅而形成導電層 （g）步驟6:剝離圖案抗蝕劑 （h）步驟6:去除銀晶種（請求項11之構成） 1: Insulating substrate 2: Silver particle layer (M1) 3: Covering layer (copper layer) 4: Conductor circuit layer (CM2) 5: blind hole 6: Palladium, conductive polymer, carbon 7: Pattern Resist 8: Conductive layer (electroplated copper layer) (a): Laminated body for semi-additive construction method (composition of Claim 1) (b) Step 1: Forming non-through holes (blind via holes) (c) Step 2: Make the blind via conductive (d) Step 3: exposing the conductive silver particle layer (e) Step 4: Pattern resist formation (f) Step 5: Forming a conductive layer by electroplating copper (g) Step 6: Stripping the pattern resist (h) Step 6: Removing the silver seed crystal (composition of claim 11)
[圖1]係請求項1所記載之半加成工法用積層體之示意圖。
[圖2]係於圖1之銀粒子層上具有底塗層之請求項2所記載之半加成工法用積層體之示意圖。
[圖3]係請求項3所記載之半加成工法用積層體之示意圖。
[圖4]係於圖2之銀粒子層上具有底塗層之請求項4所記載之半加成工法用積層體之示意圖。
[圖5]係使用圖1所示之半加成工法用積層體來製造印刷配線板之步驟圖。
[圖6]係製作例1中所製作之梳狀電極、及墊圖案之示意圖。
[圖7]係實施例22～26中所製作之印刷配線板中之內層、外層電路圖案之示意圖。
[Fig. 1] is a schematic diagram of the laminate for the semi-additive method described in claim 1.
[ Fig. 2 ] is a schematic diagram of a laminate for semi-additive processing described in claim 2 having an undercoat layer on the silver particle layer in Fig. 1 .
[Fig. 3] is a schematic diagram of the laminate for the semi-additive method described in
1:絕緣性基材 1: Insulating substrate
2:銀粒子層(M1) 2: Silver particle layer (M1)
3:覆蓋層(銅層) 3: Covering layer (copper layer)
4:導體電路層(CM2) 4: Conductor circuit layer (CM2)
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| JP3570802B2 (en) | 1995-11-14 | 2004-09-29 | 三井化学株式会社 | Copper thin film substrate and printed wiring board |
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