TW201228822A - Laminate body and fabricating method thereof, print circuit board and circuit - Google Patents

Abstract

The method of fabricating a patterned laminated body with a copper-containing plating film in the present invention includes: a step of forming a polymer layer, which forms a polymer layer on a substrate; a step of applying catalyst for a plating catalyst liquid containg copper ion and with pH over 3.0 to contact the polymer layer, so that the copper ions are applied to the polymer layer; a step of contacting first alkali aqueous for an alkali aqueous contacting the polymer layer to which copper ions applied; a step of plating for the polymer layer to be at least plated with copper after the step of contacting first alkali aqueous, so as to obtain a copper-containing plating film; a step of forming a pattern by etching the copper-containing plating film to form a pattern after the plating step, so that a patterned copper-containing plating film is formed.

Description

201228822 VI. Description of the Invention: [Technical Field to Be Invented] The present invention relates to a method of manufacturing a laminated body. Further, the present invention is a laminate having a pattern-like copper-containing money film. The prior art has been widely used for electronic parts by forming a metal wiring board using a gold wire on the surface of an insulating substrate. Or the semiconductor wafer 0 is used as the method of manufacturing the metal pattern material, and the "method" is mainly used. The subtractive method refers to a method of forming a photosensitive layer which is photosensitive by irradiation of active light on a gold formed on a surface of a substrate, and imagewise exposing the layer to the image, followed by development to form Anti-fine image, ^ ^ on the metal film to form a metal pattern, and finally the metal _ towel obtained by the anti-money _ surface financial method, Xiang (four) in the substrate is a film:: the resulting anchoring effect 'make the substrate With the metal pattern (gold is used as the winter Μ 0 adhesion property. Therefore, when the obtained metal pattern and ingredients are present, there is a problem that the south frequency characteristics are deteriorated due to the substrate interface of the metal pattern. In the case of the surface of the L-plate, there is a metal pattern which is excellent in the adhesion of the complicated board for the treatment of the surface of the L-plate, and it is necessary to solve the problem. : forming a graft polymer secret silk layer directly bonded to the silk plate on the substrate 201228822 /pif, performing recording, and then performing a surname on the obtained metal film (patent). According to the method, Substrate table In the past, in recent years, in order to cope with the small size of electronic equipment, the invention has been made to improve the adhesion between the substrate and the metal film. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. 2009-010336 In order to achieve high-performance and high-performance, the fine wiring of the printed circuit board is advanced: In this case, wiring (metal pattern) needs to be more excellent, and when wiring is produced by (10) processing, it is required to enter the step. The metal residue_removal. The I-forming method of the wiring pattern revealed by the occupant at the frequency of one towel is studied. The knot is now at the _ of the plating layer, and the metal is not necessarily removed sufficiently. Further improvement is required. In addition to the demand for high quality of electronic equipment, the production of fine wiring is excellent in the linearity of the defects such as the absence of the wiring, the reduction of the thickness, the bending, and the like. The present inventors have studied the formation method of the wiring pattern specifically disclosed in Patent Document 1, and as a result, it has been clarified that the obtained linearity of the fine matching does not necessarily meet the recent requirements. [Invention] In the above-described actual circumstances, an object of the present invention is to provide a method for producing a laminate, which can obtain a laminate having a metal residue during etching treatment, which is suppressed. And the pattern-like copper-containing ore film having excellent adhesion is studied by the ancestors in the above-mentioned problems, and as a result, it has been found that the ion specifically causes the silver ion of the smectite layer or the influence of the coating medium to generate a metal residue. The above-mentioned problem can be solved by the following configuration based on the above findings. (1.) A method for producing a laminate having a patterned copper-containing plating film, &£> a poly-δ layer 幵/forming step of contacting a substrate having a g-energy group and a polymerizable group forming a target with a steel ion on a substrate, and then applying energy to form a polymer layer on the substrate; a catalyst application step of contacting a mineralizing catalyst liquid containing copper ions and having a pH exceeding 3·〇 with the polymer layer, (4) polymerizing copper ions; and contacting the first alkaline aqueous solution to make The copper ion-imparting polymer layer is contacted with the alkaline aqueous solution; the bell coating step, after the first i-thotropic aqueous solution contacting step, the polymer layer is at least subjected to copper ore to obtain a copper-containing plating film; and a pattern forming step After the above-described mineral depositing step, the copper-containing recording film is etched into a pattern to form a pattern-containing copper-containing plating film. (2) The method for producing a laminate according to (1), wherein after the step of contacting the first alkaline aqueous solution and before the plating step, further comprising: polymerizing the polymer layer to which the copper anode is applied The reduction step of the reducing solution. (3) The method for producing a laminate according to (2), wherein after the 201228822 〇yy〇/pxf reduction step and before the plating step, the second step of contacting the polymer layer with the peak aqueous solution is further included. Aqueous aqueous contact step. (4) A laminate body obtained by the method for producing a laminate according to any one of (1) to (3). (5) A printed wiring board comprising the laminate according to (4). (6) A circuit comprising the laminated body as described in (4). [Effects of the Invention] According to the present invention, it is possible to provide a method for producing a layered body, which is capable of obtaining a layered body of a patterned copper-containing plating film having suppressed linearity and adhesion and having excellent linearity and adhesion. . [Embodiment] The laminate obtained by the method for producing a laminate which is not praised by the method will be described. First, the feature points of the present invention compared to the prior art will be described in detail. According to the above description, the inventors of the present invention performed the ^^2f problem on the disambiguation technique (4). If the content of the polymer layer is included in the polymer layer as the influence of =_, the result is a metal residue _ or; The human root 1 has been studied in the above-mentioned findings. As a result, it has been found that the use of the aqueous solution of the aqueous solution of the test aqueous solution can be solved by making the present invention =:: step '. The following five steps for producing a copper-free laminate include: 201228822, (1) a polymer layer forming step of forming a functional group having an interaction with a copper ion on a substrate, and a polymerizable group After the polymer contacts the substrate, 'energy is applied to form a polymer layer on the substrate; (2) the catalyst imparting step 'contacts the clock solution containing copper ions and having a pH exceeding 3 与 with the polymer layer' The polymer layer imparts copper ions; (3) the first alkaline aqueous solution contacting step causes the polymer layer to which the copper ions are added to contact the aqueous solution; (4) the plating step 'coats the polymer layer at least, The copper plating is obtained; (5) a pattern forming step of etching the copper-containing plating film into a pattern after the plating step to form a pattern-containing copper plating film. The materials used in each step and the method of operation thereof are described in detail below. <Step (1): Polymer layer forming step> Step (1) is to apply a polymer having a functional group that interacts with copper ions and a polymerizable group to a substrate, and then impart energy to the substrate. A step of forming a polymer layer on the substrate. The polymer layer formed by this step functions to adsorb (attach) copper ions in the catalyst application step to be described later, in accordance with the function of a functional group that forms an interaction with copper ions in the polymer. That is, the polymer layer functions as a good receiving layer (coated layer) of copper ions. Further, the polymerizable group is used for chemical bonding of polymers to each other or to a substrate (an adhesion assisting layer to be described later). As a result, excellent adhesion between the copper-containing plating film formed on the surface of the object and the substrate is exhibited. Specifically, in this step, as shown in FIG. 1(A), the 201228822 jyy〇/pit is provided with the substrate 10 of the adhesion auxiliary layer 12, and is as shown in (b) of FIG. A polymer layer 14 is formed on the upper portion of the substrate 10. Further, as will be described later, the auxiliary layer 12 is an arbitrary layer. First, the materials (substrate, adhesion assisting layer, polymer, polymer layer forming composition, and the like) used in this step will be described in detail, and the procedure of the bean step will be described in detail.八 ° [Substrate] As the substrate used in the present invention, any of the previously known substrates can be used, and a substrate which can withstand the processing conditions described later is preferable. Further, it is preferred that the two sheets have a function of being chemically bonded to a polymer to be described later. Specifically, the earth plate itself may be bonded to the polymer by energy imparting (for example, exposure), or may be provided on the substrate with an intermediate layer that can be chemically bonded by the energy-imparting layer (for example, the adhesion described later) Fuxian == Material 2: Two sub-pen materials (r° ", plastic. Specific and female, _ note" recorded in Weiwei I. Ethylcellulose, cellulose triacetate, strontium propionate , W cellulose, secret cellulose, poly-p-benzene: (10) Two: vinegar: polyethylene, polystyrene, polypropylene, polyethylene acetal, tr: money, double Malay light amine, poly benzene, liquid | is a rare material, metal materials (such as metal alloys, known or similar materials. Specifically, paper, laminated plastic paper), combinations of these, or similar to the 201228822 material In addition, the laminate of the present invention can be applied to a semiconductor package, various electric wiring boards, etc. When used for such applications, it is preferable to use a substrate containing an insulating resin as described below, specifically, a substrate (insulating substrate) containing an insulating resin, or A substrate having a layer (insulating resin layer) containing an insulating resin (a substrate having an insulating resin layer), when a substrate including an insulating resin or a layer containing an insulating resin is obtained, a known insulating property can be used. Specific examples of the insulating resin may be, for example, a thermosetting resin or a thermoplastic resin, or a mixture thereof. For example, as a thermosetting resin, an epoxy resin may be mentioned. Phenolic resin, polyimide resin, polyester resin, bismaleimide resin, polyolefin resin, isocyanate resin, acrylonitrile, butane H ethylene (A(tetra) GnitrileButadiene Styrene, ABS) resin, etc. Examples of the resin include a bismuth phthalate varnish type epoxy tree type A epoxy refractory, double bismuth type epoxy resin, silk secret oxygen removal, silk benzene (10) paint type ring fat reduction, and biphenyl test F Classes of 'Cai type epoxy resin, dicyclopentadiene type epoxy resin, age-related heterogeneous family _ epoxide of condensate, isocyanide = :=: alicyclic _, etc. These can be used alone 'As a thermoplastic resin, such as poly石 wind, I· #〜力举. This oxy resin, poly yoke, ^H, P, poly _, poly ugly imine, etc., in the board, as long as the effects of the invention are not impaired, can also include various additions 201228822 jyyo / The pif force W may, for example, be a filler filler such as inorganic particles (for example, glass fiber, oxidized crystal, oxidized crystal, clay, talc, hydrocortisone, methane, mica, rockstone) or a Wei compound (for example) Wei coupling agent or Shixi silk splicing agent, etc.), organic filler (such as hardened epoxy resin, crosslinked benzoguanamine resin, cross (tetra) _ polymer, etc.), plasticizer, surfactant, viscosity modifier, coloring Agent, hardener, impact strength modifier, adhesion imparting agent, antioxidant, UV absorber, etc. Considering the use of a substrate for a semiconductor package or various electrical wiring substrates, JIS B bribes (1994) The surface roughness Rz measured by the 10-point average height method is preferably 5 〇〇 nm or less, more preferably just below nm, and more preferably less than or equal to % nm. The lower limit is not particularly limited, but is preferably about 5 rnn, more preferably 〇. Further, the substrate may have metal wiring on one or both sides thereof. The metal may be arranged with respect to the surface of the base (four), or may be formed on the entire surface by 减', which may be exemplified by a subtractive method using an etching treatment, or a half-plus by electrolytic plating. The metal formed by the method can be used, and the metal wiring formed by any construction method can be used. Examples of the material constituting the metal wiring include copper, silver, tin, gold, nickel, chromium, crane, steel, zinc, or gallium. As the substrate having such a metal wiring, for example, a copper clad laminate (CCL) having two sides or one surface, or a substrate having a fine weave pattern of a conventional steel clad laminate can be used, and these are soft substrates. It can also be a rigid substrate. One soil 0 [adhesive auxiliary layer] 11 201228822 The adhesion auxiliary layer is an arbitrary layer which can be provided on the surface of the above-mentioned substrate, and serves to assist the adhesion between the substrate and the polymer layer to be described later. Preferably, the adhesion assisting layer is chemically bonded to the polymer when the polymer is subjected to energy imparting (e.g., exposure). Further, a polymerization initiator may be contained in the adhesion assisting layer. The thickness of the adhesion auxiliary layer must be appropriately selected according to the surface smoothness of the substrate, etc., and generally, it is preferably 〇.〇] μηι~1〇〇μηι, more preferably 〇〇5 μηι~20 μη!佳为〇〇5 μιη~1() μιη. In addition, the surface roughness of the adhesion-assisted layer is improved by the JIS Β 〇6〇1 (1994) and (7) point average height method from the viewpoint of improving the physical properties of the formed copper-containing ore film. Rz is preferably 3 or less, and Rz is more preferably 1 μηη or less. The material of the adhesion assisting layer is not particularly limited. When the Lin 1 substrate having good adhesion to the substrate is made of an electrically insulating resin, the heat transfer point, the modulus of elasticity, the coefficient of linear expansion, and the like are relatively high. Close to the resin of physical properties. Specifically, for example, from the viewpoint of adhesion, it is preferred to use an insulating resin such as an insulating resin constituting the substrate. The insulative tree t, which is used for the adhesion assisting layer, has an insulating tree which can be used for a known insulating film, and may be a resin which is not completely rim-edge HI. It is used in the present invention. As a specific example of the insulating resin, for example, a thermoplastic resin may be used, or a raw material may be used as a thermosetting property, and examples thereof include: a job, for example, a sputum, a phenol resin, and a polypeptone. Imine 12 201228822 〇yy〇/pif resin, polyester resin, bismaleimide resin, polyolefin resin, isocyanate resin, and the like. Examples of the thermoplastic resin include a phenoxy resin, a polyether sulfone, a polysulfone, a polysulfone, a polyphenylene sulfide, a polyphenylene ether, a polyether quinone, and an ABS resin. The thermoplastic resin and the thermosetting resin may be used singly or in combination of two or more. In addition, a resin containing a cyano group may be used. Specifically, an ABS resin or a unit having a cyano group on a side chain as described in JP-A-2010-84196 [0039] to [0063] may be used. polymer". In addition, if an epoxy resin or an ABS resin is used as a substrate, a Nitrile Butadiene Rubber (NBR) or a Styrene Butadiene Rubber 'SBR-like polymer is used as the adhesion auxiliary layer, and the adhesion is made. The auxiliary layer can be used to relax the stress applied to the substrate or the polymer layer upon heating, and is preferable. The method of forming the splicing auxiliary layer is not particularly limited, and examples thereof include greening the layer used on the substrate, or dissolving the essential component in a solvent which can be bathed, and then applying it to the substrate by a coating method. a method of drying on the surface, and the like. The heating temperature and time of the green towel can be adjusted by selecting a coating solvent. However, from the viewpoint of manufacturing flexibility, it is preferably in the range of 200 〇c or less and 60 minutes or less. I is a heating condition in which the heating temperature is 4 Gt to 1 GG ° C and the time is within 2 knives. Further, the solvent to be used is appropriately selected from the resin to be used (e.g., cyclohexanium, 13 201228822 methylethylguanidine). [Polymer] The polymer used in the financial system has a polymerizable group = a diradical group (hereinafter, appropriately referred to as an (interacting group) = (a) energy group and its impurities are described in detail. In the case where the polymer is polymerized or polymerized, for example, a radical polymerizable group or a cationic polymerizable group is used as a reactive defect, and a free silky group is used. For example, a propionate group, a methacrylate group, a base, a croton base, an isocyanate shout, a cis-butyl succinate, a saturated base, a phenylethyl group, a vinyl group, a decylamine a group, a methylpropenylamine group, etc. wherein 'preferably a methyl propyl group-g group (methacryl fluorenyl group), an acrylate group (propylene fluorenyl group), a vinyl group, a styryl propylene propylene group Methyl acrylamide, particularly preferably a propyl group, a propylene group, a styryl group. (Interactive group) An interactive group is a functional group that interacts with copper ions (coordinating group) , metal ion-adsorbing group), may use a functional group capable of forming electrostatic interaction with copper ions, or may form a coordination with copper ions A nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, etc. The earth as an interactive group 'is, for example, a non-dissociable functional group (a functional group which does not generate a proton by dissociation), etc. i 201228822 /pif Specific examples of the interactive group include an amine group, a guanamine group, a sulfhydryl group, a ureido group, a tertiary amino group, an ammonium group, a decyl group, a triazine group, and a diwax. , benzotrimyl, sulphate, benzoquinone, hydrazino, hydrazine, hydrazine, hydrazine, η, 啥嗤, 啥嗤, 啥, 啥a group, a triazinyl group, a piperidinyl group, a piperazinyl group, a pyrrolidinyl group, a pyrazolyl group, an anilino group, a group having a alkyl group structure, a group containing an iso-cyanuric acid structure, a nitro group, an anthranylene group, Nitrogen-containing functional groups such as azo, diazo, azide, cyano, cyanate (R_〇_CN), ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, carbonate group, m group, An oxy-functional group such as a vinegar group, a group containing an N-oxide structure, a group containing an s_oxide structure, a group having an N-hydroxy structure, a thienyl group, a thiol group, a thiourea group, Polythiocyanate group, benzothiazolyl group, mercaptotriazinyl group, thioether group, thioketo group, sulfoxide group, sulfhydryl group, sulfide group, group containing sulfone imine structure, containing trimethyl iodide a phosphorus-containing functional group such as a sulfoxide salt-based group, a sulfonic acid group, or a sulfonate-containing group-containing group; a phosphate-containing functional group such as a phosphate group, a phosphonium amino group, a phosphino group, or a phosphate group-containing group; And a salt of a halogen atom such as bromine, etc., which may be used in a functional group having a salt structure. Among them, a carboxyl group or a sulfonic acid is preferred because of its high polarity and high adsorption performance for copper ions and the like. a base group, a phosphate group, and a boronic acid group, or an ether group or a cyano group, more preferably a carboxyl group or a cyano group. In the polymer towel, two or more kinds of functional groups may be contained as an interaction. The ether group is preferably a polyoxyalkylene group represented by the following formula (X). 15 201228822 jyyo /pn

Formula (X) * '(Y〇)n-RC Formula (X) Let 'Y denote the number of extended bases, RC ~ 30. * indicates the bonding position. As the stretching group, it is preferable that the carbon number is 3 ▲ and the ethyl group and the stretching group are listed. The hexyl group and the ethyl group are preferably used as the alkyl group, and the carbon number is preferably exemplified. Specifically, 5 may preferably have a number of 1 to 30, preferably 3 to 23. The value of _ value can be determined by a known method (nuclear magnetic resonance η η: Resonance, NMR) or the like. Ear Magnetic = The molecular weight is not particularly limited, but is preferably 7 G or less, more preferably 2 or more. From the viewpoint of polymerization sensitivity, it is preferably fine (10) or more. ^, the degree of polymerization of the polymer is not _ (7) above the polymer, more than 2G polymer or more, the following is the best, especially the surface polymer lower phase is better as a toilet polymer (preferred form 1) The preferred position of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A total of 201228822 jyys/pif polymer. In addition, the so-called unit refers to the repeating unit.

(a) (b) In the above formulae (a) and (b), R1 to R5 each independently represent a gas atom or a substituted or unsubstituted alkyl group. When R1 to R5 are a substituted or unsubstituted alkyl group, examples of the unsubstituted alkyl group include a mercapto group, an ethyl group, a propyl group or a butyl group. Further, examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group substituted by a methoxy group, a gas atom, a bromine atom or a fluorine atom. Further, 'as R1, preferably a fluorenyl group substituted by a hydrogen atom, a fluorenyl group or a bromine atom. As R2, a fluorenyl group substituted by a hydrogen atom, a methyl group or a bromine atom is preferred. R3 is preferably a hydrogen atom. As R4, a hydrogen atom is preferred. As R5, a fluorenyl group substituted by a hydrogen atom, a fluorenyl group or a bromine atom is preferred. In the above formulae (a) and (b), X, hydrazine and hydrazine each independently represent a single bond or a substituted or unsubstituted divalent organic group. The divalent organic group 'is exemplified by a substituted or unsubstituted aliphatic hydrocarbon group (compared with 17 201228822 pif preferably having a carbon number of 丨~... substituted or unmodified hydrocarbons preferably having a carbon number of 6 to 12) ), -〇-, each, -SCV, -N(RM R: silk), -CO-, -NH-, ·(:〇〇_, (〇ΝΗ_, or a combination of these (for example) a stretched oxy group, a stretched oxy group, a benzyloxy group, etc.), etc. As the substituted or unsubstituted aliphatic hydrocarbon group, a methylene group, an exoethyl group, a propyl group or a butyl group is preferable. Or a group in which the group is substituted by a methoxy group, a chlorine atom, a bromine atom or a fluorine atom, etc. As the substituted or unsubstituted aromatic hydrocarbon group, it is preferably an unsubstituted extended group, or a substituted phenyl group substituted with an oxy group, a chlorine atom, a _ sub, a ruthenium atom or the like. As X, Y and Z, a single bond, an ester group (_c〇〇_), a decylamino group (-CONH-) is preferably exemplified. And an ether group (_〇_), or a substituted or unsubstituted aromatic hydrocarbon group, etc., more preferably a single bond, an ester group (_c〇〇_), an amidino group (-CONH·). a) and (b), L1 and L2 are independent The site represents a single bond or a substituted or unsubstituted divalent organic group. The definition of the divalent organic group is the same as the divalent organic group described in the above X, Y and Z. An aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a divalent organic group having a urethane bond or a urea bond (for example, an aliphatic hydrocarbon group), wherein the carbon number is preferably from 1 to 9. Further, this is The total carbon number of L1 is the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L1. As the structure of L1, more specifically, it is preferably The structure represented by the following formula (M) or formula (1-2) 201228822 wa /pif [Chemical 2] /RaNL attack

Η Η H Formula (1-1) Formula (II) In the above formula (1-1) and formula (1-2), Ra and Rb are each independently composed of a carbon atom, a hydrogen atom, and an oxygen atom. A divalent organic group formed by two or more atoms in the group. Preferably, a substituted or unsubstituted methylene group, an exoethyl group, a propyl group or a butyl group, or an oxirane group, a dioxirane group, a trioxirane group, Tetraethylene oxide group, propylene oxide group, tripropylene oxide group, tetrapropylene oxide group. Further, L2 is preferably a single bond, or a linear, branched or cyclic stretch, an aromatic group, or a combination of these. The group in which the alkylene group and the aromatic group are combined may be further combined via an ether group, an ester group, a guanamine group, a urethane group or a urea group. Among them, L2 is preferably a single bond, and the total carbon number is from 1 to 15, particularly preferably unsubstituted. Here, the "carbon number" of l2 herein means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L2. Specific examples thereof include a methylene group, an ethylidene group, a propyl group, a butyl group, and a phenyl group, and the groups are substituted by a methoxy group, a woven ring, a gas atom, a desert atom, and U. Base 'and then combine these groups. The functional group): upper: ir functional group that interacts with copper ions. 19 201228822

The preferred form of the polymerizable group represented by the above formula (3) is a unit represented by the following formula (c). [Chemical 3]

The definitions of '...^ and ^ are the same as those of the bases in the early days represented by the formula (4). A represents an oxygen atom, or N == sister group' is preferably a nitrogen atom or Wei is 1 to 5, which is not taken. (4) is used as a table: 表:表科单福(四)' can be enumerated by the formula [Chemical 4]

The definition of the formula (4) is the same as the definition of each group in the unit of R1, R2, and L! 20 201228822 〇yy〇 /pif in the formula (d) represented by the formula (a). A and T represent an oxygen atom or nR (R represents a hydrogen atom or an alkyl group ' is preferably a hydrogen atom or an unsubstituted alkyl group having a carbon number of 1 to 5). In the above formula (d), the butyl group is preferably an oxygen atom. Further, in the above formula (c) and formula (d), L1 is preferably an unsubstituted alkylene group or a divalent organic group having a urethane bond or a urea bond, more preferably an amine group. The divalent organic group of the acid ester bond is particularly preferably a total carbon number of 1 to 9. In addition, as a preferable form of the interactive group unit represented by the formula (b), a unit represented by the following formula (e) is exemplified. [5] R5

Q

In the formula (e), the above formula (e) is the same as the definition of the base represented by the formula (b). Q represents an oxygen atom, or he, U, a burnt base) / a silky substance is a hydrogen material or an unsubstituted alkyl group having a carbon number of 1 to 5 on the other dioxins. 0:: L2 is preferably a straight chain, Branch or ring extension, soil or a combination of these. 21 201228822 .-- 1 π In the formula (e), the junction with the interacting group in L2: ^ a divalent organic soil having a linear, branched or cyclic stretching group, sk, the second The organic group of the valence is preferably a total carbon number of from 1 to 10. The other two are the other preferred forms, and the L3 in the formula (4) is preferably a bivalent organic group having an aromatic group and having an aromatic group. The total carbon number is 6 to 15. Preferably, the yttrium-containing element is preferably 5 mils / Å to 5 angstroms % relative to all of the monomers 3 in the polymer. If it is less than 5 mol%, there is reactivity, (hard === case, if it exceeds 5. mol%, it is easy to gel at the time of synthesis: from a difficult point of view, it is preferable; :: ί: The adsorption axis of the diion is preferably ~95 mol%, more preferably 丨. Molar; (better form 2) 耳耳/〇. Formula 2 is a preferred form, and it can be exemplified by the following formula (8) and (c) a copolymer of the units indicated.

V (C) 22 201228822 ^yy〇 /pif _ The unit of the table T represented by the formula (A) is the same as the unit represented by the above formula (4). R5'X&L2 in the unit represented by the formula (B) is the same as R5, X and L2 in the unit represented by the above formula (b), and the description of each group is also the same. The Wa of the formula (B) towel represents a hydrophilic group which is represented by V, which will be described later, or a functional group which forms a interaction with the steel ions in the precursor group. : (C) towel 'R6 points · Stands for a hydrogen atom or a substituted == generation. The definition of the hospital base is the same as the above-mentioned ^ R1 to R5, and A represents a single bond, or a substituted or unsubstituted one = organic soil. - The organic group of the valence ^ ^ ^ ^ ^ represents the same divalent organic group. This is defined by Χ 式 in formula (C), τ3 is the divalent right-ΜV early bond, or substituted or unsubstituted: the definition of the two = organic group and the above formula (C) , ν矣-ώ Aqueous base, as long as it is a submerged-underwater base or its precursor base. The term "hydroxy" or "acid" is not particularly limited, and is, for example, a predetermined group (external 'so-called hydrophilic (four)), a carboxyl group, etc. 2_tetrapyrranyl) as a hydrophilic group, the polymer layer is easy to be wetted with various aqueous treatment liquids. 2012 20122222 jyy〇/\>iL· plating solution From the viewpoint of further emphasizing the effects of the invention, a preferred A " polar group, specifically, a polar group is exemplified as the ionic gamma & 4 L acid group, the tartaric acid group , the acid-filling group, and the boron-based group, wherein, in terms of acidity (in terms of, preferably, New Zealand, I, the base), in particular, the decomposition of the bean is represented by the formula (C). # It's early in the sputum, it is moderately acidic (not to smash other s sulfhydryl groups), drying in an alkaline aqueous solution is easy due to the ring structure (4) for the helmet, ^... / M hydrophobicity point of view, Preferably, V is a carboxylic acid group, and a Vf 1 ring structure of L3. Here, as a member of 4 to 8 members, a base magnetic, cyclooctyl group, or phenyl group having 4 to 8 members Preferably, in addition, in the unit represented by S(c), other functional groups are decomposed), in the alkaline aqueous solution, -^ is a Newtyl group, and the chain length of L3 is 6 to 18 The 'chain length of L3' at the original σ means that _ & is preferred in the formula (c). It is preferable that the U and V are separated by a distance of six and a range of the rabbit Τ 3 ΛΑΜ e U thousands.乍 is the chain length of L, more preferably 6 ~ 14 original: ~ ~ 12 atoms. More preferably, the content of the second preferred embodiment of the above polymer is as follows. The preferred unit represented by the formula (Α) is preferably relative to the polymerization port from the viewpoints of reactivity (hardenability, aggregation) and inhibition of gelation during synthesis.

24 228822

All units of Jyy8/pif contain 5 mol%~5~30 mol%. Mohr / °, more preferably 5 mol % - type of wet - developability and resistance, containing 1 〇 mol% ~ 7 〇 tt is the phase f of all the monocular % of the polymer, especially good 30 mol%~5〇莫° ear% is 2 〇mol %~60 Mo value morphological ionic pole 15 m ι based Wei group in the case of acid value), preferably U job> l / g ~ 7.0 mmol / g, more preferably 17 mm 〇 i / g ~ 5 〇: Τ 2, particularly preferably 1,9 mmol / g ~ 4.0 mm 〇 i / g. When the ionicity is in this range, the developability of the aqueous solution can be suppressed and the decrease in the adhesion of the wet heat can be suppressed. As a specific example of the above-mentioned polymer, the polymer described in paragraphs [0106] to [〇112] of JP-A-2009-007540 can be used as a radical polymerizable group and a mutual ion with copper ions. Functional polymer of the functional group. Further, as the polymer having a radical polymerizable group and an ionic polar group, the polymer described in paragraph [0065] to paragraph [〇〇7〇] of JP-A-2006-13 5271 can be used. The polymer described in paragraphs [0030] to [0108] of US2010-080964 can be used as a polymer having a radical polymerizable group, a functional group which forms an interaction with a copper ion, and an ionic polar group. 25 201228822 jyy〇 / In addition, the following polymers may also be mentioned. [chemical

26 201228822 jyy»/pif

(Method for synthesizing a polymer) The method for synthesizing the above-mentioned polymer is not particularly limited, and a monomer which is a commercially available product or a combination of a known synthesis method can be referred to Japanese Patent Publication No. 2 The paragraph of _7662 is used [Shengang's method to synthesize the above polymer. When the field polymerizable group is a radical polymerizable group, the synthesis method can be favored. a monomer having a functional group of 2 or 2 free-linking groups, having a mutual monomer and having a self-method; and U) copolymerizing a monomer having a reactive group and a precursor of the radical, and then utilizing 27 201228822 /μη test processing method for introducing a radical polymerizable group; (6) copolymerizing a monomer having an interactive group and a monomer having a reactive group for introducing a radical polymerizable group, and then introducing freedom A method of silky group. From the viewpoint of synthetic suitability, the preferred methods are the above-mentioned methods and the methods of the above iii). The type of the polymerization reaction at the time of the synthesis is not particularly limited, and it is preferably carried out by radical polymerization.

Again, When synthesizing a copolymer comprising a unit represented by the above formula (A), formula (B), and formula, a monomer having a hydrophilic group or a precursor thereof, a (four) hydrophilic group or a precursor thereof may be used. The monomer of the interactive group of the base material is a copolymer of the above-mentioned 丨) to the above-mentioned method. I (polymerization layer-forming composition) It is preferred to use the polymer and the solvent in the polymer layer-forming composition, and it can be used in the operation of the step (1). The content of the polymer in the polymer layer-forming composition is not required to be 'from 2% by mass to 50% by mass based on the total amount of the composition, and is from 5 to 3 % by mass. When # is in the above range, the composition is excellent in handleability, and it is easy to control the layer thickness of the polymer layer. Preferably, the polymer layer-forming composition contains a solvent. (10) There are no mosquitoes, such as bribes, methanol, alcohols, glycols, glycerol, propylene glycol monomethyl ether, etc., and 容 丨 m _, methyl ethyl ketone, ring Ketone, etc. _ Solvent% styrene-acrylic acid-specific nitrile solvent, acetic acid A 81, acetic acid E;

28 201228822 A carbonate-based solvent such as diterpene ester or diethyl acrylate may be an ether solvent, a glycol solvent, an amine solvent, a thiol solvent, or a halogen solvent. Wherein 'preferably a guanamine-based solvent, an oxime-based solvent, a nitrile-based solvent, or a carbonate-based solvent' is specifically acetone, dimercaptoacetamide, mercaptoethyl ketone, cyclohexanone, acetonitrile. , propionitrile, fluorenyl hydrazine, ketone, dinonyl carbonate. The content of the solvent in the polymer layer-forming composition is not particularly limited, and is preferably 50% by mass to 98% by mass, and more preferably 70% by mass to 95% by mass based on the total mass of the composition. When it is in the above range, the handleability of the composition is excellent, and the control of the layer thickness of the polymer layer is easy. (Procedure of Step (1)) A method of applying a composition for forming a layer of a layer on a substrate.

A well-known method, such as a roll coating method. 'Extrusion coating allows the above polymer to contact the substrate on the substrate (or close to the auxiliary layer) without mosquitoes. - The method of directly polymerizing the polymer onto the substrate, or transferring the polymer to the spray Shouts (aggregate F method temple. It is easy to control, preferably to coat the composition

Curtain coater, die coater, method, enamel type coating, soil AI transfer pro-coating machine, extrusion type, coating method using gravure roll 29 201228822 From the viewpoint of handling property or manufacturing efficiency Preferably, the polymer layer-forming composition is applied onto a substrate (or an adhesion assisting layer) and dried to form a composition layer containing a polymer. When the composition for forming a polymer layer is brought into contact with the substrate, the coating amount is preferably 0.1 g/m 2 to 1 Å in terms of solid content from the viewpoint of sufficient interaction between the copper ions to be described later. g/m2 'excellently 〇5 g/m2 〜5 g/m2 ° Further, when the polymer layer is formed in this step, it may be between coating and drying at 20. (: ～40° C. for 0.5 hr to 2 hours to remove residual solvent. % (Energy imparted), as a method of imparting energy to a polymer (layer containing a polymer) on a substrate in this step, for example Radiation irradiation treatment such as heat treatment or exposure can be used. For example, it can be irradiated with light such as an ultraviolet ray (UV) lamp or visible light, or heated by a heating plate or the like. Mercury lamp, metal toothed lamp, gas lamp, chemical lamp, carbon arc material. As radiation, there are electron X-ray beam, far infrared ray, etc. In addition, g-ray, i-ray two-deep ultraviolet light, high-density energy beam are also produced. (laser beam). Le Tang ^ into the heat when 'for example, can use the same heating roller, laminating machine, add plate, infrared · ^ air blow dryer, oven, plus,,, pole, and outside the line Drying machine, heating roller, etc. As the time required for energy supply, the rooting of the roots = 201228822 jyys / pif into the ^ ^ ^ when the energy is given by exposure, in order to facilitate the graft polymerization get on, Further, in order to suppress the decomposition generated, the exposure power is preferably in the range of 1 GnJ/em2 to _QnJ/em2 = more preferably in the range of 1 〇〇 mJ7 cm 2 to 3000 mJ/cm 2 , and it is also possible to use nitrogen gas, helium gas, The gas is replaced with an acid gas such as diacidified carbon, and the oxygen concentration is suppressed to 6 〇〇 ppm or less, preferably PPm or less _ shot is turned off. T Μ is · The thickness of the obtained polymer layer is not particularly limited, and From the viewpoint of the adhesion of the copper plating film to the substrate, it is preferably 〇〇1 μηη~1〇μηη ' more preferably 〇〇5 μηη to 5 μηη. Further, 'dry powder thickness is preferably 〇〇5 g/ M2 to 20 g/m2, particularly preferably 0.1 g/m2 to 6 g/m2. Further, the surface roughness (Ra) of the polymer layer is preferably from the viewpoint of wiring shape and adhesion strength. Pm~0.3 μιη, more preferably 〇〇2 μιη~0.15 μιη. Further, the surface roughness (Ra) is Ra by the non-contact interference method according to JIS B, 0601 (rev. 20010120), and It is measured using Surfcom 3000A (manufactured by Tokyo Precision Co., Ltd.) The content of the material is preferably from 2% by mass to 100% by mass based on the total amount of the polymer layer, more preferably from 1% by mass to 1% by mass. Further, the polymer layer may also contain polymerization. When a polymerization initiator is contained, an active species (for example, a radical active species) is generated by energy supply to further promote a reaction between polymerizable groups, or a polymerizable group and a substrate (or an adhesion auxiliary layer). As a result, a copper-containing plating film having a high adhesion of 31 201228822 can be obtained. The polymerization system can use a thermal polymerization initiator to light her mouth. Month j (radical small-mouth initiator, anionic polymerization initiator), or a group having a _ group and a crosslinkable group on the side bond recorded in the Japanese Patent Laid-Open No. 9===::59 Γ Polymer (polymerization starting polymer, iso-port., as an example of photopolymerization initiator, ketone, amino benzophenone, Anji Cong, benzene, benzoin, benzene Oxime ketones, 肟g genus, 贞 蒽 = 蒽: 姆, bis- fluorenylphosphine oxide, phosphine oxide ruthenium dichloride: nitrogen compounds and their derivatives. In addition, the second class, The initiator "may also be a cationic polymerization initiator": Examples of the polymerization initiator include an aromatic sulfonium salt starting sulfonium salt and the like, and derivatives thereof. In the layer of the material, various additives may be contained in the outer layer. The effect of the effect of the ... and x may be added to the polymer layer in which the pattern P is formed in a pattern. 'Formation <Step (2): Catalyst imparting step> Step (1) is a polymerization obtained by containing copper ions and =: (1); pair =: _ copper Substep. In this step, the polymer layer palpitations; = 32 201228822 ^yy» /pif The interaction of the functional groups corresponds to its Wei, attached (adsorbed) copper ions in the ore. In the application step, it acts as a catalyst for electroless copper bismuth or an electrode for electrolytic copper plating. First, the plating catalyst liquid used in this step will be described in detail, and then the procedure of the step (2) will be described in detail. ^ (plating catalyst liquid) The plating catalyst liquid used in this step contains copper ions and is more than 3.0. The supply of copper ions to the catalyst liquid is not particularly limited as long as it can be plated. (4) The liquid towel is supplied to the genus (copper-containing compound), and is not particularly limited, and is preferably a form of a metal salt which is dissolved in a solvent and dissociated into a metal ion and an anion (anion). More specifically, Listed: copper nitrate, bis(triphenylphosphine) copper (I), copper (II) carbonate, basic copper carbonate (11), copper (II) dihydrate, copper, copper, ethyl acetonitrile Copper (bismuth), copper chloride (1), copper chloride (11), anhydrous copper (II), emulsified copper (II), sulfuric acid , copper (II) sulfate, copper (II) hydroxide, copper (11) ammonium sulfate, copper tartrate (11), copper iodate, copper iodide (1), copper chromite, copper (II) citrate, Copper citrate (11), copper (11) phosphate, copper (II) 2-ethylhexanoate, copper (II) oleate, copper oxalate (11), copper 2,4-pentanedioate (11), Portuguese , copper (II) saccharate, copper (H) isobutylate, copper chlorophyll trisodium salt, copper cyanide (1), sodium copper cyanide, potassium cyanide, copper thiocyanate (1), thiophene _2_Carboxylic acid copper (1), copper nitride (1), copper sulfide (I) gas [1,3-bis(2,6-di-isopropylphenyl)imidazole_2_subunit] copper (1) cyclohexane Burning copper (II) butyrate, acetophenone g with acid copper (Η), methanol copper (II), copper ethoxide (Π), hexafluoroacetic acid copper (H), copper isopropoxide (η), Benzene 33 201228822 bis-ethyl copper (1), copper (II) bromide, copper (I) bromide, copper (I) bromide complex, cyclopentadienyl (triethylphosphine) copper (1), hexafluorophosphate tetrakis (acetonitrile) copper (1), copper (II) pyrophoric acid, copper (I), copper (II), copper (II), copper in copper, %: burning Copper (II) acid, copper neodymium bismuth (bismuth), copper oxide, copper oxynitride, copper tungstate, double (B) Pyruvic acid) copper (II), bis(acetic acid tributyl acrylate) copper (II), bis (6,6,7,7,8,8,8-heptafluoro-2,2-didecyl- 3,5-octanedione acid) copper (II), copper telluride, copper oxide (1), copper oxide (strontium), lithium strontium oxide calcium, bis (2,2,6,6-tetradecyl-3,5 - heptane di g with acid) copper (ruthenium), bis (N, N'-di-t-butyl fluorenyl) dicopper (1), borohydride bis(triphenylphosphine) copper (1), trimethylphosphine (six Fluorinated propionate) copper (1), bromine (1,10-morpholine) (triphenylphosphine) copper (I), copper (II) acrylate, copper (II) methacrylate, copper phthalocyanine (11) , copper phthalocyanine (11) tetrasodium tetrasulfonate, copper benzenesulfinate (positive, copper fluoride (π), hexafluoro-2,4_glutaric acid copper (π), l'l'l· Difluoro-2,4-glutaric acid steel (π), hexafluoro-2,4-pentanedioate (1)-cyclooctadiene complex, tetrafluoroboric acid steel, copper trifluoroantimonate 11), copper trifluoroacetate (11), copper difluoroacetate pyruvate (11), copper triflate (1) benzene complex (2: 1), ethylenediamine _N, N, N, NL copper (11) disodium salt of tetraacetate, and the same. One of them is excellent in the solubility of the solution, and the effect of the present invention is more excellent. The content of copper ions in copper acetate, copper nitrate, copper sulfate, and especially copper acetate a catalyst liquid is not particularly limited, but it is preferably 0.001 mol/1 from the viewpoint of handling properties of Beijing: It is better to say that Moer is 0. 01 Moer/1~0.5 Moer/Bu money. The PH of the solvent is more than 3.0. If it is the above range, Bay

34 201228822 The jyy«/pif ion adheres sufficiently to the polymer layer, and a copper-containing plating film having a sufficient thickness and excellent adhesion can be obtained in a plating step to be described later. Among them, the solution stability of the plating catalyst liquid and the (four) removal property of the obtained copper-containing plating film are more excellent, the pH is (4) 3, more preferably 3.2 to 1 〇〇 f-the aspect is pH When it is 3.0 or less, the copper ion is not used for the polymer layer: the precipitation of the coating in the plating step described later, the enthalpy of the two-time application of the contact medium, or the addition of the above-mentioned steel ions, After the source, hunting is appropriate by acid (such as hydrochloric acid, sulfuric acid) " Or, in particular, the solvent for plating the catalyst liquid is not particularly suitable for workability, and it is preferable to make the environment adaptable and transparent (R_seQ_sis, R〇) water. Water seepage). *Ionic water, distilled water, refining and other 'optional solvent can be used if necessary: acetone, acetamidineacetic acid for the organic solvent, such as: acetic acid vinegar, cyclohexanyl, ethyl acetylene: benzene ^ propylene glycol Acetate series, triacetin, 2 servants, oxacin, N-methylpyrrolidone, dimethyl carbonate, sterol diacetate, diacetone alcohol, γ-butyrolactone, methanol, Acetyl, monomethyl cellosolve, diol monomethyl test, f-based cellosolve, ethyl solubilized fiber, normal diol, propylene ditetrafuran, 1,4-dioxane, n-methyl alcohol Tributyl ether, preferably a water-soluble organic solvent, preferably; ==, etc., wherein 'Compared with 酉夂一甲酷, dimethyl 35 201228822 D>y〇/μη? based cellosolve, triethylene glycol single Ether ether diethyl ether. Within the diethylene glycol dimethyl ether or diethylene glycol, the inclusion of the ship may also be in the range of the wire of the present invention: =: ρ Lists Ag, A1, Ni, C. Preferably, Fe, Pd, or 1 of the above gold i. In addition, as a plating catalyst precursor, it is preferable to list the ions on the cattle (_Ag ions, Pd ions, preferably Γΐ ϋ ϋ ϋ ϋ 的 的 的 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ ϋ 1G Fukushima-cho's work is very good (the procedure of step (2)) Special: Liaobu;: The contact method of the plating catalyst liquid is not used for the use of a known method. For example, : The plating catalyst is broken in the key contact: layer = ί: or the substrate with the polymer layer is immersed as the contact time, preferably about 3 sec to 24 hours, more preferably about 1 minute to about 1 hour. The temperature of the plating catalyst liquid at the time of contact is preferably 5. 〇~8 〇, about 15 ° c to 60 t or so. The amount of copper ions adsorbed in the polymer layer (adhesion amount) is used according to The type of the polymer, the concentration of the copper ion, and the like are different, but from the viewpoint of the precipitation property of the plating, it is preferably 5 mg/m 2 to 1000 mg/m 2 , more preferably 10 mg/m to 800 mg / M2' is more preferably 20 mg/m2 to 600 mg/m2. If the amount of copper ions adsorbed is too small, the precipitation of the plating described later becomes difficult 36 201228822 /pif , Where adhesion to the substrate, there is impaired. The amount and attaching (adhering i) can be measured by a known means (e.g., mass analysis device (sensing face electrically bonded poly mass spectrometer (Inductively c〇 knock ied

Plasma-Mass Spectromete, ICP-MS))). <Step (3): 帛1 aqueous solution contact step> The step (3) is a step of dissolving the polymerization in which copper ions are imparted in the step (7). By performing this step, the stability of the _ ions adhered to the material layer is improved, and the catalyst function of the plating described later is sufficiently exhibited. In view of the above, the pH is preferably from 8 to 14, and the pH is preferably an excellent liquid to be the above-mentioned pH; ^ is suitable; the method is preferably "the alkaline water-soluble method and the = contact treatment" = for

Preferably, it is 5 ° C to 2 Fan ^ 37 201228822 jyyo / In addition, as the contact time, it is preferably in the range of 5 seconds to 120 minutes, more preferably in the range of 15 seconds to 60 minutes, and even more preferably 30 seconds to 3 seconds. The range of minutes.川刀鲤 <Step (4): Plating step> One step (4) is a step of obtaining a copper-containing plating film by at least shoveling the polymer layer obtained in the step (3). More specifically, f, as shown in Fig. 1, is formed on the polymer layer 14 to have excellent conductivity and adhesion. _ Knife and have the step towel to carry out the _ _ silk limit ^, can be listed in the spring without electroless copper, electroplated copper. In addition, the "flat copper-containing chain film" can be used to woven non-de-plated steel and other methods. Into the electricity. The following is a description of the weaving process which can be preferably carried out in this step (electroless copper plating). The term "electroless steel" refers to the precipitation of metallic copper by chemical reaction using dissolved copper. In the case of the town, the method can be carried out as a method of riding the steel without electricity, and it is preferred to carry out the method in which the polymerization of the step (3) is immersed in a bath. ..., electrolytic plating steel As the electroless copper bath used, the steel bath can be deplated. "There is no electricity. The usual electroless_bath composition is preferably a solvent containing 201228822 jyys/pif 1. copper ion, 2. reducing agent, 3. additive for improving the stability of copper ions (stabilizer). As a solvent used in the money bath order, water is mainly mentioned. In addition, it is also possible to make a solvent for the solvent as needed, and it is difficult to be an organic solvent which is soluble in water. Examples of the water-soluble organic solvent include ketones such as acetone, and alcohols such as methanol, ethanol, and isopropyl alcohol. As the copper ion source, a known copper-containing compound can be used, and for example, a copper-containing compound or the like which is added to the above-mentioned paste coated contact liquid towel can be used. Among them, it is preferable to use gambling copper, gas scent, and copper, etc., and the content thereof is preferably about aig / L 〜 5 〇 g / L in terms of copper ions. Examples of the reducing agent include sodium borohydride, a boron-based reducing agent, formaldehyde, hypophosphorous acid, and the like. Examples of the stabilizing agent include ethylenediaminetetraacetic acid (EDTA).趟 = electroless copper bath ' For example, a plating bath containing Μ% as a copper ruthenium 3 ^' containing EDTA or a Rochant salt (5) ehdlesal as a copper-based agent may be mentioned. For example, the product of the product may be produced by a manufacturer (shared company): Thru-Cup PGT ATS Add copper IW or the like. Matter ====layer and electroless copper bath 哟 Pool is 1 a~m, around, more

right. The temperature of the mineral bath is not particularly difficult, but is preferably in the range of 5t to 8〇H 39 201228822 / pii, more preferably in the range of 15 ° C to 60 ° C. The film thickness of the formed copper plating film by electroless copper plating can be appropriately controlled by the copper ion concentration of the plating bath, the dipping time in the plating bath, or the temperature of the plating bath. When plating is performed in the following steps, conductivity may be exhibited, and it is preferably 0.1 μm to 3 μm. The copper plating film using electroless copper plating obtained in the above manner was observed by a scanning electron microscope (SEM) cross-section observation, and it was confirmed that fine particles containing copper were densely dispersed in the polymer layer, and 'Copper is further precipitated onto the polymer layer. The interface between the polymer layer and the copper plating film is a state in which the resin composite and the fine particles are mixed. Therefore, even if the interface between the polymer layer and the copper plating film is smooth (for example, Ra is 1.5 or less in a region of 1 mm), the adhesion is also changed. Good. (Electroplating Copper) In this step, electrolytic copper plating can also be performed. In addition, after the above-mentioned electroless copper is not formed, it can be formed as electricity, and (the power supply can be further carried out to carry out electrolytic copper ore. Therefore, it is possible to make an electroless plating which is excellent in the bonding of the substrate, and to form a new one. A steel-plated film having an arbitrary thickness. /, as a method of electrolytic copper plating, a known plating bath can be used as previously used in the shoveling bath, and the chemical plating method is additionally used. When the copper-plated copper-plated copper is obtained, it can be controlled by adjusting the flow density according to the use in the plating, etc. The degree of the twist, or the electric power, is used for the normal electric wiring. The conductivity view 201228822 /pif point is preferably 0.5 _~5〇μιη, more preferably 3 chat~%哗. ',,, electrolytic plating, or electrolytic plating. Obtained in this step In the copper-containing shovel film ==r' contains other metals than copper (:================================================================================= ): pattern forming step 〉 = (1) is to engrave the ship containing the ship obtained in the above-mentioned record step into a pattern' The step of forming a copper-containing plating film is formed. More specifically, = (in the step (D) of FIG. 1 is formed on the polymer layer 14 by removing the unnecessary portion of the ruthenium-containing film 16 ^. The remaining copper-bearing ore film 18. By this step, the unnecessary portion of the copper-containing plating film formed on the entire substrate surface is removed, thereby forming a desired copper-containing ruthenium film in a desired pattern. In the case of the pattern, any method can be used. Specifically, a well-known subtractive method can be used (a pattern-like mask is provided on the copper-containing plating film, and the region where the mask is not formed is subjected to (four) treatment, and then freshly removed to form a pattern-like method comprising a semi-additive method (a pattern-like material is provided on the copper-containing plating film, and plating is performed in such a manner that a non-axisy area towel forms a copper-containing recording film, and then the mask is removed and The method of performing the etching treatment to form a pattern-containing copper-containing plating film.] 201228822 The subtractive method specifically refers to a method of providing a resist layer on the formed copper-containing amount by pattern exposure and development. Forming a pattern with a copper-containing electron microscope film The same pattern, then the anti-surname pattern is used and used (10) liquid silk fairy, from the (four) recorded copper-containing money film. As an anti-surname agent, any material can be used, can be used negative, positive, liquid, film In addition, as a side method, any method that can be used at the time of manufacture can be arbitrarily selected by using wet wire engraving, dry=finance. In terms of operation of the operation, thirst-type engraving means, etc. From the viewpoint of simplicity, I can read 1 as an etching solution, and for example, an aqueous solution of vaporized copper or vaporized iron can be used. More specifically, (A) to (D) of FIG. 2 are dry-etched, rice, and rice. Step _ state.) The table does not use the subtractive method, first 'by performing the weaving step of the above step (4), and preparing the map: 7: the person shows (4) the substrate 1 〇, the insulating resin layer 22, and the adhesion is assisted by FIG. 2 In (4), on the surface of the substrate 及其) and its wiring 20. Insulating resin layer 22, dense: 'The surface of the face plate 1G is provided with the copper-containing surface 16, but the village is placed in the case of two cases = the number of the cover = 2 (8) is set on the top of the pattern (1) c) a copper-bearing ore film 16 that is not provided with a masked area by a finishing process (eg, dry..., M)

42 201228822 jyy« /pif The mask 24 is removed to obtain a patterned copper-containing coating 18 . Finally, the laminate of the present invention is obtained except for '. Force two into: !2 body refers to the following method: in the same pattern of the formed embossed pattern, and then the anti-butter pattern electrolysis key copper, the anti-pattern is removed, and the fast etched film is removed into a pattern. The method described above can be used by forming a pattern-containing steel-plated coating, a button-proofing agent, a buttoning solution, or the like, which can be used in the same manner as the subtractive method. More specifically, '(Α)~(Ε) of Fig. 3 shows a form in which the etching step of this embodiment is used. + + Addition Method First, the substrate 1 (), the gold wire 20, the insulating resin layer 22, the adhesion assisting layer 12, the polymer acoustic μ, and the copper-containing plating film 16 as shown in FIG. The layered body.曰 二 : : 4 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Then, as shown in (9) of FIG. 3, the mask is removed, and a etch process (for example, dry 湿, wet _) is performed to obtain a copper-containing plating film 18 having a pattern as shown in FIG. Laminated body. Further, the polymer layer may be removed together by a known means (e.g., dry etching) while removing the copper-containing plating film. Further, when the credit engraving step is carried out by the semi-additive method, as shown in FIG. 43 201228822 to (8), it is also possible to perform reading as shown in FIG. 4 (4) in order to obtain a multilayer wiring board. First, it is prepared to have a substrate. 1(), the wiring 20, the insulating resin layer 22, the adhesion assisting layer 12, the polymer genus, and the laminate of the copper-containing plating film 16. Α 〇 θ 4, next, as shown in (8) of FIG. 4, through the laser processing or drilling, the copper-containing lining 16, the polymer layer 14, the adhesion auxiliary layer 绝缘 the insulating resin layer 22, and the metal wiring are reached. 2 〇 square +, need, and then remove the slag treatment. When #成通孔. As shown in Fig. 4 (C), the through-hole wall formed by the field is pre-plated with a metal film 26 which is not twisted and is in contact with the metal wiring 20. After the plating is performed, the coating is performed, and as shown in Fig. 4(D), the mask 24 is placed on the metal film %, and electrolytic plating is performed (see (E) of Fig. 4). After the mask 24 is removed (refer to (F) of FIG. *), j processing (for example, dry type, wet side) is performed to obtain a pattern of gold and 々 30 (refer to (6) of FIG. 4). . Thereafter, the polymer layer 14 and the adhesion assisting layer 12 may be removed by electrical processing or the like as needed. 7 乂<arbitrary step (1): reduction step> upper, ten, 2, 1 aqueous solution contact step (step (1)) and before the second work 4 (step (4)) 'optional A reduction step of contacting the Jingyu layer with the reducing solution is carried out. By carrying out this step, the precipitation of copper-containing (tetra) in the hybrid step is improved, and the copper-containing ore film desired by the 2012 201228822 ^yys/pif can be obtained, and the surname characteristics and the like are further improved. The reducing liquid used in this step is not particularly limited as long as it is a solution capable of reducing copper ions imparted to the polymer. Usually, the reducing solution contains a reducing agent. As the reducing agent, various known reducing agents can be used. Among them, as far as the water-soluble (four)-transfer (four) viewpoint is concerned, it is preferably a water-soluble compound having a reducing action. Examples of the reducing agent include hydrogen, carbon monoxide, hydrazine, and amine borane (Dimethylamine Borane (DMAB), Trimethylamine Borane (TMAB), etc.), sulfurous acid, and Luo. Xerium salt, boron compound, organic boron compound, boron hydrogen compound (potassium borohydride, sodium borohydride, etc.), phosphite, hypophosphite (sodium hypophosphite, potassium hypophosphite, etc.), aldehyde (formaldehyde, etc.) ), phosphonates (肼, sodium phosphinate), hydroquinone, sugars and organic acids. It is not limited to the above-mentioned reducing agent, and is preferably an amine borane or an aldehyde. Among them, dimethylamine borane (DMAB) or formaldehyde is preferred. The reducing agent may be used singly or in combination of two or more.

The concentration of the reducing agent in the reducing solution is preferably such that the excess amount is in contact with the amount of copper ions in the polymer layer, and is preferably set to about 〇1 m〇1/L to 〇5 m〇1/L. It is preferably set to about 0.01 mol/L to 0.2 mol/L. The reducing solution may contain a solvent, and examples thereof include water, an alcohol such as 1-methoxy-2-propanol, and a glycol such as diethylene glycol dichloride. The pH of the reducing solution is not particularly limited, and may be appropriately set to a range in which the reducing performance is good and the stability of the reducing agent is not appropriate depending on the type of the reducing agent to be used. Usually, it is preferred to set the pH to 3 or more. The method of bringing the reducing solution into contact with the polymer layer is not particularly limited, and a method of applying the reducing solution to the polymer layer or a method of immersing the substrate having the polymer layer in the reducing solution may be mentioned. The contact time is not particularly limited, and from the viewpoint of productivity, it is preferably from 5 seconds to 120 minutes, more preferably from 30 seconds to 30 minutes. Further, the temperature of the reducing liquid at the time of contact is not particularly limited, and from the viewpoint of facilitating the original reaction, it is preferably 5 ° C to 8 ° C, more preferably 15 ° C to 60 ° C. <Steps of Rensi (Part 2): Second aqueous solution contact step> Preferably, after the above-described reduction step and before the above-described mineralization step, a polymer layer and an alkaline aqueous solution subjected to the reduction treatment are provided. The second alkaline aqueous solution in contact is contacted. By carrying out this step, the impurities generated in the reduction step can be removed from the polymer layer, and the precipitation of the mineral deposit in the plating step described later can be carried out more efficiently, and the surname characteristics and the like are further improved. The alkaline aqueous solution used is the same as the alkaline aqueous solution used in the step of contacting the above-mentioned second alkaline aqueous solution. Further, the aqueous solution to be used in this step may contain a reducing agent, and in particular, may also contain a reducing agent used in the plating step. By containing a reducing agent, the plating deposition property in the bonding step is more effectively performed, and the characteristics and the like are further improved. ^ The reducing agent to be contained may, for example, be a reducing agent or the like used in the above reduction step.

46 201228822 3yys7pif Further, the preferred amount of the reducing agent contained is the same as the range of the reducing agent in the reducing solution used in the above reduction step. Further, the method of contacting the polymer layer and the aqueous test solution in this step, the contact conditions, and the like can be carried out by the method and conditions of the above-described first aqueous solution. I. Phase Step Gate <Laminated Body> By carrying out the above steps, a laminate having a substrate, a polymer sound, and a patterned copper-containing plating film in this order can be obtained.积 The layered body of the present invention is preferably provided with a layered body containing a copper-containing ore film on a substrate having a surface roughness of 2 nm of 5 nm to nm (more preferably just nm or less). Further, the adhesion between the substrate and the copper-containing yam is preferably in the square test, and is 10 or less in 100 cells, and particularly preferably. That is, the laminated body of the present invention is characterized in that the surface of the substrate is smooth and the substrate and the copper-containing plating film are excellent in adhesion. 'The obtained laminate can be used in various fields, for example, for electrical. ^Sub.communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, coal, stone' oil, rubber, leather, automobile, precision machine , a wide range of industrial fields such as wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, it can be used in printers, personal computers, word processors, keyboards, personal digital assistants (PDAs), telephones, photocopiers, fax machines, electronic cash registers (ECC). ), calculator, electronic organizer, card, holder, hacking machine, office automation (〇ffice Automation, OA) machine 'washing machine, refrigerator, vacuum cleaner, microwave oven, lighting, game 47 201228822 machine, hopper, quilt Household appliances such as furnaces, televisions (Televisi〇n, τν), video tape recorders (VTRs), camcorders, cassette recorders, tape recorders, mini-discs, compact discs (c〇mpactDisk, CD) players , Yangsheng n, liquid crystal display audio-visual (AudiQVisud, AV) machine 'connector, relay, capacitor, switch, printed circuit board, winding 菅, semiconductor sealing material, LED (LightEmittingDi〇de, LED) sealing material, Wires, cables, transformers, biased light, distribution boards, semiconductor wafers, various electrical distribution boards, flexible printed circuit boards Flexible Printed Circuit 'FPC), Chip 〇n Film (c〇F), Tape Automated Bonding (TAB), Copper Clad Laminate (CCL), Electrical Wiring Uses such as materials, multilayer wiring boards, motherboards, antennas, electromagnetic wave prevention films, clocks, etc., electrical and electronic parts, and communication equipment. In particular, since the smoothness of the interface between the copper-containing plating film and the polymer layer is improved, it can be applied to, for example, decorations (eyeglass frames, car decorations, beads, game frames, western tableware, water pipe fittings, lighting fixtures, etc.) ) It is necessary to ensure various uses such as the use of high-cycle transmission. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. x The following is a detailed description of the synthesis method of the polymer used in the present example (Synthesis Example 1: Polymer A) To a 2 L three-necked flask, ethyl acetate 1 [, 2-aminoethanol 48 201228822 159 g ' was added. And use an ice bath for cooling. So that the internal temperature becomes 2〇. Adjust in the following manner and add 15 〇 g of 2-bromoisobutyric bromide to it. Thereafter, the inner; ΰπι· was topped up to the temperature (25 C) and reacted for 2 hours. After the completion of the reaction, 300 mL of water was added to the reaction and the reaction was stopped. Thereafter, the ethyl acetate layer was washed four times with 300 mL of distilled water, and then dried under magnesium sulfate, and then the ethyl acetate was taken into consideration to obtain the raw material AgOg. Next, a raw material A 47.4 g, pyridine 12 g, and ethyl acetate 150 mL were placed in a 500 mL three-necked flask, and the mixture was cooled in an ice bath. The internal temperature was adjusted to 20 ° C or less, and 25 g of acrylonitrile chloride was added dropwise thereto. Thereafter, it was raised to room temperature and reacted for 3 hours. After the reaction was completed, 300 mL of Rhodes water was chased and the reaction was stopped. Thereafter, the ethyl acetate layer was washed four times with steamed water, and then dried by sulfuric acid, thereby taking care of acetic acid. Thereafter, the following monoterpenes were purified by column chromatography to obtain 20 g of hydrazine. [Chemistry 9]

To a 500 mL three-necked flask, 8 g of hydrazine, hydrazine-dimethylacetamide was added, and heated to 65 ° C under a nitrogen gas stream. The monomer hydrazine was added dropwise thereto over 4 hours: 14.3 g, acrylonitrile ( </ br> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> 49 201228822 /pif After the completion of the dropwise addition, the reaction solution was further stirred for 3 hours. It was added with N, dimethyl acetamide 41 g, and the reaction solution was cooled ==. To the reaction solution, a 4-hydroxyl TEMp shirt was added as ti_g and a circle of 54.8 g, and it was made into a small amount at room temperature (4), and then a 70 mass% methanesulfonic acid aqueous solution 54 was added to the reaction liquid. Re-sinking the hall, and then taking out the solid matter ^ Α Α (weight average molecular weight is 3 4 magic (Mw / Mn = is in the polymerization potential difference automatic titration device (Kyoto Electronics Industry Co., Ltd.) as a titration Gl Μ &amp; Oxygen water-soluble silk measurement = the acid value of the extract A, and the acid value of the polymer a was 3 9 '. ♦ &amp; using an infrared (infrared 'IR) measuring machine (manufactured by Horiba): Identification of the obtained polymer A. (The compound was dissolved in _ and was carried out using KBr crystal. Ir = 吏 果 ' observed peaks around 2240 cm · 1 and is known;; = the nitrile has been Inductively into the polymer. In addition, by acid value, it is known that acrylic acid is added as a unit. In addition, the polymer is dissolved in 300 MHz manufactured by DimethylSUlfoxide (DMSO) tq_JBruk7r. NMR (AV-3〇0) was measured and observed in 2 5 〇 7 (5H) The broad peak of the nitrile-containing unit is 7.8-8.1 ppm 5.8-5.6 ppm(lH^).5; 4.52 ppm (m), 4.2_3.9 ppm (2H), 3·3_3 5 ppm (2h In 2.5-〇·7ρΡΙη (6Η), a broad peak corresponding to the polymerizable group was observed at 2.5-0.7 ppm (3Η), and a broad peak corresponding to Wei Weifan was observed, and the polymerizability was observed. Base unit: nitrile-containing unit: 201228822 jyy» /pif minus 2Γ0:30:40 —%)

40 mol% OOH O^o CN d; 0 (HN 〇人(Synthesis Example 2: Polymer B) To a 1000 ml Erkouzhi #山a 粍 bottle, 35 g of Ν-methylpyrrolidone was added and heated to 75 t: To this, 2.5-hour of acrylic acid was added dropwise to the 2-hydroxyethyl ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium. 65 g of N_methyl to bite _ 35 g solution. After the completion of the dropwise addition, the reaction solution was heated to 8 GC until further 3 hours. Thereafter, the reaction solution was cooled to room temperature. To the above reaction solution, 29 g of dibutyl butyl hydroquinone oxime, 0.29 g of dibutyltin dilaurate, 18.5 g of Karenz AOI (manufactured by Showa Denko KK), and N-mercapto guanidone 19 were added. g, and the reaction was carried out at 55 ° C for 6 hours. Thereafter, 3.6 g of methanol was added to the reaction liquid, and the reaction was further carried out for 1.5 hours. After the completion of the reaction, 'reprecipitation was carried out in water, and then the solid matter was taken out to obtain a polymer B25 g. (Identification of structure) 51 201228822 Polymer B was dissolved in heavy DMSO, and 300 MHz of NMR (AV-300) was measured and manufactured by Bruker. At 4.3-4.05 ppm

2.5-1.3 ppm (3H points) 1 bee, at 7.2-7.3 ppm (1H (2H points), 2.9-2.8 ppm (2H points), 2.5-1 observed a broad-wave bee corresponding to nitrile-containing units, ), 6.4-6.3 ppm (1H points), 6.2-6.1 ppm (1H points), 6.0-5.9 PPm (1H points), 4.3-4.05 PPm (6H points), 3·3_3.2 ppm (2H points), 2.5 A broad peak corresponding to the polymerizable group-containing unit was observed in -1.3 ppm (3H minutes), and it was found that the polymerizable group-containing unit: nitrile group-containing unit = 2 〇: 8 〇 (mol%). (Measurement of molecular weight) Polymer B was dissolved in tetrahydrofuran (THF) and molecular weight was measured using a high-speed gel permeation chromatograph (GPC) manufactured by Tosoh (HLC-8220GPC). . As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 53000 (Mw / Mn = 1.9) in terms of polystyrene. Further, the numerical values in the chemical formula of the following polymer B represent the molar % of each unit. [化11]

&lt;Example 1 &gt; 52 201228822 jyye/pif [Production of substrate] A glass epoxy substrate (MCL-E679W manufactured by Hitachi Chemical Co., Ltd.) was used as a substrate to have the roughness as described in Table 1 ( Grinding is carried out in the manner of Rz), and washing with water and alcohol. Then, the coating liquid (M) having the composition described later is applied by spin coating so that the film thickness after drying is 2 μm, and the adhesion assisting layer is provided by drying. Further, as shown in Table ,, thermal hardening is performed at a predetermined degree. [Formation of Polymer Layer] Thereafter, the coating liquid A having the composition described later was applied by a spin coating method, and uv exposure was performed on the surface. Thereafter, the "di(4) hydrogencarbonate layer = the polymer directly bonded to the auxiliary layer of the plate [the application of the catalyst]

The substrate of the polymer layer thus described was impregnated in Table 1 and further in the τ catalyst liquid (immersion time: 10 minutes' liquid temperature: 40 Å). : The pH of the di-layer was decreased, and the surface of the polymer layer was gently washed in the -L-H polyi-e1, and then the compound was broken down to the (4) core towel described in Table 1. Thereafter, in an aqueous solution containing 40 mmol/L NaOH 蛊29, which is 12) (corresponding to a % of replacement), the reducing component of the molten steel from the polymer is dehydrated. The reducing agent) is washed, and the polymer layer is used for the remainder of the above-mentioned reducing liquid. 53 201228822 /pif Externally produced sample Further, the amount of catalyst attached to the polymer layer is additionally quantified by mass analysis. [Plating] The electroless copper plating is carried out on the polymer layer to which the catalyst is added. The electroless plating is an electroless plating bath using the following composition using Thru-Cup PGT (manufactured by Uemura Industrial Co., Ltd.). The polymer layer was impregnated at a bath temperature of 30 ° t, and copper plating was formed so that the plating deposition thickness became 0.6 μm. The electroless plating solution was prepared as follows. Steaming water approximately 60% by volume PGT-A9.0 Capacity % PGT-B 6.0 Capacity % PGT-C 3.5 Capacity % Formaldehyde liquid * 2.3% by volume The last 'distilled water is used to make the total amount 1% by volume Surface adjustment. * The formaldehyde used here is the furfural liquid of Wako Pure Chemical (Special grade) Then, an electrolytic copper plating bath having the following composition was used to carry out electrolysis (so 6 A/dm 2 : 15 minutes, 3 A/dm 2 : 35 minutes) so that the copper thickness became 20 μm, thereby obtaining conductivity. Layered layer. (Composition of electrolytic copper plating bath) 1000 parts by weight 110 parts by weight 270 parts by weight 0.2 parts by weight • Water • Copper sulfate pentahydrate • 98% sulfuric acid • 35% hydrochloric acid 201228822 jy^o/pu • Made by Meltex 'Copper Gleam ST-901M 30 parts by weight&lt;Evaluation: Adhesiveness&gt; The obtained plating film was subjected to a hundred-bar peeling test by a checkered peel test (HS-K5600-5-6: 1999). In the form. [Tactile]

After heat-treating the substrate subjected to electrolytic copper plating at a temperature of 1 〇 ° C / 1 hour, the dry resist film was formed at 70 C and 0.2 MPa by a vacuum laminator (manufactured by Naji Seisakusho Co., Ltd.: mvlp_600). (Stock) manufactured, RY3315' film thickness is Ι5μιη) laminated on the surface of the substrate. Then, the substrate in which the dry resist film is laminated is adhered to the glass mask which can form the comb wiring (according to jPCA_bu〇1_2〇〇7) defined in JpCA_ET〇1, and the exposure machine with a center wavelength of 405 nm is used. The sputum is irradiated with 7 〇mJ Μ UZ Mh spray pressure on the exposed substrate by spraying 1% Na2 (: 〇3 aqueous solution and it is in the county. Thereafter, the rider is washed, machined, and formed on the bond copper film. A resist pattern for forming a method. The substrate having the resist pattern formed thereon is immersed in a FeC^/HCl aqueous solution (side liquid) at a temperature of 4 (TC), whereby the resist is not formed and the anti-money agent is not formed. The film in the patterned area towel is removed. Thereafter, a 3% Na〇H aqueous solution is sprayed onto the substrate by a spray pressure of ΜMPa, and the pattern is swollen and peeled off, and then the G% sulfuric acid aqueous solution is introduced into the substrate and processed into ^Washing' L/S = 20 μηη/75 μηι of the wiring obtained by the comb-shaped wiring (patterned copper film). <Evaluation: Etching characteristics (fine wiring formation property)> Using a microscope The obtained pattern-like film is observed at 55 201228822 jy^o /μιι, and the wire breakage or In the case of a defect such as thinness, thickening, or bending, it is evaluated as "X". The case where the defect is not observed and the linearity of the wiring is excellent is evaluated as "〇". The obtained result is described as "fine wiring formation property" in the table. In addition, the thinning of the wiring means that the wiring is reduced to 2/3 or less of the design value. The thickening of the wiring means that the wiring is thicker than 4/3 of the design value. ' is a width region that exceeds the width of the designed wiring, and the wiring is 蜿蜒. <Evaluation: Etching characteristics (metal residue removal)> Using a commercially available gasified iron liquid (manufactured by Tsurumi Soda (share), 4〇°Be,) The copper recording film obtained in the above bonding step is completely etched, and the catalyst residue in the button portion is observed. Specifically, in the above solution (liquid temperature: 40). (:), the copper plating film was treated for 2 minutes using an etching apparatus ED-1200 manufactured by Mikasa Co., Ltd., and then etched. The color of the surface of the substrate after etching was the same as that of the original substrate as metal (copper). Is roughly removed In the case of "〇", it is assumed that the change in color tone is "△", and the case where the color is noticeably colored in brown or black is "x". The obtained result is referred to as "metal residue removal property". "S" is shown in Table 1. <Example 2 - Example 14> The coating liquid for forming the adhesion assisting layer to be used was changed as described in Table 1 in the same procedure as in Example 1. 1 to J-4, and κ), a coating liquid (A to C) for forming a polymer layer, a catalyst liquid (S-1 to S-4), and a reducing solution (Z-1 to Z_3), and Smoothness of the substrate, and pattern plating

56 201228822 jyy» /pif Copper film. In addition, it is shown in Table 1. The same evaluation as in Example 1 was carried out, and the result was also - and <Comparative Example 1> was patterned-plated_1 = knot = ^^. 14 mesh_program system &lt;Comparative Example 2&gt;

J. Aegis ctmtorMAT-2-A containing palladium salt (Supreme 丄 有限 有限 有限 触 触 触 触 — 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不 不A patterned copper plating film was produced in the same manner as in Example 1. The evaluation results are shown in Table i. &lt;Comparative Example 3&gt; Bayside 1 replaced the actual _[catalyst material] in Example 1 by the addition of the catalyst of the standard method of the commercially available liquid contained in the following five, and by way of example, 1 phase _ program to make a picture of the remaining mine _. The evaluation results are shown in Table 1. (Standard method of commercially available liquid) The substrate having the polymer layer obtained above was immersed in Thru-CupACL-009 (temperature: 50 〇C, immersion time: 5 minutes), and then washed with water, and After that, the substrate was immersed in an ALCUP Activator MAT-2 (manufactured by Uemura Kogyo Co., Ltd.) (temperature: 6 ° C, dipping time: 5 minutes) and washed with water. Further, the substrate was then immersed in an ALCUP Reducer MAB (manufactured by Uemura Kogyo Co., Ltd.) (temperature: 35 C 'bay time. 3 minutes) and washed with water. Further, 57 201228822 /pif Thereafter, the substrate was immersed in ALCUP Accelerator MEL_3-A (manufactured by Uemura Industrial Co., Ltd.) (temperature: 26 ° C, dipping time: 1 minute). Furthermore, even if Activator MAT-31 (manufactured by Uemura Kogyo Co., Ltd.) is used instead of Activator, the same result can be obtained. &lt;Comparative Example 4 to Comparative Example 6 &gt; When a catalyst was added, a commercially available ALCUP Activator MAT-2-A (manufactured by Uemura Kogyo Co., Ltd.) containing a salt was used instead of the forging fluid S-1. In the same manner as in Example 1, except that the coating liquid (J-2) to the coating liquid (j_4) were used instead of the coating liquid for the production of the adhesion assisting layer, the pattern copper ore was produced by the same procedure as in Example 1. membrane. The evaluation results are shown in Table 1. &lt;Comparative Example 7&gt; A prepreg of a commercially available colloidal tin-palladium catalyst (Thru_Cup PED-104 manufactured by Uemura Kogyo Co., Ltd.) and a commercially available product were used without using an adhesion assisting layer. Instead of the plating catalyst liquid, a colloidal tin-palladium catalyst (Thm-CupAT-105 manufactured by Uemura Industrial Co., Ltd.) and a commercially available active treatment liquid (Thru-Cup AL-106 manufactured by Uemura Industrial Co., Ltd.) In the same manner as in Example 1, except for the above, a patterned steel-plated film was produced. &lt;Comparative Example 8&gt; In addition to changing the smoothness of the substrate, a pattern-shaped copper plating film was produced by a procedure similar to that of _7 (4). The evaluation results are shown in Table j. &lt;Comparative Example 9&gt; The coating liquid (J-2) was used instead of the coating liquid (M), and the metal copper colloid produced by the method described later in 58 201228822 /pif was used instead of the plating catalyst liquid (S -1) Except for this, a patterned copper plating film was produced by the same procedure as in Example 。. The evaluation results are shown in Table i. (Metallic copper colloid) 30 g of gelatin was added to 7 μl of pure water at a liquid temperature of about 6 Torr. This was dissolved in 〇, and then 5 〇g of copper sulfate pentahydrate and 1 〇g of polyethylene glycol (average molecular weight of 20,000) were added, and the solution was dissolved. Then, 'add α,α-bipyridine 20 mg, dissolve it, add 12 〇ml of dimethylamine borane solution at a concentration of loo g/i, and reduce copper ions to metal copper at liquid temperature 6 (rc) Further, after aging for about 1 hour at the liquid temperature, the liquid temperature was cooled to room temperature, and pure water was added to make the volume of the aqueous solution 1 liter. Extract 100 ml of the solution and add about 800 ml of pure water for dilution. The pH of the diluted solution was adjusted to 6 with an aqueous sodium hydroxide solution, and then pure water was added to make the total amount of the diluted solution 1 liter, thereby preparing a metallic copper colloid. <Comparative Example 1 〇> Using a coating liquid (J -2) Instead of the coating liquid (J-1), and using commercially available nano copper powder (particle size 20 nm to 40 nm) (C〇pper nanopowder, Wako Pure Chemical Industries 045504, manufactured by Alfa Aesar) A pattern-shaped copper plating film was produced by the same procedure as in Example 1 except that the catalyst liquid (S-1) was plated. The evaluation results are shown in Table 1. <Comparative Example 11> In addition to using plating touch A pattern-like copper plating film was produced by the same procedure as in Example 1 except that the vehicle liquid (S-5) was used instead of the plating catalyst liquid. 59 201228822 The evaluation results are shown in Table 1. <Comparative Example 12> A patterned steel plating was produced by the same procedure as in Example 1 except that the plating catalyst liquid (S-6) was used instead of the plating catalyst liquid. The evaluation results are shown in Table 1. '&lt;Comparative Example 13&gt; The same procedure as in Example 1 was used except that the plating catalyst liquid (S-7) was used instead of the plating catalyst liquid (si). A patterned copper ore film was produced. The evaluation results are shown in Table 1. <Comparative Example 14> In addition to using a plating catalyst liquid (S-8) instead of the plating catalyst liquid (S-1), The pattern-like shovel copper film was produced in the same procedure as in Example 1. The evaluation results are shown in Table 1. In addition, the surface roughness of the substrate in Table 1 was a laser microscope (manufactured by Keyence Corporation), and JIS B 0601 was used. (1994), surface roughness Rz measured by the 10-point average height method. 201228822 J-az, 866rn etching characteristics metal detachment 〇 &lt;&lt;1&lt;1&lt;1&lt; Ο &lt; 〇〇Ο 〇〇〇XXXXXXXXX Fine wiring formability 〇Ο 0 0 〇Ο 〇Ο 〇〇〇〇Ο 〇XXXXXXXXX Square peeling grid residual 100% 100% 100% 100% 100% 90% 100% 100% 100% 100% 100% ! loo% 100% 100% 100% 100% 100% 100% 100% 100% ο 100% 〇 Reduction solution N Ν Ν Ν Ν τ-Η Ν Ν CN Ν Ν 1&quot;Η Ν Ν Ν SI Ν Contact amount of catalyst 50 mg/m2 80 mg/m2 100 mg/m2 30 mg/m2 40 mg/m2 80 mg /m2 200 mg/m2 30 mg/m2 120 mg/m2 50 mg/m2 50 mg/m2 50 xng/m2 50 mg/m2 CN tso 100 mg/m2 50 mg/m2 50 mg/m2 30 mg/m2 40 mg /m2 50 mg/m2 10 mg/m2 30 mg/m2 50 mg/m2 Plating Catalyst Τ-Η ζλ &lt;s ΓΟ fO ζλ 00 CN CZ3 °? xk Η ζΛ υη Η ζλ t/1 CO Salt palladium salt salt salt ίε salt colloidal tin palladium colloidal tin palladium metal copper colloid &lt; CC (Ώ U &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;C&lt; Carbon &lt; Adhesive support layer (thermosetting) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J- 1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) κ (without heat hardening) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J- 2 (180 ° C, 30 minutes) J-3 (17 0 ° C, 60 minutes) J-4 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J-2 (180 ° C, 30 minutes) J-3 (170 ° C, 60 minutes) J-4 (170 °C, 60 minutes) J-2 (180°C, 30 minutes) Substrate surface roughness (Rz) 0.2 μπι 0.2 μηι 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μιη 0.2 μπι 0.2 μπι 2.1 μπι 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μΐΏ 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μπι 0.2 μηι 0.2 μηι 2.1 μπι 0.2 μηι Implementation 1 Implementation 2 Implementation 3 Implementation 4 Implementation 5 Implementation 6 Implementation 7 Implementation 8 Implementation 9 1 Implementation 10 Implementation 11 Implementation 12 1 Implementation 13 1 Implementation 14 Comparison 1 Comparison 2 Comparison 3 1 Comparison 4 I Comparison 5 Comparison 6 Comparison 7 Comparison 8 Comparison 9 19 201228822 Ja oo66e / / / / / / 1 No plating deposition, no plating deposition, no plating deposition Plating is carried out without plating, no adhesion, no adhesion, no adhesion, 20 mg/m2, 5 mg/m2, metal copper powder, C/3 '•Ο Rt t/3 00 Xfl &lt; C &lt;&lt;&lt; J-2 (180 ° C, 30 minutes) J-1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) J- 1 (170 ° C, 60 minutes) J-1 (170 ° C, 60 minutes) 0.2 μπι 0.2 μιη 0.2 μπι 0.2 μπι 0.2 μπι Compare 10 Compare 11 Compare 12 Compare 13 Compare 14 201228822 〇yy〇/pif &lt; Coating liquid for layer&gt; (composition of coating liquid (J-1)) • 52 parts by weight of cyclohexanone • Liquid double F-type epoxy resin JER806, manufactured by Mitsubishi Chemical 15 parts by weight • Phenoxy resin YP- 50EK30, 30 parts by weight of Nippon Steel Chemical Co., Ltd. PHENOLITELA-7052, 3 parts by weight of DIC, 0.2 parts by weight of 2-ethyl-4-mercaptoimidazole (composition of coating liquid (J-2)) 67 parts by weight of pentanone • 5 parts by weight of methyl ethyl ketone • Liquid double F-type epoxy resin JER806, 15 parts by weight of Mitsubishi Chemical • Phenoxy resin YP-50, 10 parts by weight of Xinyi Iron Chemical Co., Ltd. • Novolak resin PHENOLITELA-7052, 3 parts by weight of DIC•0.2 parts by weight of 2-ethyl-4-mercaptoimidazole (composition of coating liquid (J-3)) • 72 parts by weight of cyclopentanone • Double F in liquid form Epoxy resin JER806, manufactured by Mitsubishi Chemical 15 parts by weight • Phenoxy resin YP-50, Nippon Steel Chemical Co., Ltd. 10 parts by weight 63 201228822 • Nonylphenol novolac resin, Resitop PS-6937 Manufacture. 2-Ethyl-4-曱基α米嗅 (coating solution (J-4) New Cheng) 'Qunrong Chemical Gong Xiao · 3 parts by weight 〇 · 2 parts by weight • 72 parts by weight of cyclopentanone. Liquid double F type epoxy resin JER806 , Mitsubishi Chemical manufactures 15 parts by weight. Phenoxy resin ΥΡ-50, 10 parts by weight of Xinyi Iron Chemical Co., Ltd. • Phenolic styrene resin PHENOLITELA-3018-50P, DIC Manufactured 3 parts by weight • 2-ethyl-4-methylimidazole 0.2 parts by weight (coating liquid composition) Nipoll 561 manufactured by Zeon Zeon Co., Ltd. *Aqueous dispersion having a solid concentration of 40.5 mass% &lt;coating liquid for polymer layer&gt; (coating liquid A Composition) • 1-oximeoxy-2-propanol 75 parts by weight. Water 20 parts by weight • Polymer A 5 parts by weight (composition of coating liquid B) • Acetonitrile 95 parts by weight • Polymer B 5 parts by weight ( Composition of coating liquid C) • 1-methoxy-2-propanol 75 parts by weight 64 201228822 jyyo /pif • Water • Polymer A • Irga Cure907, Ciba refined to produce 1 part by weight &lt;plating catalyst liquid&gt; (composition of plating catalyst liquid S-1). Water • Copper acetate (II) Further, plating catalyst liquid S-1 The pH is 5.6. (Composition of plating catalyst liquid S-2) Water • Copper acetate (II) • Silver nitrate Further, the pH of the plating catalyst liquid S-2 was 4.2. (Composition of plating catalyst liquid S-3) Water • Copper acetate (II) • Acetic acid I bar Further, the pH of the plating catalyst liquid S-3 was 5.3. (Composition of plating catalyst liquid S-4) Water • Copper acetate (II) • Copper sulfate (II) Further, the pH of the plating catalyst liquid S-4 was 3.2. (Composition of plating catalyst liquid S-5) 20 parts by weight 5 parts by weight 100 parts by weight 2 parts by weight 100 parts by weight 2 parts by weight 0.2 parts by weight 100 parts by weight 2 parts by weight 0.05 parts by weight 100 parts by weight 2 parts by weight 1 weight Part 65 201228822 jf pii . Water • Copper (II) sulfate Further, the pH of the plating catalyst S-5 was 3.0. (Composition of plating catalyst liquid S-6) • Water • Gasified copper (II) Further, the pH of the plating catalyst liquid S-6 was 1.0. (Composition of plating catalyst liquid S-7) • Water • Acidic silver (composition of plating catalyst liquid S-8) • Water • acetic acid &lt;reducing liquid&gt; (composition of reducing liquid 2_1) • Diamine borane (DMAB) (composition of reducing solution Z-2) • Water • 1 mol/L sodium hydroxide • Diamine borane (DMAB) • Furfural (reducing liquid Z-3 composition) • Water 100 parts by weight 2 parts by weight 100 parts by weight 2 parts by weight 100 parts by weight 0.2 parts by weight 100 parts by weight 0.05 parts by weight 100 parts by weight 1 part by weight 100 parts by weight 5 parts by weight 0.5 parts by weight 0.5 parts by weight 100 parts by weight 66 201228822 j^y〇/pif parts by weight • Sodium borohydride 1 (four) 'The present invention _ Manufactured green _ A copper plating film which is excellent in film etch characteristics and excellent in adhesion. In particular, it has been confirmed that if the Kawasaki ship does not contain S-1 or silver, the amount of metal residue is less. On the other hand, as in Comparative Example 比较 to Comparative Example 6, and Comparative Example 13 to Comparative Example 14 lion, in the It fine liquid made of only the silver sulphate or the salt, which is made by the company When plating is not carried out, or the characteristics of the surname are not used, the use of a metal-copper colloid or a metal-copper-like material containing a copper-based colloidal liquid is not preferable, or the etching property is poor or the etching property is insufficient. good. Further, when the plating catalyst liquid S-5 and the money application catalyst liquid S-6 having a pH not in a predetermined range are used, the plating catalyst does not adhere to the polymer layer, and plating deposition does not occur. Further, in the above Example 1, the coating liquid for forming a polymer layer was applied by a spin coating method, but the same evaluation results were obtained even by the dip coating method or the spray coating method. Further, in the above Example 1, the polymer layer was immersed in the plating catalyst liquid, but the same evaluation result was obtained even if the plating solution was sprayed or spin-coated. Further, in Example 1, exposure was carried out to impart energy to the polymer layer thief, but the same result was obtained when It was hardened by heating at 150 ° C for 30 minutes instead of exposure. 67 201228822 /pu &lt;Example 15&gt; The L/s of the example is changed to 1G Mm/1G, and the pattern is etched by the order. As in the case of Example 1, copper showed excellent adhesion and properties ("microwire $her", "gold m removal"). &lt;Example 16&gt; A pattern exposure of the household illumination was used instead of the polymerized light (4) in Example 1; the unexposed "polymerized layer" was subjected to the example 1 in the case of the 1% carbonic acid gas nano-water: "Pre-" and "plating", and a copper plating film is obtained on the polymer layer. The pattern temple obtained by the rhyme is used to adjust the superiority of the peers. Scales _ Occupation and Example 1 f outside 'in the upper shot by laser riding =:: _ by using metal chrome to form a round case, the same as above, also shows excellent &lt;Example 17&gt The same procedure as in the pattern-like plating example 1 obtained in Example 1 was carried out to form a multilayer wiring structure. H 2 is on the surface of the __ touch _, 1 <Example 18> J ^ on the glass epoxy substrate on which the conductive layer (copper) is formed in advance,

68 2〇1228822f The ring gas-based insulating material GX-13 (film thickness: 45 μm) manufactured by Ajinomoto Fine-Techno Co., Ltd., which is an electrical insulating layer, is heated and pressurized, and then vacuum-layered at a pressure of 0.2 MPa to 10 (The insulating film is formed by bonding under conditions of TC to 110 ° C. Then, [formation of polymer layer], [application of catalyst], [plating] performed in Example 1 are sequentially performed, and obtained a laminated body of a conductive film. [Formation of via holes] Then, for a laminated body, a UV-YAG laser is used at a frequency of 5000 HZ at a frequency of 200 to 300, and a pulse energy is 〇.〇5 mJ to 0.12 mJ. The adjustment is made to form a through hole having a top diameter of the through hole of 60 μm to the surface of the conductive layer. [Slag removal treatment] As a desmear method, at 70. (: The laminate is contained in 20% by volume. MLB211 (manufactured by Rohm and Hass Electronic Materials Co., Ltd.) and 10% by volume of CupositZ in a swelling bath for 7 minutes, and then contained 10% by volume of MLB213A (manufactured by RohmandHass Electronic Materials Co., Ltd.) at 80 °C. With 15% capacity of MLB213B (Rohm and Hass Minutes impregnation treatment in the money bath of the Material Co., Ltd., and then immersed in a neutralization bath containing 20% by volume of MLB216-2 (manufactured by Rohm and Hass Electronic Materials Co., Ltd.) The desmear treatment of the through holes was carried out for 7 minutes. [Catalyst application] Electrolytic plating was applied to the through-hole wall surface of the layered body subjected to the desmear treatment by the same catalyst application method as in Comparative Example 7. Catalyst 69 201228822 Then, the Thru-Cup PGT manufactured by Uemura Industrial Co., Ltd. is used for the laminated enamel to which the mineralizing catalyst is applied, and the electroless plating bath having the following composition is used at the electroless plating temperature. 26. (: 2 hours of electroless plating is carried out) and an electroless copper plating film (thickness: 0.3 μm) is formed so that the conductive layer on the substrate is electrically connected to the mineral film. The liquid transfer order of the electroless plating solution The raw materials are as follows: Distilled water approximately 60% by volume PGT-A9.0 Capacity % PGT-B 6·0 Capacity % PGT-C3.5 Capacity % Furfural liquid ice 2.3% by volume Finally, the total amount is 100% by volume The method uses distilled water for liquid level adjustment. * The furfural used here is a formaldehyde solution (special grade) of Wako Pure Chemicals. [Formation and patterning of a plating resist layer for electrolytic plating] After washing the copper surface with a 1% sulfuric acid aqueous solution, the temperature is used.

110±10°C, pressure 0.35±0.05Mpa laminated dry film resist (ALPHO NIT3025: manufactured by Nichigo-Morton Co., Ltd.). The pattern is baked, and the pattern is exposed by irradiating ultraviolet rays with an ultrahigh pressure mercury lamp at 12 〇mj/em2 using a pilot hole as a reference, and then using a 1% sodium carbonate aqueous solution at 30 ° C with a spray pressure of 0.15 MPa on the dry film. The etchant is developed to form a plating resist pattern. [Electrolytic plating] A conductive layer, a plated film, and an electroless copper plating film were used as a power supply layer, and an electrolytic copper plating bath having a plating composition of 45 minutes was used for 3 minutes at 3 A/dm2 using 201228822 ~&gt;yy〇/yif. Condition (composition of electrolytic plating bath)

• Copper sulfate 38 g • Sulfuric acid 95 g • Hydrochloric acid 1 mL

Copper Gleam PCM (Meltex (share) manufacturing,

Water 500 g ; 3mL

[Peeling and etching of resist] 4/% by weight of sodium hydroxide was dissolved in water to prepare an anti-_ liquid, which was applied to the surface i at a pressure of G·2 MPa. . In seconds, the _ removal process is performed on the = anti-touch. Thereafter, the copper film of the underlying conductive layer of the pattern portion is removed, and the conductive film is formed by removing it with hydrogen peroxide liquid (see ", Fig. 4 (G)). (A) to (D) of Fig. 1 are schematic cross-sectional views showing the manufacturing steps of the body and the manufacturing method of the present invention from the substrate to the laminated body, respectively. y^ ^ (Α) of Fig. 2 (D) is a schematic cross-sectional view showing an embodiment of an etching step in the method for producing a layered product of the present invention in order. ^(A) to (E) of FIG. 3 are sequential views showing a method of manufacturing a layered body of the present invention. A schematic cross-sectional view of another embodiment of the etching step. (A) to (H) of FIG. 4 are schematic cross-sectional views showing the steps of manufacturing the multilayer wiring substrate in sequence. 2012 20122222 W ^ Λ. 【. Substrate 12: adhesion assisting layer 14: polymer layer 16, 16b: copper-containing plating film 18: patterned copper-containing plating film 20: metal wiring 22: insulating resin layer 24: mask 26, 28: metal film 30 : Patterned metal film

72

Claims (1)

201228822 VII. Patent application scope: ι· A method for manufacturing a laminate having a patterned copper-containing coating, comprising: a polymer layer forming step of forming a functional group and a polymerizable property which interact with copper ions on a substrate After the base polymer contacts the substrate, energy is applied to form a polymer layer on the substrate; and a catalyst application step is performed to bring the plating catalyst liquid containing copper ions and having a pH exceeding 3. 接触 into contact with the polymer layer. Providing copper ions to the polymer layer; contacting the first alkaline aqueous solution to contact the polymer layer to which the copper ions are added, and the alkaline aqueous solution; and plating step, after the first aqueous solution contacting step, the polymer The layer is subjected to at least copper plating to obtain a copper-containing plating film, and a pattern forming step of etching the copper-containing plating film into a pattern after the plating step to form a patterned copper-containing plating film. 2. The method for producing a laminate according to claim 1, wherein the first aqueous solution is contacted and the plating step further comprises a polymer layer which is coated with copper ions. The reduction step with the reducing solution. J 3. The method for manufacturing a laminate according to claim 2, wherein the reduction step is microscopic and before the plating step, and further comprises a crucible layer and a miscellaneous water. Water soluble step. The intermediate body is obtained by a method for producing a laminated body as claimed in any one of claims 1 to 3 of the patent application. 5. A printed wiring board comprising the laminated body as described in claim 4, 201228,222. 6. A circuit comprising the laminate as described in claim 4 of the patent application. 74