TW201226627A - Method for manufacturing laminate having metal film, metal pattern material and method for manufacturing the same, and printed wiring board - Google Patents

Abstract

A method for manufacturing a laminate having a metal film in the disclosure includes: a step of forming underlayer, performed on a substrate such that a composition for forming a underlayer contacts with the substrate, thereby forming the underlayer including a silane coupling agent; a step of forming polymer layer, performed at the underlayer including a silane coupling agent, such that a composition for forming a polymer layer contacts with the underlayer including a silane coupling agent, and energy is supplied to form the polymer layer; a step of supplying catalyst, at which a plating catalyst or its precursor is supplied to the polymer layer; and a plating step, at which plating is performed on the plating catalyst or its precursor, and a metal film is formed on the polymer layer. The composition for forming the underlayer and/or the composition for forming the polymer layer include a polymerizable compound containing a P=O group.

Description

201226627 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a laminate having a metal film. [Prior Art] Metal wiring boards which have previously formed wirings of metal patterns on the surface of an insulating substrate have been widely used for electronic parts or semiconductor elements. The method of manufacturing the metal pattern material mainly uses a "reduction method". The subtractive method is to provide a photosensitive layer which is exposed to light by irradiation with active light on a metal film formed on the surface of the substrate, imagewise exposing the photosensitive layer, and then developing to form a resist image, followed by a metal film. A method of etching to form a metal pattern 'finally stripping the anti-surname agent. In the metal pattern obtained by this method, the adhesion between the substrate and the metal pattern (metal film) is exhibited by the adhesion-increasing effect by providing irregularities on the surface of the substrate. Therefore, when the obtained metal pattern is used as the metal wiring, there is a problem that the high-frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal pattern. Further, in order to perform the roughening treatment on the surface of the substrate, it is necessary to treat the base surface by a corrosive acid such as chromic acid. Therefore, in order to obtain a metal pattern excellent in adhesion to the substrate, a troublesome step is required. ^ 2 Don't worry, for glass substrates or ceramic substrates, there is no way to compare the surface roughness, but to use a method of mixing gold unboiled in glass frit, or New Zealand or Lin. Vacuum method. However, calcination must be very high in temperature, while in equipment or production, and organic

4 S 201226627 There is a problem with the matching of substances. 'The vacuum knives are also problematic in terms of equipment or productivity' and there is a problem that the adhesion to the metal is weak. A method for solving this problem is known, in which a graft polymer (tetra)-filament layer directly bonded to the filament is formed on a substrate having a layer of a lithographic coupling agent, and the polymerization (4) is carried out on the polymer layer, and the polymer layer is obtained. The method of metal film into the engraving (patent reading 1). (4) In this method, the adhesion between the substrate and the metal film can be improved without roughening the surface of the substrate. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-242412. In recent years, it has been conceived that a semiconductor element having a metal wiring substrate is used under more severe high temperature conditions, and (iv) development金属 A metal film that exhibits sufficient adhesion even when exposed to such an environment. The inventors and the like refer to the patent documents! In the disclosed invention, the use of Shi Xi and the coupling agent layer f is made to have a metal lanthanum, and the adhesion of the metal film after such a severe high temperature condition is studied. As a result, it has been found that a large amount of "bumping" due to insufficient adhesion of the metal film is observed on the metal film exposed to the temperature condition, and the adhesion of the metal film is not necessarily a satisfactory result in practical use. SUMMARY OF THE INVENTION The present invention has been made in the above-described actual circumstances, and an object thereof is to provide a two-layer body-made shirting method which can be formed into a gel and has an excellent adhesion to a substrate under the high temperature ring. A layered body of a metallic film. The inventors of the present invention have conducted intensive studies on the above problems, and as a result, the polymerizable compound of 201226627 has been produced, and the above problem can be solved by using p==〇. The inventors and the like have found that the above object is achieved by the following. (1) A method for producing a laminate having a metal film, comprising: forming a base layer containing a Wei couple on a substrate by forming a base layer having a reactive base; and forming a polymer layer; On the undercoat layer containing the ceramsite coupling agent, the polymer layer forming composition containing the polymerizable group and the functional group that interacts with the surface contact or the money is contacted, and then the energy is supplied. Forming a polymer layer; a catalyst supply step of supplying a plating catalyst or a precursor thereof to the polymer layer; and a plating step of plating the plating catalyst or its precursor to the polymer layer A metal film is formed thereon; and a polymerizable compound containing a P=fluorenyl group is contained in the base layer forming composition and/or the polymer layer forming composition. (2) The method for producing a layered product according to the above aspect, wherein the polymerizable compound containing p = fluorenyl group is a compound represented by the following formula (?). (3) The method for producing a laminate according to (1) or (2), wherein the reactive group is methyl propyl sulfonyl group, propyl fluorenyl group, glycidyl group, cyclyl group, styrene group, Vinyl, sulfhydryl, ureido, thio, isocyanate or carboxyl. ~

The method for producing a layered product according to any one of the aspects of the present invention, wherein the polymer layer forming composition further contains a reactive base. Coupling agent. (5) The method for producing a layered product according to any one of the aspects of the present invention, wherein the polymer layer-forming composition contains a sulphur coupling agent having a reactive group, and yttrium-containing A polymerizable compound of a mercapto group. (6) The method for producing a laminate according to any one of (1) to (5) wherein the substrate is a glass substrate or a ceramic substrate. (7) The method for producing a laminated body according to any one of (1) to (6) wherein the heating step is performed after the plating step. (8) The method for producing a layered product according to any one of (1) to (7), wherein, in the step of forming the base layer, after the base layer forming composition is brought into contact with the substrate, the solvent is used to perform the above. Cleaning of the substrate. (9) A method of producing a metal pattern material, comprising a pattern formation = a metal in a laminate obtained by the method for producing a laminate according to any one of (1) to (8) The film is etched into a pattern to form a patterned metal film. (10) A metal pattern material obtained by the method for producing a metal pattern material as described in (9). (11) A printed wiring board comprising the metal pattern material as described in (1). [Effect of the Invention] According to the present invention, there is provided a method for producing a laminate, which can easily form a laminate having a metal film which exhibits adhesion to a substrate which is excellent in adhesion to a substrate even when exposed to a high temperature environment. [Embodiment] The manufacturing method and the detailed method of the borrowing method are as follows: The present invention is applied to a substrate containing a decane coupling agent. = fluorenyl (four) compositive compound _ is characterized in terms of the formation of a Wei (4) fluorene-containing substrate or a polymer layer. By adopting such a structure, the adhesion between the substrate and the impurity-containing coupling layer, and the adhesion between the base layer and the polymer layer of the mixture are further improved, and the result is obtained. (4) A layered body exhibiting excellent adhesion at the base (four) gold ^ under high temperature conditions. < The method for producing a layered product of the present invention comprises the following steps: a polymerizable compound containing a p=0 group in the base layer forming composition and/or the polymer layer forming composition. (1) a base layer forming step of contacting a base layer forming composition containing a decane coupling agent having a reactive group on a substrate to form a base layer containing an anthracene coupling agent; (2) forming a polymer layer The step of contacting a polymer layer-forming composition containing a polymer on a base layer containing a decane coupling agent, and supplying energy to form a polymer layer having a polymerizable group and a plating catalyst Or a precursor thereof to form an interacting functional group; (3) a catalyst supply step 'which supplies a plating catalyst to the polymer layer or

S 8 201226627+ precursor; (4) a plating step, in which a medium or a precursor thereof is applied, and a metal film is formed on the polymer layer. The method of operation and the following are described in detail in the materials used in each step. <Step (1): basal layer forming step> v (1) contacting the basal layer axial test composition containing the reactive base of the Shi Xiyuan coupling agent on the substrate, and (iv) forming a Wei-containing coupling agent The step of the base layer (hereinafter also referred to as the base layer). By this step, the hydrolyzable group of the stagnation coupling agent can be used to form a chemical bond with the surface of the substrate: the layer containing the shi wei wei mixture and the underlayer ‘this layer functions as the basal layer of the polymer layer to be described later. Further, the base layer and the polymer layer to be described later may form a chemical bond via the reactive group (tetra), and as a result, the metal film having a surface formed on the surface of the polymer layer and the substrate exhibit excellent adhesion. More specifically, by this step, the underlayer 12 containing the decane coupling agent is formed on the substrate 10 as shown in Fig. (A). First, the materials used in this step (a sulphur coupling agent, a polymerizable compound containing a p-based group, a composition for forming a base layer, a substrate, and the like) will be described in detail, and the order of this step will be described in detail. (decane coupling agent) The decane coupling agent used in this step has a reactive group. Preferably, the reactive group reacts with a polymer described later to form a covalent bond between the polymer layer and the underlayer. — The type of the reactive group is not particularly limited to 201226627 as long as it reacts with a polymer to be described later, and examples thereof include a mercapto acrylonitrile group, an acryl fluorenyl group, a glycidyl group, an amine group, a carboxyl group, a vinyl group, a fluorenyl group, and the like. Styryl group, urea group, sulfur group, isocyanate group, and the like. Among them, the reactivity with the polymer layer is good, and the adhesion of the metal film is more excellent, and examples thereof include a mercapto propylene group, an acryl fluorenyl group, a glycidyl group, an amine group, and a stupid vinyl group. , isocyanate groups, and the like. Further, the reactive group may contain two or more of the decane coupling agents. A preferred embodiment of the decane coupling agent used in the present step is a compound represented by the following formula (3). (fjO m Formula (3) Za-Lc-Si-eW) n In the formula (3), 'za' represents a reactive group. The definition of the reactive group is as described above. R independently represents a hydrogen atom or a hydrocarbon group. The hydrocarbon group may, for example, be an aliphatic group (e.g., an alkyl group or an alkenyl group, preferably having a carbon number of 1 to a carbon number of 12) or an aromatic hydrocarbon group (e.g., a phenyl group or a naphthyl group). Among them, the hydrocarbon group is preferably a methyl group or an ethyl group. When there are a plurality of R, they may be the same or different. W represents a hydrolyzable group. Specific examples thereof include an alkoxy group (preferably an alkoxy group having a carbon number of 1 to a rabbit number of 8, for example, a decyloxy group or an ethoxy group), a halogen atom (a fluorine atom, a gas atom, a bromine atom, or an iodine atom). An alkoxy group (acetoxy group, 201226627, alkoxy group, etc.), etc., is preferably a decyloxy group, an ethoxy group or a chlorine atom in terms of good reactivity. To represent a single bond, or a divalent organic group. The divalent organic group may, for example, be a substituted or unsubstituted aliphatic hydrocarbon group (for example, a stretching group, preferably a carbon number of 1 to a carbon number 8), a substituted or unsubstituted aromatic hydrocarbon group (for example, an extended aryl group). Preferably, carbon number 6 to carbon number 12), -Ο-, -S-, -SOr, -N(R)_(R: alkyl), -CO-, -NH-, -COO-, - CONH- or a group in which the groups are combined (for example, an alkoxy group, an alkyleneoxycarbonyl group, an alkylene group, or the like). Among them, in terms of the production of the compound, a stretching group, _〇_, or a combination of the groups is preferred. When it is a single bond, za which shows the general formula (3) is directly connected with Si. m represents an integer 〇 〜 2 η represents an integer of 1 to 3 and satisfies the relationship of ^ + m = 3. Wherein m is preferably 〇~1. η is preferably 2 to 3. The decane coupling agent to be used may, for example, be γ-glycidoxypropyltriethoxy sulphur, γ-glycidoxypropyltrimethoxy oxysulphate, glycidoxypropyl fluorenyldiacetate. Oxydecane, hydrazine-glycidoxypropyl-decyldimethoxy decane, 2-(3,4.epoxycyclohexyl)ethyltrimethoxy decane, vinyltrimethoxydecane, vinyl three Ethoxy decane, allyl dimethoxy decane, 3-trimethoxy decyl propyl methacrylate, 3 - (acryloxy) propyl trimethoxy decane, 2 · (3, 4- Epoxycyclohexyl)ethyltrimethoxy decane, aminopropyltrimethoxydecane, aminopropyltriethoxydecane, 3-(2-aminoethyl)aminopropyltrimethoxydecane , 3_mercapto acryloxypropylmethyl decyloxydecane, 3-mercaptopropyltrimethoxydecane, 201226627 »/〆〆〆νγ** 3-mercaptopropylmethyldimethoxy Decane, 3-mercaptopropyltriethoxydecane, vinyl trioxane, and the like. (Constituent for forming a base layer) The composition for forming a base layer contains the above-mentioned composition; The content of the Shixiyuan coupling agent in the base layer-forming composition is not particularly limited, and the operability, the ease of controlling the layer thickness of the underlayer, and the adhesion strength of the produced metal film are relatively The total amount of the composition is preferably from 0.1% by mass to 100% by mass, more preferably from 5% by mass to 2% by mass. (Polymerizable compound containing fluorene = fluorenyl group) The base layer forming composition and/or the polymer layer forming composition to be described later contain a polymerizable compound containing a fluorene = fluorenyl group. The polymerizable compound having a Ρ=0 group is a compound having a fluorene = fluorenyl group (phosphoryl group i and a polymerizable group). When the composition for forming a base layer contains the compound, the coupling agent with a decane via a p=0 group A strong coherent bond is formed between the polymer layers described later, and a compound having a polymerizable group can form a strong covalent bond between the polymer layers described later. The polymerizable compound having a P = 0 group may contain a p = fluorenyl group and a polymerizable group. Examples of the conjugate group include a radical polymerizable group and a cationic polymerization 1" In the case of reactivity, a radical polymerization base is preferred. Examples of the radical polymerizable group include mercaptopropenyl group, propylene 201226627 fluorenyl group, itaconate group, and butyl group. An acrylate group, a methacrylate group, a maleate group, a stupid vinyl group, a vinyl group, a acrylamide group, a methacrylamide group, etc. Among them, a mercapto propylene group or a propylene group is preferred. Sulfhydryl, vinyl, stupid The alkenyl group, the acrylamide group, the mercapto acrylamide group, particularly preferably an acrylonitrile group, a mercapto propylene group or a styryl group. A preferred embodiment of the polymerizable compound containing a P = fluorenyl group is as follows: The compound represented by the formula (1): In the formula (1), in the formula (1), xa represents a polymerizable group. The definition of the polymerizable group is as described above.

La is not a single bond or a divalent organic group. The definition of an organic group is synonymous with the organic group shown by the above lc. 〃

Ya represents a hydrogen atom or a substituent having no polymerizable group. Examples of the substituent having no polymerizable group include an aliphatic nicotyl group (example), an aromatic hydrocarbon group (e.g., an aryl group), or a group 4 obtained by combining the groups. Further, the substituent may contain _〇_, _c〇_, _nh_, or a divalent organic group such as a group in which the groups are combined. Specific examples of the human soil 1 w y y, especially the siloxane base: methyl group, ethyl group, propyl group, butyl group: hexyl group. The base may be linear or 'branched' or may be a ring method 13 201226627

Good for straight green. Silk can be replaced by secret, silk, and base. The carbon number of the aryl group is preferably 6 to 14' or more preferably 6 to 1 (). Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group may be substituted by a silk, an alkoxy group, an aryloxy group or the like. p represents an integer of 1 3, q represents an integer of 〇 〜 2, and p and q satisfy a relational expression of P + q = 3. Among them, P is preferably 1 or 2, and q is preferably i or 2 较佳. A preferred embodiment of the compound of the formula (1) is a compound represented by the formula (2). General formula (2) (xb-〇-Lb-〇kiL(〇Ya) q General formula (2)+ 'The definitions of Ya, p and q are synonymous with the general formula. In the general formula (2), 'Xb indicates Acryl fluorenyl or fluorenyl acrylonitrile. General formula (7) t, Lb represents a stretching wire, a stretching residue, an extended oxygen group, an alkylcarbonyloxy group, or a combination of these groups. Specific examples of the stretching group of the exfoliating oxygen group, the exchanging oxygen group, and the exfoliating group-carbonoxy group include a methylene group, an exoethyl group, a propyl group, a butyl group, and a pentyl group. The stretched wire may be a linear chain or a branched shape, preferably a linear stretchable base. Among them, in terms of more excellent adhesion of the metal film, it is preferably 201226627

Lb contains 2 or more alkyl groups, an extended oxy group, an alkoxy group or an alkylcarbonyl group, and the carbon number is preferably 3 to 12, Good for 5 to 8. For the polymerizable compound containing a P = 0 group, for example, a commercially available compound such as the KAYAMER series manufactured by Nippon Kayaku Co., Ltd. or the Phosmer series manufactured by Uni-Chemical Co., Ltd. can be used as it is, or a new synthesis can be used. compound of. The following 'is a specific example of the polymerizable compound containing p=fluorenyl group, but the monomer usable in the present invention is not limited to these polymerizable compounds. [Chemical 4]

When the polymerizable compound containing a P=0 group is contained in the base layer forming composition, the base layer forming composition is used in terms of the adhesion between the underlying layer and the substrate and the adhesion between the underlying layer and the polymer layer. The mass ratio of the polymerizable compound containing P = fluorenyl group to the decane coupling agent (poly 15 201226627 conjugated compound/decane coupling agent containing p = fluorenyl group) is preferably 1/1 〇〇〇 1/2 1/2. More preferably, 1/3 ° ', , (solvent) The base layer-forming composition may contain a solvent as needed. The solvent is not particularly limited as long as it is a reagent coupling agent of (4), and examples thereof include water, an alcohol solvent, ethanol, and propanol, and a ketone solvent (for example, acetone or mercaptoethyl hydrazine). , cyclopentanone, etc.), guanamine-based solvents (such as formamidine, dimethylamine oxime-methyl ketone, etc.), nitrile-based solvents (eg, B., C., etc. = solvent) (eg methyl acetate) , ethyl acetate, etc., carbonic acid, such as carbonic acid, 曱S, carbonic acid, etc.), _ a bulking agent (for example, propylene glycol, etc.), a halogen type solvent (for example, gas, etc.). The operability of the solvent in the basal layer formation test, the layer thickness control of the basal layer, and the stability are preferably the sulphur coupling agent and the comparative polymerizable compound in the basal layer forming composition. The total concentration is 〇1% by mass to 5 hrs to adjust the amount of solvent. The composition of the base layer forming layer may include, for example, a pH adjusting agent such as an acid or an assay (for example, acetic acid: acid: sulfuric acid, sulfuric acid, carbonic acid, oxalic acid, formic acid, etc., 4, potassium). , sodium bicarbonate, sodium carbonate, ammonia, etc.)), etc. Weiner, oxygen oxidation (substrate) The substrate 1 used in the present invention may also be a previously used substrate, preferably a substrate 1 capable of withstanding the processing conditions described later.

16 201226627 jyyyupif Glue substrate, glass substrate, ceramic substrate, metal substrate, etc. Among them, in terms of excellent reactivity of the fish decane coupling agent, a glass substrate or a ceramic substrate is preferred. ^The material of the plastic substrate may be a thermosetting resin (for example, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, or the like) or a thermoplastic resin (for example, a phenoxy resin, a polyethersulfone, a polysulfone, or a polyphenylene). Sulfone, etc.). The material of the ceramic substrate may, for example, be alumina, aluminum nitride, oxidized ox, ruthenium, tantalum nitride or ruthenium. Examples of the material of the glass substrate include soda glass, potassium glass, borosilicate glass, quartz glass, aluminum bismuth glass, lead glass, and the like. Examples of the material of the metal substrate include, for example, zinc, copper, and the like. In consideration of applications in semiconductor packages, various wiring boards, and the like, the substrate preferably has a surface roughness Rz of 5 〇〇 nm or less as measured by JIS B 0601 (1994) and a 10-point average height method. It is 〇〇 以下 ^ below, especially preferably below 50 nm, and most preferably below 20 nm. The lower limit is not particularly limited, and is preferably about 5 nm, more preferably 〇. Further, unlike the metal film formed in the present invention, the substrate may have a metal wiring on one or both sides of the substrate. The metal wiring may be formed on the surface of the substrate in a case-like manner or may be formed on the entire surface. As a typical metal wiring, a metal wiring formed by a subtractive method using an etching treatment or a metal wiring formed by a semi-additive method using an electric ore can be used, and a metal wiring formed by any of the methods can be used. . Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc or gallium. 17 201226627 (Step Ο) The method of bringing the substrate into contact with the underlayer forming composition containing the decane coupling agent having a reactive group is not particularly limited, and the composition for forming the underlayer layer is impregnated. The method of the base (4) or the method of applying a base layer forming composition to a substrate. The method of applying the composition onto the substrate is preferred in terms of the thickness of the underlayer obtained by the impact. The coating method is not particularly limited, and a specific method can be used: using a two-roll coater, a slit coater, an air knife coater, a bar coater, a slide funnel (slide h〇Pper), and a spray Mist coater, blade coater, knife coater (d() etGr (7) age), extrusion coater (-with coater), reverse roll coater, transfer roll ( Transfer r〇u) coating machine, extrusion coater, curtain coater (3) other than coater, dip coater, die coater, gravure roll coater A known method such as an extrusion coating method or a roll coating method. When the base layer forming composition is brought into contact with the substrate, the adhesion between the underlying layer disk composition layer and the adhesion of the formed metal film is as follows: the coating amount of the underlying layer forming composition on the substrate ± It is preferable to change the rh in the Wei coupler to G.GG1 g/m2 to 〇丨g/m2, more preferably to read 15 coffee 2 to 0.05 g/m2. After the base layer forming composition is brought into contact with the substrate, The substrate may be subjected to heat treatment as needed to remove the solvent. The heating condition is appropriately selected according to the solvent contained in the composition. The heat/dish degree is preferably 30\:~20 (TC 'the heat time of the mouth is preferably i minutes to 1 hour. 201226627 Υρ-if r is preferably after the base layer forming composition is brought into contact with the substrate, j or after the heat treatment, and the substrate is cleaned using a solvent. By performing α washing with vj, the unreacted ceramsite coupling agent deposited on the substrate can be removed, and as a result, the adhesion of the formed metal film is further improved. The solvent to be used is appropriately selected depending on the type of the decane coupling agent, and for example, a solvent which can be contained in the base layer-shaped composition towel can be mentioned. Among them, preferred are water, an alcohol solvent, and an oxime solvent, and particularly preferably used: isopropyl alcohol, methanol, ethanol, cyclohexane, and cycloheximide. Further, after the base layer forming composition is brought into contact with the substrate (or after washing with a solvent), the substrate can be dried as needed. The drying conditions are not particularly limited to 'drying at a temperature of 2 (rc~·.C, drying time is i minutes to 1 hour. (base layer containing a decane coupling agent), a decane-containing coupling agent formed according to the above procedure The base layer is mainly composed of the above-mentioned smelting coupling and is formed as a base layer of a polymer layer to be described later. The base layer is between the substrate and the polymer layer, whereby the adhesion between the two is advanced. When the step is increased, the adhesion of the metal film is also improved. The thickness of the underlayer is not particularly limited, and is preferably a thickness of one molecule to a few molecules of the Wei coupler used. The contact angle of the substrate to water can be borrowed. The ceramsite coupling agent or the like to be used is controlled by the ceramsite coupling treatment using the composition for forming the underlayer layer, and the change in the value of the contact angle on the surface of the substrate is observed, and it is possible to investigate whether or not the underlayer is formed on the substrate. In addition, by the combination of the constituent components of the underlayer and the polymer component constituting the polymer layer, the preferred contact angle of the substrate surface 19 201226627 changes. Refers to the static contact angle, using the droplet method of the antennae measuring device at 27 ° C. Here, "static contact angle a refers to the contact in the basal layer under conditions where the state does not change with time due to flow or the like. Preferably, the decane coupling agent is contained as a main component. The main component means that the content of the samarium coupling agent is 5 〇 or more, preferably 70% by mass or more, based on the total amount of the undercoat layer. The maximum value is 1 〇〇 mass. In addition, when the base layer forming composition contains a polyvalent compound containing a ρ = fluorenyl group, the underlayer also contains a polymerizable compound containing ρ = =0. Q < Step (2): Polymer layer (Step of forming) Step (2) is a step of supplying a polymer-forming polymer layer-forming composition onto the base layer obtained in the step (1), and supplying energy to form a polymer layer. a polymerizable group and a functional group that interacts with a plating catalyst or a precursor thereof. In this step, by supplying energy to a substrate having a composition for forming a base layer and a polymer layer, a decane couple is provided. Reactive group, polymer The polymerizable group and the polymerizable group in the polymerizable compound containing p = fluorenyl group are activated to form a parent bond between the polymers or to form a covalent bond between the base layer and the polymer layer. The layer is more firmly adhered to the substrate layer. More specifically, as shown in Fig. 1(B), a polymer layer i4a is formed on the base layer 12 containing a decane coupling agent. First, the material used in this step is used. (Polymer, polymer layer forming composition, etc.) will be explained in detail, and the order of this step will be described in detail.

S 20 201226627 jyyyvpif (Polymer) The polymer used in the present invention has a polymerizable group and a functional group (hereinafter referred to as an interaction group as appropriate) which interacts with the mineral catalyst or its precursor. Hereinafter, the functional group contained in the polymer or its characteristics will be described in detail. The polymerizable group is a functional group which forms a chemical bond between the polymers or the polymer and the underlayer by supplying energy. The definition of the polymerizable group is synonymous with the polymerizable group in the above polymerizable compound having a P = 0 group, and the preferred form is also the same. The functional group (coordinating group, metal ion-adsorbing group) which interacts with the plating catalyst or its precursor can be used to form electrostatic interaction with the plating catalyst and its precursor (electrostatic The S-group of the interaction, or a nitrogen-containing functional group, a sulfur-containing functional group, an oxygen-containing functional group, or the like which can form a coordination with the plating catalyst or its precursor. Examples of the interactive group include a non-dissociable functional group (a functional group which does not form a proton by dissociation) and the like. More specifically, the interactive group may be exemplified by an amine group, a decylamino group, a quinone imine group, a gland group, a secondary amine group, an ammonium group, a sulfhydryl group, a triterpene ring, a tris- ring ring, a benzotriazolyl group, and an imidazolyl group. , benzimidazolyl, quinolyl, pyridyl, pyrimidinyl, pyrazinyl, oxazolinyl, quinoxalinyl, fluorenyl, triazinyl, piperidinyl, piperazinyl. Pyrrolidinyl, pyrazolyl, anilino, a group containing an alkylamine structure, a group comprising a heterodiisocyanate structure, a cleavage group, an anthracene group, an azo group, a diazo group, an azide group, a cyanogen group Base, cyanate group (R_0_CN), etc.

201226627 jyyyyjyiL functional group; ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, carbonate group, carbonyl group, ester group, group containing N-oxide structure, group containing s_oxide structure, group containing N-hydroxy structure An oxygen-containing functional group; a thienyl group, a thiol group, a thiourea group, a thiotrisocyanate group, a benzothiazolyl group, a decyltriazinyl group, a thioether group, a thioketone group, a sulfoxide group, a sulfone group, Sulfite group, sulfur-containing functional group including a sulfonimide structure= group, a group containing only a small burdock diterpene salt structure, a sulfonic acid group containing a % acid ester structure, and the like; And a phosphorus-containing functional group such as a 7-member K group, a phosphino group, a group containing a phosphate structure, a group containing a halogen atom such as a gas or a bromine, etc., and a functional group having a salt structure may be used. Salts of some functional groups. Among them, in terms of the high polarity, the adsorption function f of the plating catalyst or its precursor, etc., it is particularly preferably a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, or a cation or a cyanide group. Base, especially good for secret or cyano. These functional groups as an interactive group may contain two or more kinds in the polymer. Further, the above ether group is preferably a polyoxyalkylene represented by the following formula (χ): (X) * - (L40) n-Rc In the formula (X), L4 represents an alkylene group, and RC represents an alkyl group. n represents a number from 1 to 30. * indicates the bonding position. The alkylene group is preferably a carbon number of 1 to a carbon number of 3, and specifically, it is preferably an ethyl group and a propyl group. The base is preferably Wei i ~ carbon number 1 〇, specifically

S 22 201226627^ 'Car father is 3~, preferably 曱 group, ethyl group. η represents a number from 1 to 30, 鲂4. In addition, η represents the average

The value can be measured by a known method (nuclear resonance, NMR) or the like. There is no particular limitation, and it is preferably 1000^200,000 or less. In particular, the weight average molecular weight of the polypolymer is more than 700,000 or less, more preferably 2,000 or more, and 2 is preferably 2 Å (10). Further, the degree of polymerization of the polymer has no specific polymer. The above polymer is more preferably an eicosomer', and it is preferably used in an amount of preferably less than seven mer polymers, more preferably a tributary polymer. Further, the polymer is preferably one or less of a polymer or less. , especially good for two thousand (preferred form 1)

The twin base unit) and the element (hereinafter, the first preferred embodiment of the polymer is as follows: one female is as follows: (a) and the other is a heavy weight.

23 201226627 In the above formula (a) and formula (b), Ri to R5 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. When R1 to R5 are a substituted or unsubstituted alkyl group, the unsubstituted alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. Further, examples of the substituted alkyl group include a mercapto group, an ethyl group, a propyl group and a butyl group substituted by a decyloxy group, a chlorine atom, a bromine atom or a fluorine atom. Further, R1 is preferably a hydrogen atom, a fluorenyl group or a fluorenyl group substituted by a bromine atom. R is preferably a hydrogen atom, a fluorenyl group or a fluorenyl group substituted by a bromine atom. R3 is preferably a hydrogen atom. R4 is preferably a hydrogen atom. R5 is preferably a hydrogen atom, a fluorenyl group or a methyl group substituted by a bromine atom. In the above formula (a) and formula (b), X, γ, and 2 each independently represent a single bond or a substituted or unsubstituted divalent organic group. The divalent organic group may, for example, be a substituted or unsubstituted aliphatic hydrocarbon group (for example, an alkylene group, preferably a carbon number of 1 to a carbon number of 8), a substituted or unsubstituted aromatic hydrocarbon group (for example, an extended aryl group). Preferably, the carbon number ό~ carbon number 12), -0-, -S-, -S02-, •N(R)-(R:alkyl), _c〇·, _ΝΗ·c〇〇, c〇 NH or a group in which the groups are combined (for example, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, etc.). The substituted or unsubstituted aliphatic hydrocarbon group is preferably an anthracenylene group, an extended ethyl group, a propyl group, or a butyl group, or the group is a decyloxy group, a chlorine atom, a bromine atom, or a fluorine atom. Substituted base.

S 24 201226627^^yyyyjyif The substituted or unsubstituted aromatic hydrocarbon group is preferably an unsubstituted phenyl group or a phenyl group substituted by a methoxy group, a gas atom, a filler atom, a silk atom or the like. . X, Y, and Z are preferably a single bond, an ester group (_C00_), an amidino group (__CONH_), a shry (·〇_), or a substituted or unsubstituted aromatic hydrocarbon group, etc., more preferably It is a single bond, an ester group (_c〇〇_), a guanamine group (-CONH-). In the above formulae (a) and (b), Li and L2 each independently represent a single bond or a substituted or unsubstituted divalent organic group. The definition of the divalent organic group is synonymous with the divalent organic group described in the above i^X, Y, and Z. L· is preferably an aliphatic hydrocarbon group, or a divalent organic group having a urethane bond or a urea bond (for example, an aliphatic hydrocarbon group), more preferably a monovalent organic group having a urethane bond, wherein Jia always broke the number of ~ 碳 9 carbon number. Further, the total carbon number of 'L1' herein means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L1. More specifically, the structure of L1 is preferably a structure represented by the following formula (M) or formula (i_2). Formula (1-1) Formula (1-2) In the above formula (M) and formula (1-2), Ra and 圮 are independently used such that 25 201226627 is selected from carbon atoms. A monovalent organic group formed by opening two or more atoms of a hydrogen atom and a group of oxygen atoms. Preferably, it is a substituted methylene group, an extended ethyl group, a propyl group, or a butyl group, or an epoxy group, a dioxirane group, a trioxirane group, or a tetra-substituted ethylene group. Ethylene oxide group, di% oxypropyl group, tripropylene oxide group, tetrapropylene oxide group. Further, L is preferably a single bond, or a linear, branched or cyclic extended aromatic group or a group in which the groups are combined. The group in which the alkylene group is combined with the aromatic group may also intervene in an ether group, an ester group, a decyl group, a carbazate group, or a ureido group. Wherein L2 is preferably a single bond or a total carbon number of j 15, particularly preferably unsubstituted. Further, here, the total carbon number of l2 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, a phenyl group, and a group in which the group is substituted with a methoxy group, a hydroxyl group, a chlorine atom, a bromine atom, a fluorine atom or the like. And a combination of the bases. In the above formula (b), W represents a functional group which interacts with a plating catalyst or a precursor thereof. The definition of this functional group is as described above. A preferred embodiment of the polymerizable unit represented by the above formula (a) is a unit represented by the following formula (c). [Chemistry 7]

S 26 201226627 jyyyupif

In the formula (c), R, R2, Z and the units represented by the formula (a) have the same definitions of the respective groups. A represents an oxygen atom or NR (R represents a hydrogen atom, and the alkyl group is preferably a hydrogen atom or an unsubstituted alkyl group having a carbon number of 1 to a carbon number of 5). A preferred embodiment of the unit represented by the formula (c) is a unit represented by the formula (d). [化8] 〇人τ

〇丫 A R2 person (d) Each of the ^^^^^ is the same as the unit shown in the formula (4). Α & τ is not an oxygen atom, or cis (& represents hydrogen atom or silk, secret hydrogen hydrogen or money 丨 ~ carbon number 5 unsubstituted 27 201226627 burnt base.). In the above formula (d), T 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 an amino phthalate bond or a urea bond, and more preferably an amine group. The divalent organic group of the acid ester bond is particularly preferably a divalent organic group having a total carbon number of 1 to 9. Further, a preferred embodiment of the interactive group unit represented by the formula (b) is a unit represented by the following formula (e). [Chemistry 9]

In the above formula (e), R5 and L2 are the same as defined in each unit of the formula (b). Q represents an oxygen atom or NR' (R' represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an unsubstituted substituent having a carbon number of 1 to a carbon number of 5.). Further, L2 in the formula (e) is preferably a linear, branched, or cyclic stretching group, an aromatic group, or a group in which the groups are combined. Particularly, in the formula (e), it is preferred that the linking moiety with the interactive group in L2 is a divalent organic group having a linear, branched or cyclic alkyl group.

28 S 201226627 wherein, preferably, the total carbon number of the divalent organic group is from 1 to 10. Further, in another preferred embodiment, it is preferred that the linking portion of the formula (e) has an aromatic group. The organic group known in the earth is preferably a total carbon number of 6 to 15. The base unit is entangled in the financial content of the polymer towel, preferably 3 to 5 mol% to 50 mol%, more preferably 5 / if the above polymerizable unit is less than 5 mol%, there is an anti-f f When the polymerizable group is lowered, the polymerizable group is more likely to be gelled during synthesis than the super stone 2, and it is difficult to synthesize during synthesis. In addition, the above-mentioned interactive base unit is resistant to plating. From the viewpoint of the adsorptivity of the medium or the straight material, it is 'relative to poly n: the area is mol%, more preferably 丨. More preferably (the preferred form 2), the second preferred embodiment of the polymer is exemplified : a copolymer comprising the units shown in the following (B) and formula (C). (A), formula [10]

(c) 29 201226627 The unit of ί (A) is the same as the unit shown by the above formula (1), and the description of each base is also the same. R5, X and L2 in the unit of - ^ 2) / kg are the same as the above formula (8), and R5, X and L2 in the early 70 are the same, and the description of each group is also the same. The Wa in the skin of the skin:) is not a hydrophilic group or a functional group other than the rigid substrate which forms an interaction with the plating catalyst or its precursor, in the case of 弋(C), R independently represents a halogen atom or a substituted or unsubstituted filament. The definition of the filament is synonymous with the above-mentioned alkyl group represented by R1 to R5. In the formula (C), u represents a single bond, or substituted or not The substituted divalent organic group. The definition of the divalent organic group is synonymous with the above-mentioned &, γ, and Z. The organic group is the same as the above. In the formula (C), L3 represents a single bond, or substituted or not. a substituted divalent organic group. The definition of the divalent organic group is synonymous with the above-mentioned divalent organic group represented by L1 and L2. In the formula (C), v represents a hydrophilic group or a precursor thereof. Hydrophilic group /, The group which exhibits hydrophilicity is not particularly limited, and examples thereof include a group, a carboxylic acid group, etc. Further, a precursor group of a hydrophilic group means a treatment by a specific treatment (for example, by an acid or a base) The group which generates a hydrophilic group is, for example, a carboxyl group protected by THP (2-tetrahydropyranyl group). In view of the fact that the polymer layer is easily wetted with various aqueous treatment liquids or plating solutions, the effect of the present invention is further expressed as an ionic polar group. Specific examples of the ionic polar group include a carboxylic acid group and a continuous acid group. Base, 201226627 field thiol-based group. Among them, in terms of moderate acidity (does not decompose other functional groups), it is preferably a carboxylic acid group. In particular, in the unit shown by formula (c), In the case of moderately acidic (not decomposing ^ s silk), the secret water pure towel, the water is dried, and the water is easily expressed by the child-like structure, preferably V is a few acid groups' and The connection portion between L3 and V has a ring structure of 4 to 8 members. Here, the ring structure of the 4 member and 8 member rings may be exemplified by cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, anthracenyl, and stupid. Among them, a cyclohexyl group and a phenyl group are preferred.

In addition, the unit towel shown in the formula (C) is moderately acidic (does not decompose other official filaments), and the water-repellent towel exhibits hydrophilicity. After drying the water, the dream is made of a long-bonded silk structure. In terms of it, it is also better to ^ V for New H L3 _ long for 6 Xuan ~ 18 atoms. Here, the distance between U and V in the formula (c) of W, preferably U", is separated by a range of 6 atoms to 18 atoms. 6, sub ~ 14 atoms, especially preferably 6 atoms ~ 12 atoms. The preferred content of each unit in the second preferred embodiment of the virgin dipolymer is such that the unit represented by the formula (A) is reactive (in terms of inhibition of gelation during hard synthesis) and Preferably, the unit contains all of the -30% of the 5% and 5% of the 5%. . ,. Further, the unit shown in the form of 5 mol/0 (B) is in the view of the plating touchability, relative to the adsorption of ^/, ytterbium in the polymer, 5 mol% to 75 mol. %, more preferably = early 疋 'preferably contains, present / 〇 ~ 70 mol%. 31

201226627 • The square of J) The m unit is δ in terms of water solubility_developability (iv) wet adhesion, relative to the mole in the polymer. /. ^Na, _ 2. (d) ~ 6 () two, = 30 mol % ~ 50 mol%. Wu Jin. It is particularly preferable that the ionic polar valence (10) polar group in the second preferred embodiment of the polymer is an acid value when it is a few acid groups, and preferably i 5 _ 〇 mn ^ g ' Mh 7 mm 〇 1 / g 〜 5〇mm〇i/g, ^uK9 mmo g 4·〇mm〇i/g. When the ionic polar valence is in this range, the (four) property in the aqueous solution and the suppression of the decrease in the adhesion strength during the moist heat are simultaneously established. As a specific example of the above-mentioned polymer, a polymer described in paragraph [〇i Q6] to paragraph [Q丨丨2] of JP-A-2009-0G754G < Base polymer. Further, the polymer having a radical polymerizable group and an ionic polar group can be used as described in paragraph [〇〇65] to [0070] of JP-A-2006-135271. As the polymer having a radical polymerizable group, an interactive group, and an ionic polar group, the polymer described in paragraphs [0〇3〇] to [0108] of US2010-080964 can be used. Further, a polymer such as the following may also be mentioned.

32 S 201226627 jy^yyjpif [化η]

33 201226627 [Chem. 12]

(Method for synthesizing polymer) The method for synthesizing the above polymer is not particularly limited, and the monomer to be used may be a commercially available product or a combination of a known synthesis method. For example, the above polymer can be synthesized by referring to the method described in paragraphs [0120] to [0164] of Patent Publication No. 2009-7662. More specifically, when the polymerizable group is a radical polymerizable group, the method for synthesizing the polymer is preferably the following method. There may be mentioned: i) a monomer having a radical polymerizable group, having each other

S 34 201226627 ^yyyupif A method for copolymerizing a monomer; ϋ) copolymerizing a monomer having an interactive group and a monomer having a radical polymerizable precursor, followed by treatment a method of introducing a radical polymerizable group; and a method of bonding a monomer having an interactive group and a monomer having a reactive group for introducing a radical polymerizable group, and introducing a radical polymerizable group method. From the viewpoint of synthetic suitability, the preferred method is the above-mentioned Η) and the above-mentioned 111). 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. Further, in the case of synthesizing a filament comprising the unit represented by the above formula (A), formula (B), and formula (c), a monomer having a hydrophilic group or a precursor group thereof may have a hydrophilic group. The monomer of the interactive group outside its precursor group 'synthesizes the desired copolymer by the above methods i) to m). (The composition for forming a polymer layer (the composition for forming a layer to be plated, the polymer layer forming composition contains the polymer. The content of the polymer in the polymer layer forming composition is not particularly limited, as opposed to The total amount of the composition is preferably 2% by mass to 5% by mass, and preferably 5% by mass to 30% by mass. When the content of the polymer is within the above range, the handleability of the composition is excellent, and the polymerization is easily controlled. The layer thickness of the layer of the material layer is preferably a solvent. The solvent to be used is not particularly limited, and examples thereof include a solvent used for the composition for forming a base layer, and the like. And a guanamine-based solution, a ruthenium/yellow agent, a nitrile-based solvent, a carbonic acid-based solvent, and an alcohol-based solvent. Specifically, water, propylene, the same, dimercaptoacetamide, decylethyl hydrazine are preferred. , 35 201226627 Cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, dimethyl carbonate, j-methoxy-2-propanol, etc. -

Further, the content of the solvent in the polymer layer forming composition of the polymer layer is not particularly limited, and the ruthenium is true with respect to the total amount of the composition. ^ Good for 70 mass ° / 〇 ~ The composition is excellent in handleability, system, etc. (decane coupling agent) The polymer layer-forming composition may contain the above-mentioned decane coupling agent having a reactive group as needed. By containing a decane coupling agent, the adhesion between the base layer and the polymer layer is further increased and the film properties of the polymer layer are controlled. The type of the smoldering coupling agent used is as described above, and the preferred embodiment is also the same. When a decane coupling agent is contained in the polymer layer-forming composition, the composition of the polymer layer is excellent in terms of workability, adhesion between the polymer layer and the underlayer, and adhesion of the metal film. The mass ratio of the decane coupling agent to the polymer (the oxime coupling agent/polymer) is preferably from 1/1000 to 1/5, more preferably from 1/100 to 1/10. (Polymerizable compound containing P = 0 group) As described above, the base layer-forming composition and/or the polymer layer-forming composition described later contain the above-mentioned p=o group-containing polymerizable compound. When the polymer layer forming composition contains the compound, a strong interaction with the underlayer is formed via the p=0 group. Moreover, via aggregation

S 36 201226627 = The base forms a covalent bond with the above polymer, and * acts to improve the adhesion between the underlayer and the polymer layer. When the polymer layer-forming composition contains a poly-human compound having a p==0 group, the handleability and the adhesion between the polymer layer and the underlayer and the adhesion to the metal film are more excellent. The mass ratio of the ρ=fluorenyl group-containing polymerizable compound to the polymer in the polymer layer-forming composition (polymerizable compound/polymer containing Ρ=0 base) is preferably 1/1 〇〇〇~ 1/5, more preferably 1/100~1/10. (Step of Step (2)) The method of bringing the composition for forming a polymer layer into contact with the underlayer is not particularly limited, and examples thereof include a method of impregnating a substrate in a composition for forming a polymer layer, or a polymer layer. A method of forming a composition for coating on a base layer or the like. In terms of easily controlling the thickness of the obtained polymer layer, a method of applying a composition onto a substrate is preferred. The coating method can be carried out using the coating method described in the above step (1). When the polymer layer-forming composition is brought into contact with the underlayer, the coating amount of the polymer layer-forming composition is sufficient to form a structure of a sufficient interaction with a later-described catalyst or a precursor thereof. The solid content conversion is preferably 0.1 g/m 2 to 10 g/m 2 , and particularly preferably 〇 5 g/m 2 to 5 g/m 2 . Further, when the polymer layer is formed in this step, if necessary, a drying treatment may be carried out in order to remove the solvent in the composition layer for forming a polymer on the underlayer. For example, after coating, the remaining solvent can be removed by placing it at 2 Torr to 403⁄4 for 0.5 hour to 2 hours. The energy supply method for supplying energy to the polymer layer forming composition on the underlayer in this step can be irradiated with radiation such as heat or exposure. For example, it can be irradiated with light such as an ultraviolet (uv) lamp or visible light, or heated by a heating plate or the like. The light source for exposure is, for example, a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, a light emitting diode (LED) lamp, or the like. Radiation: electron beam, xenon ray, ion beam, far red line, etc. In addition, g-line, i-line, deep ultraviolet (Deep_uv) light, and high-density energy beam (laser beam) can also be used. For heating, for example, a usual heating pro, laminating machine, hot stamp, hot plate, thermal head, laser, air blow dryer, oven, heating plate, infrared dryer, heating drum Wait. The time required for energy supply varies depending on the light source, and is usually between seconds and 5 hours. The other energy supply methods can be combined and supplied. For example, exposure and heating can be combined. Further, the exposure supply energy day $' is preferably in the range of Η) η^η^8_ for the purpose of facilitating graft polymerization and controlling decomposition of the graft polymer formed, and more preferably (10) m2 ~ Recommended range of mJ/cm2. Further, the irradiation can be carried out in an environment in which the concentration of nitrogen gas, helium gas, carbon dioxide replacement === is controlled to be _ppm or less, preferably at least ppm. According to the needs, it can be used as a catalogue to supply energy. Then, after the energy supply, the composition can be appropriately supplied from the energy.

S 38 201226627 ==:::物=法法, ==仪,钱^== (polymer layer (coated layer)) The plate == is not particularly limited, as the metal film is based on the base, 3 Good for °·. One. More preferably, it is o.U/X6::r"^°·05^20^-- The surface roughness (Ra) of the layer is preferably in the form of wiring shape and adhesion strength, preferably μιη~〇3, more preferably 〇2 μπι~0.15 μιη. In addition, the surface roughness (Ra) is measured by a non-contact interferometry method according to the Ra described in JIS B 0601 (20010120), using a SUrfcom 3000A (manufactured by Tokyo Seimi Co., Ltd.). Further, the content of the polymer in the polymer layer is preferably from 2% by mass to 1% by mass based on the total amount of the polymer layer, more preferably from 1% by mass to 1% by mass. <Step (3): Catalyst Supply Step> Step (3) is a step of supplying a plating catalyst or a precursor thereof to the polymer layer obtained in the step (2). In this step, the interaction group in the polymer layer adheres (adsorbs) the supplied plating catalyst or its precursor depending on its function. More specifically, as shown in Fig. 1(C), a polymer layer 14b to which a plating catalyst or a precursor thereof is supplied is formed. 39 201226627 Subtracting A and Bistimulation: The catalyst or its precursors can be listed in the following step (4) (10). The plating catalyst or the precursor of the catalyst or electrode of the field or the precursor (4) the entangled medium or its precursor according to the mineral deposit of the step (4), spring, preferably electroless plating catalyst or Precursor. Precursor The material used in this step (electroless plating catalyst or its =#) feed fine _, _ this surface _ sequence detailed (electroless plating catalyst) when applied = catalyst as long as it becomes Electroless mineral energy metal (Pi: ^ 举. Eight catalysts with self-catalyst reduction reaction

Pt, AU, C〇f list. Pd, Ag, Cu, Ni,

Ag, Pd, Pt, iu. In terms of higher catalyst function, it is particularly preferable to use a metal colloid by means of a catalyst. Usually, the metal colloid can be produced by reducing the metal ruthenium, the electrical interface/tongue agent or the solution of the charged protective agent (4). The metal glue _ charge amount can be adjusted by the surfactant or the protective agent. ..., electrolytic plating catalyst precursor) The electroless nickel-free catalyst precursor used for chemical reaction can be electroless (4) catalyst precursor deplating touch as long as it can be used as an electroless plating catalyst. ^ Do not use it with restrictions. It is mainly possible to use metal ions as the above-mentioned electroless, enumerated metals. As a non-electrolytic mineral, the metal ion of the precursor of 201226627 is a valence metal which is an electroless plating catalyst by a reduction reaction. The metal ions as the electroless plating catalyst precursor are supplied to the polymer layer and can be changed into a valence metal by an additional reduction reaction before being immersed in the electroless plating bath as an electroless ore. Apply the catalyst. Further, the electroless plating catalyst precursor can be directly impregnated into the electroless plating bath and changed into a metal (electroless plating catalyst) by a reducing agent in the electroless plating bath. ^ As the metal ion of the electroless plating catalyst precursor, gold is preferably used, and the salt is supplied to the polymer layer. The (tetra) metal salt is a metal salt which is dissolved in a suitable two doses and is dissociated into a metal ion and an anion (anion), and is limited to: M(N〇3)n, MCln, M2). Metal ions can preferably be used as described above: gold ions. For example, cerium ions, CU can be multi-dentate #, strontium ions, Pd^. Among them, 'preferably and in terms of catalyst function, it is preferred; Ag ion, 'dimer ion. Hold the von Ag ion, Pd ion, cu case (free) or its precursor (Ji ion) as a plating touch, and then become an active nuclear ruthenium metal, 'that will play a role in mineral deposits' and In the case of the plating treatment, it is used as a core: if the palladium compound is packaged, 例如', for example, 13 (11) 趟, with 'there is no special household material, no electrolysis bond catalyst or its precursors 201226627 ^ ^ ^ As a better example. When silver ions are used, silver ions which are dissociated by a silvered person as shown below can be preferably used. Specific examples of the silver compound may be listed as silver acetate, silver acetate, silver sulfate, silver carbonate, silver cyanide, thiocyanate, silver vapor, silver bromide, silver chromate, silver chloroantimonate, salicylic acid. Silver, diethyl bis-dithiocarbamate, silver diethyldithiocarbamate, bismuth/acid. Among them, from the viewpoint of water solubility, silver citrate is preferred. (Other Catalyst) In the present invention, a zero-valent metal can be used as the catalyst used for direct plating without electroless plating of the polymer layer. The price of gold >i^^j^:Pd>Ag>Cu>Ni>Pt^AU>Co ψ « , metal capable of coordination with multiple teeth, especially adsorption (adhesion) to interactive groups In terms of higher catalyst function, it is preferably pd, Ag, or Cu. (Water or Organic Solvent) The plating catalyst or its precursor as described above is preferably a solution (ugly ship) secret to the polymerization leak. The solvent for the plating solution may be water or an organic solvent. By containing the organic catalyst, the permeability of the polymer or its precursor to the polymer layer is improved, and the mineral catalyst or its precursor can be efficiently adsorbed to the interactive group. The water used in the mineral-catalyzed liquid is preferably free of impurities. In this view, it is better to use reverse osmosis (10), 聪 〇 ( (5) water or ionized water, money water, purified water, etc. Use deionized water or steam

S 42 201226627 Line: = liquid = organic solvent as long as it can penetrate the polymer layer into the lamp, there is no particular limitation. For example, acetone: ethyl acetate, ethyl acetate, _ 1 ' 7 ^τ Ethylene glycol diacetate, cyclohexanone, ethyl sulfonate (IV), acetamidine, 2 servant hexaacetic acid vinegar, glycerol triacetate vinegar, diethylene: bismuth, ethyl ketone , carbonic acid (four), dazzle, N-曱τ 日-methyl cellosolve, etc. Especially with mineral coating catalyst or its precursors, she is a C-class, carbonated organic solvent, preferably ^ τ 丞, A fiber, a triethylene glycol monoterpene ether, a diethylene glycol dimethyl ether, a diethylene glycol diethyl ether. In addition, in a dispersion or a solution, an agent may be contained depending on the purpose. · Expanding _, or interface activity, etc. Port (the order of step (3)) t The method of supplying the slab or its precursor to the silk layer is not particularly limited, for example, the preparation of dispersing the metal Preparing a solution containing dissociated metal ions by dispersing a suitable dispersion medium or dissolving a metal salt by a suitable solvent, and The dispersion or the surface (the method of applying the recording medium to the polymer layer; the method of subdividing or submerging the substrate on which the polymer layer is formed, etc. v. Polymer layer and plating catalyst liquid The contact time is preferably from 3 sec to Μ an hour or so, preferably from about 1 minute to about 1 hour. The temperature of the plating catalyst at the time of contact is preferably from 5 ° C to 8 (about rc, more preferably 15). °C~60. (: Left and right. 43 201226627 W〆〆〆 As described above, the interaction of intermolecular forces by van der Waals can be utilized by contacting the plating catalyst or its precursor The electrostatic interaction such as an ionic bond or the interaction of the plating catalyst or its precursor in the polymer layer by the interaction of the coordination bonds of the isolated electron pair is sufficiently performed. From the viewpoint of such adsorption, the metal concentration or the metal ion concentration in the chain-contacting catalyst liquid is preferably in the range of 0.0Q1% by mass to mass%, more preferably in the range of 0.005% by mass to 30% by mass. Step (4): Plating step 〉 Step (4) is to supply the ruthenium catalyst or its precursor to the step (3) towel The polymer layer of the object performs the step of forming a metal film on the polymer layer. The metal film formed by this step has excellent conductivity and adhesion. More specifically, as shown in FIG. As shown, the metal film 16 is formed on the polymer layer state to obtain the laminated body 18. The type of the plating treatment performed in this step may be electroless plating or electric material, and the above step (1) The polymer layer is selected to form an interaction between the plating catalyst or its precursor. Among them, the formability and adhesion of the hybrid structure expressed in the polymer layer are preferably 'higher Electroless plating is carried out, and in order to obtain the metal film 16 having a desired film thickness, it is more preferable to perform electroplating after electroless plating. Hereinafter, the plating which is suitably performed in this step will be described. (electroless plating) Electroless plating refers to the use of a solution in which metal ions to be precipitated are dissolved.

201226627^. jyyyKjpiL As a plating, the metal is precipitated by a chemical reaction. In the electroless plating in this step, for example, the substrate to which the electroless plating catalyst is supplied is washed with water, and the excess electroless plating catalyst (metal) is removed, and then impregnated in the electroless plating bath. . A well-known electroless plating bath can be used for the electroless plating bath to be used. Further, the substrate to which the electroless plating catalyst precursor is supplied is subjected to water washing when the electroless ortho-catalyst precursor is adsorbed or impregnated in the polymer layer while being impregnated in the electroless mineral bath. After removing excess precursor (metal salt, etc.), it is immersed in an electroless plating bath. At this time, reduction of the plating catalyst precursor and subsequent electroless plating were carried out in an electroless plating bath. As the electroless plating bath used herein, a known electroless plating bath can be used in the same manner as described above. Further, the reduction of the electroless plating catalyst precursor may be carried out by using a catalyst activation liquid (reducing liquid) as an electroless plating solution as described above, and may be carried out as another step before electroless plating. . The catalyst activating solution is a solution in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly a metal ion) to a zero-valent metal is dissolved, and the concentration of the reducing agent is preferably 0.1% by mass based on the total solution. ~5〇% by mass, more preferably i% by mass to 30% by mass. As the reducing agent, a boron-based reducing agent such as sodium borohydride or dinonylamine borane, a reducing agent such as furfural or hypophosphorous acid can be used. In the case of impregnation, it is preferred that the concentration of the electroless plating medium or its precursor which is close to the polymer layer in contact with the electroless gold-free catalyst or its precursor is kept constant while stirring or stirring is applied. Immersion. The composition of a conventional electroless plating bath is in addition to the solvent stomach (e.g., water). 45 201226627 mainly contains an additive for reducing the stability of the additive, 3, and a metal ion, and may also contain #. In the plating bath, well-known additives such as the ore-forming agent: diene agent are included. In this respect, it is preferred to use a solvent which is soluble in water, such as an alcohol such as an alcohol. In order to use the ketones such as propylene and the like, methanol, ethanol, and isopropyl hydride are added. The types of metals used for vocabulary and use are known as copper, tin, copper, gold, and f', of which 'in terms of conductivity. 2 In addition, according to the above metal, the best reducing agent is selected from the electroless mineral deposit thus formed by the metal ion of the mineral bath, and the metal (four) metal film can be impregnated in the plating bath, or From the viewpoint of conductivity, it is preferably W or more, more preferably 0.2 μΓη to 2 μιη. The metal film formed by the electroless recording is preferably used to uniformly supply at least the film. Further, the impregnation time in the plating bath is preferably from about J minutes to about 6 hours, more preferably from about 1 minute to about 3 hours. The metal film obtained by electroless plating obtained as described above is confirmed by a cross-sectional observation by a scanning electron microscope (SEM) to include a plating catalyst or a polymer layer in the polymer layer. The metal-coated fine particles are dispersed at a high density, and the plating metal is precipitated on the polymer layer. The interface between the polymer layer and the metal film is resin

S 46 201226627 The state of the composite and the fine particles is mixed. Therefore, even if the interface between the polymer layer and the metal film is smooth, the adhesion is good. (Electroplating) In this step, when the plating catalyst or its precursor supplied in the above step (3) has a function as an electrode, the polymer layer to which the catalyst or its precursor is supplied can be plated. Further, after the electroless plating described above, the formed metal film is used as an electrode, and further electroplating can be performed. Thereby, an electroless plating film excellent in adhesion to the substrate can be used as a base layer, and a metal film having a new arbitrary thickness can be easily formed thereon. Thus, electroplating is performed after electroless plating, whereby the metal film can be formed to have a thickness corresponding to the target, and therefore it is suitable to use the metal film for various purposes. The method of the electric clock can use a previously known method. Further, examples of the metal used for the plating include copper, chromium, erbium, nickel, gold, silver, tin, and zinc. From the viewpoint of conductivity, copper, gold, and silver are preferable, and copper is more preferable. Further, the film thickness of the metal film obtained by electroplating can be controlled by adjusting the metal concentration, current density, and the like contained in the plating bath. Further, when applied to a general electrical wiring, a wire or the like, the film thickness of the metal film is preferably 〇.5 μπι or more from the viewpoint of conductivity, and more preferably! , claws ~ 30μιη. The thickness of the electric wiring is not limited. The thickness of the electric wiring is such that the line width of the electric wiring is changed (that is, the finer the electric wiring), and the electric wiring is made thinner in order to maintain the aspect ratio. Therefore, the layer thickness of the metal tantalum formed by electroplating can be arbitrarily set in addition to the above layer thickness. 47 201226627 <Laminated body> By the above steps (1) to (4), the substrate layer 12 having the substrate 1〇 and the decane-containing coupling agent as shown in Fig. 1(D) can be obtained. The polymer layer 14b and the layered body 18 of the metal film 16 (product of a metal film; body). The obtained laminated body 18 is used, for example, for a metal wiring substrate, and more specifically, can be applied to a printed wiring board, an electromagnetic wave resistant film, a coated film, a two-layer copper clad laminate (CCL 'Copper Clad Laminate) material, and electrical Various electronic device applications such as wiring materials. <Optional Step: Heating Step> After the plating step described above, the laminate having the metal film may be subjected to heat treatment (heating step) as needed. The heat treatment may be performed after the plating treatment, and the adhesion of the metal film (plating film) formed by the plating step is further improved. Further, when the electroless plating treatment and the plating treatment are carried out by the plating step, the heating step may be carried out after the electroless plating treatment, and the heat treatment may be performed after the treatment. The heating condition in the heating step differs depending on the polymer or metal film material used, and the heating temperature is preferably 8 (rc~2〇(rc,) in terms of improving the adhesion of the metal film. More preferably, the heating time is preferably from 5 minutes to 2 hours, more preferably from 3 minutes to about 1 hour, in terms of productivity and adhesion improvement. Further, in the heating step, the heat treatment may be performed twice in succession.

S 48 201226627u 2 Metal pattern material, and method for producing the same (1)> As shown in Fig. 1(E), the ugly forming step of forming the surface of the layered body 18 = the gold film 16 can be performed. A metal pattern material (layered body) having a patterned metal film 20 on the surface is produced. This pattern forming step is explained in detail below. (Pattern Forming Step) η. The step of etching the metal film into a pattern by the plating step described above: a step of forming a metal film. More specifically, as shown in FIG. The unnecessary portion of the metal film 16 is removed, and the patterned metal film 2 is formed on the polymer layer 14b. In the formation of the pattern, any method can be used, and specifically, the subtraction can be used. Forming method (providing a pattern mask on the metal film, = 阙 forming a mask to perform 阙 processing, removing the mask to form a patterned metal film), and semi-additive method (setting on the metal film) Pattern-like masking: plating is performed in such a manner that a non-formed region of the cover forms a metal film =) 'The mask is removed and processed to form a state of the remaining metal film. Fig. 2(A), 2(D) show Using the pattern of the subtractive method to form the shape of the step first, by performing the mineralizing step of the above step (4), the substrate 1G, the base layer 12 containing the Wei coupler, the U layer 14b, and the metal film 16 are not used. The laminated body 18. The metal film 16 is provided on one side of the substrate 10, but the metal film 16 is also provided. Both sides of the board 49 49 201226627 Next, as shown in FIG. 2(B), the pattern mask 22 is placed on the metal film 16. ° ' Then ' as shown in FIG. 2 (C), the mask 22 is not provided. The metal film 16 of the region is removed by a residual process (for example, dry etching or wet etching) to obtain a patterned metal film 20. Finally, the mask 22 is removed to obtain a metal pattern material 24. Λ The mask 22 can be fabricated. A well-known resist material can be used, for example, a resist layer can be provided on the metal film, and a mask of the same pattern of the pattern metal film can be formed by pattern exposure and development. The resist material can also be made of any material. 'A negative, positive, liquid, or film-like material can be used. In addition, the 'last name method can be any known method, etching, dry etching, etc., and can be arbitrarily selected. In the operation of the job; It is preferable to use it in terms of the simplicity of the apparatus, etc. _ If an aqueous solution of copper fluoride, ferric chloride or the like is used, Fig. 3 (Α) to Fig. 3 (Ε) show a form in which a semi-additive method is used. Forming the first 'preparation of the straight ancient Α & mixture of Figure 3 (A) The bottom layer 12, the polysilicon substrate 1G, the impurity-containing layer 18, the material layer 14b, and the metal film 16 are laminated on the film 16 as shown in Fig. 3. The pattern mask 22 is disposed on the gold connector. The mineral deposit treatment (for example, on the center of the region where the mask 22 is not provided) is as shown in Fig. 3 (C), and the metal film 16b is formed into a metal film to obtain a convex portion and a concave portion 50.

201226627 . ______II Then, as shown in Fig. 3 (D), the same material as the subtractive method can be used for the metal film (4), the residual liquid, and the like. Further, the method described above can be used for the plating method. For example, J2 may be removed from the metal film at the same time as the known method (Example L; J, electric f; ashing), etc., and the base layer and the polymer layer 14b are removed. The resulting metal pattern material can be used in various fields, for example, for electrical/electronic/communication, agriculture, forestry and fisheries, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automotive, precision equipment, Wood's extensive industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments. More specifically, it can be used for printers, personal computers, word processors, keyboards, personal digital assistants (PDAs), telephones, photocopiers, fax machines, electronic cash registers (ECR, electjOnic cash registers). ), calculators, electronic notebooks, cards, holders, stationery, etc. Business equipment, office automation (〇A, Office Automation) equipment, washing machines, refrigerators, vacuum cleaners, electric stoves, lighting appliances, game consoles, irons, ovens, etc. Home appliances 'TV (TV), VTR (videotape recorder), camcorder, tape recorder, tape recorder, mini disk, CD (compact disk) player, speaker, LCD display, etc. (AV, Audio Video Equipment, connectors, relays, 51 201226627 〆v/plt capacitors, switches, printed circuit boards, bobbins, semiconductor sealing materials, light-emitting diode (LED) sealing materials, wires, cables, transformers, Bias yoke, distribution box, semiconductor wafer, wiring substrate, flexible printed circuit (FPC, Flexibl e Printed Circuit), COF 'Chip On Film, Tape Automated Bonding (TAB), 2 CCL (Copper Clad Laminate) Material, Electrical Wiring Material, Multilayer Wiring Board, Motherboard , antennas, anti-electromagnetic waves, electrical and electronic parts such as watches and clocks, and communications equipment. In addition, when a metal pattern material is used as the wiring board, an insulating resin layer (interlayer insulating film) may be further laminated on the surface of the metal pattern material, and wiring (metal pattern) may be formed on the surface of the insulating layer (interlayer insulating film). ) or forming a solder resist on the surface of the metal pattern material. <Manufacturing Method of Metal Pattern Material (Part 2)> A method of producing a metal pattern material having a patterned metal film on the surface - a method of producing a film polymer layer. Φ = 言 'First, as shown in Fig. 4(A), in the above step (1) _ this 3 ==? (for example, exposure), followed by development processing, "14e. ^ into a base layer 12 containing /f coupling agent A specific mask may be used in the form of a pattern. When the energy is supplied to the pattern, the method of using a well-known method may be exemplified as needed (for example, a hydroxide solution; ^ = Sodium strontium carbonate water, an aqueous solution, and then, as shown in the figure, etc. The catalyst described in the step (1); ^ = the polymer layer 14c is subjected to the above-mentioned step, and is supplied with a plating catalyst.

S 52 201226627 - Patterned polymer layer 14d of At or its precursor. Finally, the mineral layer 14d is subjected to the mineralizing step described in the above step (4), whereby the patterned metal film 20 is formed on the polymer layer 14d as shown in Fig. 4(C). <Manufacturing Method of Metal Pattern Material (Part 3)> As another aspect of the method for producing a metal pattern material having a patterned metal film on the surface, a metal pattern material can be obtained by the following method. Specifically, 'after the above step (1), 'the base layer containing the decane coupling agent is patterned to supply energy (for example, exposure), and then the step (2) is carried out, and the development process of the polymer layer is performed, whereby only A patterned polymer layer is obtained on the uncharged region on the underlayer of the decane-containing coupling agent. Steps (3) and (4) are carried out on the polymer layer to obtain a metal pattern material. Further, this method is applicable to a case where a polymerizable compound containing a P = 0 group is contained in a composition for forming a base layer, or a reactive group in a samarium coupler is lost by energy supply such as a radical polymerizable group. Live situation. Specifically, first, as shown in Fig. 5(A), a base layer 12 containing a decane coupling agent is formed on the substrate 10 by the above step (1)'. Next, the base layer 12 containing the decane coupling agent is supplied with energy (e.g., exposure) in a pattern. More specifically, as shown in Fig. 5(B), a mask 30 of a specific pattern is placed on the base layer 12 containing a decane coupling agent, and the mask 30 is subjected to exposure treatment. Next, as shown in Fig. 5(C), the polymer layer 14a is formed on the underlayer 12 containing the decane coupling agent by the above step (2). Next, after the development of the polymer layer 14a, as shown in FIG. 4 (D) 53 201226627, pattern-like polymerization is obtained only in the unexposed regions of the underlayer 12 containing the decane coupling agent which are not exposed by the mask 30. The layer 14c. In the exposed region, the polymerizable group of the P = fluorenyl group-containing polymerizable compound in the base layer 12 containing the decane coupling agent disappears or the reactive group in the base layer 12 containing the decane coupling agent (for example, radical polymerization) The base is inactivated, so that even if step (2) is carried out, no chemical bond is formed between the underlayer 12 containing the decane coupling agent and the polymer layer 14a. Therefore, the resistance of the polymer layer on the exposed region of the underlayer 12 containing the decane coupling agent to the polymer layer on the unexposed region is different, and can be applied to the substrate containing the ceramsite coupling agent. The unexposed regions of layer 12 selectively form polymer layer i4c. Further, the method of the development treatment is not particularly limited, and examples thereof include a method of using a known developer (for example, sodium hydrogencarbonate water or an aqueous alkaline solution (for example, sodium aqueous solution)). As shown in Fig. 5(E), the pick-up layer 14c is subjected to the above-described, (1), and the patterned polymer layer 14d to which the ore or its precursor is supplied. Finally, the polymer layer 14d is subjected to the above step (4), whereby the patterned metal is formed on the polymer layer 14d as shown in Fig. 5(F). 20, [Example] The invention of Si is described in more detail. The value is explained in detail, and the synthesis method of the polymer of the money in this example is detailed.

S 54 201226627 (Synthesis Example 1: Polymer A) Ethyl acetate 丨l and 2-aminoethanol H9g' were placed in a 2 L three-necked flask to be cooled by an ice bath. 2# is added to the mixture to adjust the internal temperature to 2 (TC or less. Then, the internal temperature is raised to room temperature (25 ° C) and reacted for 2 hours. After the reaction is finished, 'additional distilled water The reaction was stopped by 3 〇〇 mL. Then, the ethyl acetate layer was washed 4 times with 300 mL of steamed water, dried by magnesium sulfate, and then ethyl acetate was distilled off to obtain 80 g of the starting material A. 20 g. Next, in a 500 mL three-necked flask, 47.4 g of a raw material, 22 g of D-pyridine, and 150 mL of ethyl acetate were charged and cooled by an ice bath, and 25 g of acrylonitrile chloride was added dropwise thereto. The temperature was adjusted to 2 〇. (: The following. Then, the temperature was raised to room temperature and reacted for 3 hours. After the completion of the reaction, 3 mL of distilled water was added to stop the reaction. Then, the ethyl acetate layer was washed by 3 mL of distilled water. After 4 times, it was dried by magnesium sulfate, and then the ethyl acetate was removed by evaporation. Then, the following monomer M was purified by column chromatography to obtain [Chem. 13].

8 g of N,N-dimethylacetamide was placed in a 500 mL three-necked flask and heated to 65 ° C under a nitrogen stream. The monomer M was added dropwise for 4 hours, 14_3 g, acrylonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), 3 〇g, propylene 55 201226627 ^ ^ acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 65 g, including v_65 (manufactured by Wako Pure Chemical Industries, Ltd.) 4 g of N,N-dimethylacetamide 8 g solution. After the completion of the dropwise addition, the reaction solution was stirred for 3 hours. Then, N,N-dimethylacetamide 41 g ' was added dropwise, and the reaction solution was cooled to room temperature. To the above reaction solution, 0.09 g of 4-hydroxyzirconium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 54.8 g of dioxane (DBU) were added, and the mixture was reacted at room temperature for 12 hours. Then, 54 g of a 70% by mass aqueous methanesulfonic acid solution was added to the reaction liquid. After the completion of the reaction, the solid component was taken out by reprecipitation by water to obtain a polymer A (weight average molecular weight: 370,000) (Mw/Mn = 18) l2 g. The acid value of the obtained polymer a was measured by using a potentiometric auto-titration device (manufactured by Kyoto Electronics Co., Ltd.) and using a sodium hydroxide aqueous solution as a titration solution, and as a result, the acid value of the polymer A was 3 9 faces 〇 1々. The obtained polymer A was examined using an infrared (IR' infrared ray) measuring machine (manufactured by Horiba). The measurement was carried out by dissolving the poly(P) in C with the use of KBr crystals. It is known from the IR measurement that a peak was observed around 224 Gcm and the nitrile was introduced into the polymer. In addition, by the acid value can be = ί 丙 稀 纽 。 。 。 。 导 导 。 。 Branch, silk early (dimethyl sulfoxide), determined by NMR (AV-3〇0;) of Brucella weathered blue 80. 3〇〇 MHz

The peak value of the element is in the 2. 5 ppm sentence _ (5H two US cyano group only when the peak of the unit containing the polymerizable group is wider at 78 -7, the phase is divided), 5.8 ppm -5.6 PPm (1H), Add PPm (1H 4.2 ppm -3.9 ppm (2H points) PP 5·2 touch (1H points), .3ppm-3.5Ppm(2H*)25 s 56 201226627_ιι ppm-0.7 ppm (6H points) was observed to be wider The peak corresponding to the carboxylic acid-containing monoterpene was observed to be wider at 2.5 PPm-0.7 ppm (3H), and the unit containing a polymerizable group: a unit containing a cyano group: a carboxylic acid group unit = 29 : 30 : 41 (mol%). [Chem. 14]

HN 丫, 〇 (Synthesis Example 2: Polymer B) 35 g of N-methylpyrrolidone was placed in a 1000 ml three-necked flask, and heated to 75 ° C under a nitrogen stream. In the course of 2.5 hours, 2-hydroxyethyl acrylate (commercial product, manufactured by Tokyo Chemical Industry Co., Ltd.) 6·6〇g, acrylic acid 2_cyanoethyl vinegar 28.4 g, and ν_6〇ι (made by Wako Pure Chemical Industries, Ltd.) were added dropwise. The N-thiol of g is converted to a 35 g solution. After the completion of the dropwise addition, the reaction solution was heated to 80 C' and then stirred for 3 hours. Then, the reaction solution was cooled to room temperature. To the above reaction solution, hydroquinone dibutyl ether hydride 29 ruthenium, dibutyl tin dilaurate 0.29 g, Karenz AOI (manufactured by Showa Denko KK), 18.S6 g, and N-mercaptopyrrolidone 19 g were added. At 55. The 〇 was reacted for 6 hours. Then, 3 6 g of decyl alcohol was added to the reaction liquid, followed by a reaction for 1.5 hours. After completion of the reaction, reprecipitation was carried out by water, and the solid component 57 201226627 was taken out to obtain 25 g of polymer B. (Identification of Structure) Polymer B was dissolved in ruthenium osmium], and was measured by NMR (AV-300) of 3 〇〇 MI^z manufactured by Bruker. It can be seen that the peak corresponding to the cyano group-containing unit is observed to be wider at 4.3 ppm_4.05 ppm (2H minutes), 2.9 ppm-2.8 ppm (2H minutes), and 2.5 ppm -1.3 ppm (3H minutes).

The peak corresponding to the polymerizable group is 7 2 ppm _7 3 pprn (1H min), 6.4 ppm -6.3 PPm (1H min), 6.2 ppm -6.1 PPm (1H min), 6.0 ppm -5.9 ppm (1H min ), 4.3 ppm _4 〇5 ppm (6H points), 3.3 ppm -3.2 ppm (2H points), 2.5 ppm -1.3 ppm (3H points) were observed to be wider, units containing polymerizable groups: units containing cyano groups =20 : 80 (mol% ). (Measurement of molecular weight) Polymer B was dissolved in tetrahydrofuran (THF, tetrahydrofuran), and determined by a gel permeation chromatograph (GPC, manufactured by Tosoh) (HLC-8220GPC). Molecular weight. As a result, it was found that a peak appeared at 23.75 minutes, and Mw = 60000 (Mw/Mn = 1.9) in terms of polystyrene. Further, the numerical values in the chemical formula of the following polymer B represent the mole % of each unit. [化15]

S

58 201226627ιτ ---- -Γ Al <Example 1> [Preparation of base layer containing decane coupling agent] On a glass substrate (EAGLE 2000 (50 mm x 50 mm x 〇. 7 mm) of Corning), by spin The base layer forming composition X1 containing 3-(acryloxy)propyltrimethoxydecane (KBM_5103) and KAYAMER PM_2i (manufactured by Sakamoto Chemical Co., Ltd.) was applied by coating, and dried at n〇°c for 5 minutes. . Then, the substrate was washed with isopropyl alcohol, followed by washing with water, and a two-gas dry button was applied to obtain a base layer containing a dream-burning coupler. Further, the mass ratio of '3-(propylene decyloxy) propyl tridecyloxylate to PM-21 was 1:0.25. Further, the base layer forming composition XI contains cyclopentanone as a solvent, and the content of the cyclopentanone is 94% by mass based on the total amount of the composition. The surface water contact angle of the glass substrate and the surface water contact angle of the glass substrate after the above treatment were measured, and the results were each measured as 3. 25. By the above treatment, it was confirmed that the underlayer containing the decane coupling agent was formed on the glass substrate. [Formation of Polymer Layer] Then, a polymer layer comprising polymer A and 3-((acryloxy)oxypropyl trimethoxy group, a composition of γι, was coated by a spin coating method to have a Wei-containing coupling Lying on the substrate of the basal layer, the thief relies for 5 minutes. Then, uv exposure (exposure: 12 〇〇〇 mJ/cm 2 ) was carried out on the entire surface of the substrate U 254 nm with 1% sodium hydrogencarbonate water. Thereby, a polymer layer (thickness: 1 μm) directly bonded to the underlayer containing the ceramide coupling agent on the substrate was obtained. 59 201226627

Further, the content ratio of 3-(acryloxy)propyltrimethoxydecane was 5.7% by mass based on the total mass of the polymer A. Further, the polymer layer-forming composition Y1 contains a mixture of water and diterpeneoxy-2-propanol (current mass ratio (hydroxyloxy-2-propanol) = 2/8) as a solvent, water The content of the mixture with 1-methoxypropanol was 92.6% by mass based on the total amount of the composition. [Supply of Catalyst] A 1% by mass aqueous silver nitrate solution was prepared and used as a money-contacting catalyst liquid. The substrate having the polymer layer was immersed in the plating catalyst liquid for 5 minutes, and then washed with pure water. [Forging treatment and heat treatment] Next, the polymer layer to which the catalyst was supplied was subjected to electroless plating. The electroless plating was performed using an electroless plating bath having the following composition using a Through-Copper PGT (manufactured by Uemura Industrial Co., Ltd.) at a bath temperature of 3 (rc impregnated the polymer layer to a plating thickness of 〇·5 μιη). The method forms a mineral copper film (metal ruthenium). " The liquid preparation sequence and raw materials of the electroless plating solution are as follows. Distilled water PGT-A PGT-B PGT-C Formalin liquid wood about 60% by volume 9.0% by volume 6.0 Volume% 3.5% by volume 2.3% by volume Finally 'liquid level adjustment by distilled water to a total volume of 丨〇〇 volume 0 / 〇. * The formalin used here is a phthalic acid solution (special grade) of Wako Pure Chemical. 201226627 — Then, the obtained substrate was subjected to a heat treatment for 30 minutes on a loot: and then heat-treated at 14 (TC for 30 minutes). After the heat treatment, the surface of the metal film was degreased using a 1 mass% sulfuric acid aqueous solution. Then, the metal film obtained above was used as a power supply layer, and electrolytic copper plating (3 A/dm 2 : 30 minutes) was carried out with a copper thickness of 12 μm using a copper shovel copper bath having the following composition to obtain a laminate having a metal film. (electrolytic copper bath Composition) • • Water 1,000 parts by mass 110 parts by mass of copper sulfate pentahydrate • 98% sulfuric acid 270 parts by mass • 0.2 mass parts 35% hydrochloric acid

• Made from Meltex, 30 parts by weight of Copper Gleam ST-901M Next, the obtained substrate was subjected to heat treatment for 30 minutes at 10°. <Example 2> The base layer forming composition X2 having the following composition was used instead of the base layer forming composition XI, and the polymer layer forming composition Y2 having the following composition was used instead of the polymer layer forming composition Y1. Other than this, a laminate was obtained in the same order as in Example 1. (Substrate layer forming composition X2) • 3-(propylene decyloxy) propyl trimethoxy decane 4.8% by mass • Cyclopentanone 95.2% by mass (polymer layer forming composition Y2) • Polymer A 7.0 mass % 61 201226627 • 3-(propylene decyloxy)propyltrimethoxydecane is 5.7% by mass relative to polymer A relative to 3-(propylene KAYAMER PM-21 decyloxy)propyl tridecyloxydecane And it is a mixture of 25% by mass of water and 1-nonoxy-2-propanol (mixing mass ratio (water 92.5 mass% / 1-decyloxy-2-propanol) = 2/8) <Example 3&gt A laminate was obtained in the same order as in Example i except that the polymer layer-forming composition Y2 was used instead of the polymer layer-forming composition Y1. <Example 4> The 3-(acryloxy)propyltrimethoxy decane used in the base layer-forming composition XI and the polymer layer-forming composition Y2 was changed to 3-trimethyl methacrylate. A laminate was obtained in the same manner as in Example 3 except for the oxyalkylalkylpropyl ester. <Example 5> A laminate was obtained in the same manner as in Example 1 except that the polymer layer-forming composition γ3 having the following composition was used instead of the polymer layer-forming composition Y1. (Polymer layer forming composition Y3) • Polymer A 6.9 mass 〇 /0 • 3-(acryloxy) propyl trimethoxy decane was 10.0% by mass relative to the polymer A. • KAYAMER PM- 21 relative to 3 · (internal

62 201226627. 醯oxy)propyltrimethoxydecane and 25% by mass • Mixture of water and 1-methoxy-2-propanol (mixed mass ratio (water/1-methoxy-2-propanol) (2), the amount of the product of (manufactured by the company) 'In addition to this, a laminate was obtained in the same order as in Example 3. <Example 7> An aggregate body was obtained in the same order as in Example 1 except that the polymer layer-forming composition Y4 having the following composition was used instead of the polymer layer-forming cone-formed product Y1. (Polymer layer forming composition Y4) • Polymer A 7 mass% • Mixture of water and methoxypropanol (mixing mass ratio (water octa-methoxy-2-propanol) = 2/8) 93.0% by mass <Example 8> 3—(Propyloxy)propyltrimethoxy decane used in the base layer-forming composition XI and the polymer layer-forming composition Y2 was changed to 3 —glycidyloxy group A laminate was obtained in the same order as in Example 3 except for propyltrimethoxydecane (LS2940). <Example 9> The polymer A used in the polymer layer-forming composition Y2 was changed to the polymer 抒' and the mixture of water and 1-nonoxy-2-propanol was changed to 63 201226627 ^ ^ ^ A mixture of dinonyl carbonate and acetonitrile (mixing mass ratio: dinonyl carbonate / acetonitrile = 1/2) was obtained, except that in the same procedure as in Example 2, a product was obtained. <Example 10> The polymer A used in the polymer layer-forming composition Y4 was changed to the polymer B, and the mixture of water and 1-nonoxy-2-propanol was changed to dinonyl carbonate and A laminate was obtained in the same order as in Example 7 except that a mixture of acetonitrile (mixing mass ratio: dinonyl carbonate / acetonitrile = 1/2) was obtained. <Comparative Example 1> A laminate was obtained in the same manner as in Example 1 except that the underlayer formation composition X2 was used instead of the underlayer formation composition XI'. Further, in Comparative Example 1, neither the base layer-forming composition nor the polymer layer-forming composition contained a polymerizable compound containing p==fluorene group. <Comparative Example 2> The polymer layer forming composition 丫4 is used in place of the polymer layer forming composition XI4 in place of the polymer layer forming composition Y1, in addition to the underlying layer forming composition X2. The laminate was obtained in the same order as the example. In addition, in the comparative example 2, neither the base layer forming composition nor the polymer layer forming composition contained the polymerizable compound containing p = fluorenyl group, and the polymer layer forming composition was not Containing Shi Xizhuo coupling

S 64 201226627 agent. &lt;Comparative Example 3&gt; In addition to KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.) used in the base layer forming composition X1, the acid-containing diethyl vinegar (manufactured by Daihatsu Chemical Co., Ltd.) was used. In the same manner as in the example 1, the laminate was produced. The metal film at the time of the plating step was described after the third step, and the evaluation method (one) was not carried out. The obtained laminate was at 14 Å. The surface of the laminate (5:2:1 horrible heat treatment. Magnification 25 times for observation, when the watch is swelled, any one of the laminates (4) will have poor adhesion in the raft. In addition, Spoon, the result is that the metal is not better than the table. It is better to be non-"χ". The result is ^〇": no uplift; △". Observed 2 or less 吉你ς "V view _3_上/ The ridges under 彳Γ5(4); the ridges up to 5 inm straight. The bulges or observations of straight I5·belows. In addition, when the ridges are not round, the above evaluation is carried out by the round phase fires ^ equivalent () (projection) Area circle <Evaluation method (Part 2)&gt; When the above evaluation method (one of the above) is used, The time is changed to 2, and the evaluation is performed on the basis of the table b. The result is 65 201226627 &lt;Evaluation method (3)&gt; The heat treatment condition at 140 ° C for 1 hour in the above evaluation method (one) The evaluation was carried out according to the same criteria as above except that the temperature was changed to 180 ° C for one hour. The results are shown in Table 1. In Table 1, the "Si agent" column indicates the decane coupling agent in each composition. The presence or absence of the case is described as "〇", and the case where it is not included is marked as "x". In addition, in Table 1, the column "P = Tanning agent" indicates the polymerizability of P = 0 group in each composition. The presence or absence of the compound is described as "〇", and the case where it is not contained is referred to as "x". The "-" in Table 1 means not implemented. [Table 1] Table 1

Evaluation result of composition for forming a polymer layer for forming a base layer Si agent P=0 Agent Si agent p=o agent evaluation (one) Evaluation (Part 2) Evaluation (Part 3) Example 1 〇〇〇X 〇 〇 - Example 2 0 X 〇〇〇〇 - Example 3 〇〇〇〇〇〇〇 Example 4 〇〇〇〇〇 0 〇 Example 5 0 〇〇〇〇〇 0 Example 6 〇〇 0 〇〇〇 Δ Example 7 〇 〇XX 〇Δ - Example 8 〇〇〇〇〇〇Δ Example 9 〇X 〇〇〇〇Δ Example 10 〇〇XX 〇〇Δ Comparative Example 1 0 X 〇XXXX Comparative Example 2 0 XXXXXX According to the results of Table 1 above In the laminate obtained by the production method of the present invention, almost no bulging or the like was observed, and the metal film exhibited excellent adhesion.

66 S 201226627 if, according to the comparison between Example 1 and Example 7, it was confirmed that a more excellent effect can be obtained by including a decane coupling agent in the polymer layer. Further, according to the comparison between Example 3 and Example 6, it was confirmed that a more excellent p = fluorenyl group-containing polymerizable compound having a longer alkyl group of Lb in the formula (2) can be used. effect. Further, according to the comparison between Example 3 and Example 8, it was confirmed that a more excellent effect can be obtained by using a decane coupling agent having a propylene group as a radical polymerizable group as a reactive group. On the other hand, in Comparative Example 1 and Comparative Example 2 in which neither the base layer-forming composition nor the polymer layer-forming composition contained the polymerizable compound containing p=fluorenyl group, 'the specific effect was not obtained. Laminated body. &lt;Pattern formation&gt; On the surface of the metal film of the laminate obtained in the above Example 1, a dry resist film (Hitachi Chemical Co., Ltd.) was produced by a vacuum laminator (manufactured by Nagoya Co., Ltd.: MVLP-600). (manufacturing); RY3315, film thickness: 15 μm) Lamination at 70 ° C at 0.2 MPa. Next, the substrate on which the dry resist film is laminated is adhered to a glass mask which can form a comb-shaped wiring (according to jpcA-BUO 1-2007) prescribed by JPCA-ET01, by the center wavelength The 405 nm exposure machine irradiated the resist with a light energy of 70 mJ. The exposed substrate was sprayed with a 1% Na2C〇3 aqueous solution at a spray pressure of 〇 2 MPa, and developed. Then, the substrate was washed with water and dried to form an anti-reagent pattern for the subtractive method on the ore film. The substrate on which the resist pattern is formed is immersed in an aqueous solution of FeCl 3 /HCl (money engraving) at a temperature of 4 Torr, and the copper plating film is formed in the non-formation region of the pattern of the anti-sand 67 201226627 pattern. Remove.

Then, a 3% Na〇H aqueous solution was sprayed on the substrate with a spray pressure of 0.2 MPa, and the resist pattern was swollen and peeled off, neutralized by a 1%% sulfuric acid aqueous solution, and washed with water to obtain a comb type. Wiring (patterned copper film). The resulting wiring was L/S = 20 μm / 75 μιη. Then, the polymer layer and the underlayer between the wirings are removed by plasma ashing. -« Next, the solder resist (PFR800; manufactured by Sun Ink Manufacturing Co., Ltd.) was 70. (: Vacuum lamination on the obtained comb-shaped wiring under conditions of 0.2 MPa.) 420 mJ of light energy was irradiated by an exposure machine having a center wavelength of 365 nm. Next, the substrate was subjected to 80. (:/10 minute heat treatment) Thereafter, a 1% aqueous solution of NafO3 was sprayed onto the surface of the substrate by a spray pressure of 2 MPa, and developed, washed with water, and dried. Then, the substrate was irradiated with a light energy of 1000 mj by an exposure machine having a center wavelength of 365 nm. Heat treatment at 150 ° C / 1 hr was performed to obtain a comb-type wiring (wiring substrate) covered with a solder resist. <Example 11> The preparation of the base layer containing a decane coupling agent of Example 1 was obtained. A glass substrate containing a base layer of a decane coupling agent. Then, the polymer layer-forming composition Y1 was applied onto a substrate having a base layer containing a decane coupling agent by spin coating, and dried at 80 ° C for 5 minutes. Then, the glass mask of the comb-type wiring (according to JPCA-BU01-2007) defined by JPCA-ET01 was formed, and the entire surface of the substrate was UV-exposed at 254 nm (exposure: i2000 mJ/cm2). By 1〇/.

68 S 201226627 . Wash with sodium bicarbonate water. Thus, a patterned polymer layer (thickness: 1 μ! Π) directly bonded to the underlayer containing the decane coupling agent on the substrate was obtained. Then, the [supply of catalyst] and [plating treatment and heat treatment] of Example 1 were carried out to obtain a laminate having a patterned metal film. &lt;Example 12&gt; The [base material layer containing a decane coupling agent] of Example 1 was obtained, and a glass substrate having a base layer containing a decane coupling agent was obtained. Next, a glass mask of a comb-type wiring (according to JPCA-BU01-2007) prescribed by JPCA-ET01 can be formed, and the entire surface of the underlayer containing the decane coupling agent is UV-exposed in a pattern of 254 nm (exposure amount: 12,000) mJ/cm2) ° Then, the [formation of the polymer layer] of Example 1 was carried out, and only the unexposed region of the base layer of the decane-containing coupling agent which was not subjected to UV exposure, which was not subjected to UV exposure, was transferred to the substrate containing the decane coupling agent. A patterned polymer layer (thickness: 1 μηι) in which the layers are directly bonded. Then, [supply of catalyst] and [plating treatment and heat treatment] of Example 1 were carried out to obtain a laminate having a patterned metal film. &lt;Example 13&gt; A laminate was obtained in the same order as in Example 1 except that the glass substrate used in Example i was used instead of the sapphire substrate (manufactured by KYOCERA Co., Ltd., SEMI standard). The obtained laminate was evaluated according to the above evaluation method, and as a result, the same results as in Example 1 were obtained. 69 201226627 In addition, when the sapphire substrate (Optostar Co., Ltd., single crystal 4 inch standard) was used instead of the sapphire substrate, an alumina substrate (manufactured by Kyocera Co., Ltd., a substrate for a film), and the same results as in Example 1 were obtained. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1(A) to FIG. 1(E) are schematic diagrams showing the respective steps from the substrate to the layered body having the patterned metal film in the respective manufacturing steps in the method for producing a layered product of the present invention. Sexual profile. 2(A) to 2(D) are schematic cross-sectional views showing the steps of manufacturing a metal pattern material having a patterned metal film in order. 3(A) to 3(E) are schematic cross-sectional views showing the steps of manufacturing a metal pattern material having a patterned metal film in order. 4(A) to 4(C) are schematic cross-sectional views showing the steps of manufacturing a metal pattern material having a patterned metal film in order. 5(A) to 5(F) are schematic cross-sectional views showing the steps of manufacturing a metal pattern material having a patterned metal film in order. [Main component symbol description] 10: Substrate 12: Base layer 14a, 14b, 14c, 14d containing a decane coupling agent: Polymer layer 16, 16b: Copper-containing ore film 18: Laminate 20: Patterned metal film 22 , 30: mask 24: metal pattern material

Claims (1)

201226627, VII. Patent Application Range: 1. A method for producing a laminate having a metal film, comprising: a base layer forming step of forming a base layer comprising a ceramsite coupler having a reactive group on a substrate The composition is contacted to form a base layer containing a sulphur coupling agent; a polymer layer forming step on the base layer of the decane-containing coupling agent to contain a polymerizable group, and a plating catalyst or a precursor thereof a polymer layer forming composition of the interacting functional group polymer is contacted, and then supplying energy to form a polymer layer; and a catalyst supply step of supplying the mineral catalyst basin precursor to the polymer layer; a plating step of plating the plating catalyst or a precursor thereof to form a metal film on the polymer layer; and the composition for forming the underlayer layer and/or the composition for forming the polymer layer The material contains a polymerizable compound containing p=fluorenyl group. The method for producing a laminate having a metal film according to the first aspect of the invention, wherein the polymerizable compound having a P=0 group is a compound represented by the formula (1): [Chemical Formula 1] In the formula (1), V represents a polymerizable group; La represents a single bond, or 71 20122662Jx divalent organic group; Ya represents a hydrogen atom or a substituent having no polymerizable group; p represents 1 An integer of ~3, q represents an integer of 〇~2, and 卩 and q satisfy the relationship of p + q = 3.) 3. The method for producing a laminate having a metal film according to the invention of claim 2, wherein the reactive group is a mercaptopropenyl group, an acrylonitrile group, a glycidyl group, an amine group, or a benzene group. Vinyl, vinyl, fluorenyl, ureido, thio, isocyanate or carboxyl. 4. The method for producing a laminate having a metal film according to the above aspect of the invention, wherein the polymer layer-forming composition further comprises a cerium-burning coupling agent having a reactive group. 5. The method for producing a laminate having a metal film according to the invention of claim 2, wherein the polymer layer-forming composition comprises a decane coupling agent having a reactive group, and p = A polymerizable compound of a mercapto group. 6. The method of producing a laminate having a metal film according to the first or second aspect of the invention, wherein the substrate is a glass substrate or a Tauman substrate. 7. The method for producing a laminate having a metal film according to claim 1 or 2, wherein the towel has a heating step of performing a heat treatment after the plating step. 8. The method for producing a laminate having a metal film according to the above item, wherein in the base layer forming step, the base layer forming composition is contacted on the substrate. The substrate is cleaned by dissolution. S 72 201226627〆9. A method of producing a metal pattern material, comprising a pattern forming step of fabricating a laminate having a metal film according to any one of claims 1 to 8. The metal film in the laminate obtained by the method is etched into a pattern to form a patterned metal film. A metal pattern material obtained by the method for producing a metal pattern material as described in claim 9 of the patent application. A printed wiring board comprising the metal pattern material as described in claim 10 of the patent application. 73