CN104025722A - Copper foil for lamination - Google Patents

Abstract

The purpose of the present invention is to provide a copper foil for lamination, said copper foil exhibiting excellent adhesion to a substrate and being capable of forming a high-precision wiring pattern. This copper foil for lamination is a copper foil to be laminated on a substrate, wherein the surface roughness (Rz) on the side to be faced to the substrate is 0.500um or less, and the fractal dimension of a cross-sectional profile on the side to be faced to the substrate is 1.020 to 1.400 as calculated by applying a box counting method wherein the side length of the square boxes is set to 1 to 10nm.

Description

Attaching Copper Foil

Technical field

The present invention relates to a kind of attaching Copper Foil.

Background technology

Metallic copper is electric good conductor, relatively cheap, and operation is also easy, so Copper Foil is widely used as the basic material of printed wiring board etc.

When manufacturing printed wiring board, conventionally by Copper Foil and the specific overlapping lamination of base material, add thermo-compressed and obtain copper-cover laminated body.In addition, the face with base material laminating of Copper Foil can be implemented roughened processing (patent documentation 1) in order to improve with the adhesion of base material conventionally.

On the other hand, strongly expect in recent years densification, high reliability and the miniaturization and of printed wiring board, require to form that width is narrow, the Wiring pattern of fine thereupon.

Yet, if use, existingly implemented the Copper Foil of roughened processing and formed Wiring pattern, have the surperficial concavo-convex impact through roughened processing due to Copper Foil, and the inequality of the distribution width of the Wiring pattern of gained becomes large problem.

In order to form the Wiring pattern of fine, and there is the lower method of asperities height that makes Copper Foil.Yet, in the method, because the adhesion of Copper Foil and base material reduces, therefore produce the problems such as the peeling off of copper foil circuit, protuberance, layering.

So, in the past,, the high-precision refinement of Wiring pattern exists the relation of mutually compromise (trade off), be difficult to meet the two with the high adhesion of base material simultaneously.

Prior art document

Patent documentation

Patent documentation 1: No. 3476264 communique of Japan Patent

Summary of the invention

The problem that invention will solve

The present invention completes in view of above-mentioned actual conditions, and object is to provide and a kind ofly shows with the good adhesion of base material and can form the attaching Copper Foil of the Wiring pattern of fine.

In addition, the object of this invention is to provide and use above-mentioned attaching with Copper Foil and the laminate and the printed wiring board that obtain.

The technological means of dealing with problems

The inventor carries out active research, found that, uses the surface of the side that is attached at base material of Copper Foil to have specific structure, and can address the above problem by attaching.

Find, by method shown below, can reach above-mentioned purpose.

(1) an attaching Copper Foil, it is in order to be attached on base material,

The surperficial surface roughness (Rz) that is attached at the side of base material is below 0.500 μ m;

The fractal dimension (fractal dimension) of surperficial outline line that is attached at the side of base material in the section of Copper Foil is 1.020～1.400, and described fractal dimension is that application is set as the size on a limit of square box the box dimension of 1nm～10nm and calculates.

(2) laminate, it comprises: base material and be attached at the attaching Copper Foil as described in (1) on base material.

(3) printed wiring board, it contains just like the laminate (2) Suo Shu.

(4) attach the manufacture method with Copper Foil, it,, for the manufacture of the attaching Copper Foil as described in (1), comprising:

On supporter, the layer that formation comprises polymer, then to the layer that comprises polymer, provide energy, and on supporter, form by the operation of plating layer, wherein above-mentioned polymer has and forms interactional functional group and polymerism base with plating coating catalyst or its predecessor;

To the operation of plating coating catalyst or its predecessor is provided by plating layer;

To what plating coating catalyst or its predecessor be provided, by plating layer, carried out copper plating treatment, on by plating layer, form Copper Foil, and obtain sequentially there is supporter, by the operation of the laminate of plating layer and Copper Foil;

From laminate, remove supporter and by plating layer, obtained the operation of Copper Foil.

The effect of invention

According to the present invention, can provide and show with the good adhesion of base material and can form the attaching Copper Foil of the Wiring pattern of fine.

In addition, according to the present invention, also can provide and use laminate and the printed wiring board of Copper Foil for above-mentioned attaching.

Accompanying drawing explanation

Fig. 1 (A) is the schematic perspective view of Copper Foil for attaching of the present invention.(B) be the enlarged drawing of the face side of A-A line section.

Fig. 2 means the flow chart of the manufacturing process of an example of the manufacture method of Copper Foil for attaching of the present invention.

Fig. 3 (A)～(D) sequentially represents the schematic cross sectional view of each manufacturing process of an example of the manufacture method of Copper Foil for attaching of the present invention.

Embodiment

Below, the attaching of this example is described with Copper Foil.

The attaching Copper Foil of this example, its attaching face shows specific surface roughness Rz, and the fractal dimension that attaches the outline line of face in the section of calculating by box dimension shows specific value.By attaching face, show specific surface roughness Rz, and in this attaching face large concavo-convex few (low level (low-profile)), result when forming, pattern can form the Wiring pattern of fine.And, by attaching the section profile line of face, show specific fractal dimension, and there is small and complicated surface texture.That is,, even if the surface roughness Rz of the face of attaching is little, also because its complicated surface configuration has sufficient surface area, result shows sufficient tackify (anchor) effect to base material, and base material is shown to excellent adhesion.That is, can realize in the past simultaneously raising for the adhesion of trade-off relation, with the fine of Wiring pattern.

First, below to attaching, by the form of Copper Foil, be described in detail, then the manufacture method of this Copper Foil be described in detail.

[attaching with Copper Foil (laminating Copper Foil)]

The Copper Foil for attaching of this example (below also referred to as Copper Foil) is in order to be attached at substrate surface.The base material that description is used.

Fig. 1 (A) is the schematic perspective view attaching with Copper Foil 10, and Fig. 1 (B) is the enlarged drawing of the near surface of the A-A line section in Fig. 1 (A).In addition, in Fig. 1 (B), attach the surperficial outline line that top with Copper Foil 10 is equivalent to be attached at the side of base material.As shown in the drawing, attach with Copper Foil 10 little with the surperficial surface roughness Rz of side base material attaching, in macroscopic view, be smooth face, but on microcosmic, there is complicated surface configuration.

The surperficial surface roughness Rz of the side that is attached at base material of Copper Foil is below 0.500 μ m.If surface roughness Rz is in above-mentioned scope, can form efficiently the Wiring pattern of fine.Wherein, with regard to can forming the aspect of the narrower Wiring pattern in gap, surface roughness Rz is preferably below 0.300 μ m, more preferably below 0.200 μ m fine.In addition, there is no particular restriction for the lower limit of surface roughness Rz, most preferably is 0 μ m, but with regard to industrial productive aspect, more than being mostly 0.050 μ m.

In addition, when Rz surpasses 0.500 μ m, the inequality of distribution width can become greatly, and cannot obtain the Wiring pattern of fine.

In addition, so-called surface roughness Rz, the maximum height roughness of JIS B0601 (calendar year 2001) defined, moral gram iron gram 150 (Dektak150)) etc. can be by known surface-profile measuring instrument (such as exabyte: Ai Fake (ULVAC), device name: measure.

In the section of Copper Foil, the surperficial outline line of the side that is attached at base material of Copper Foil (section profile line) is minute shape, and the fractal dimension of applying the surperficial outline line that the size on a limit of square box is set as to the box dimension of 1nm～10nm and calculates is 1.020～1.400.If fractal dimension is in above-mentioned scope, Copper Foil shows excellent adhesion to base material.Wherein, with regard to regard to the more excellent aspect of the adhesion of base material, fractal dimension is preferably 1.050～1.400, and more preferably 1.100～1.300, be especially preferably 1.150～1.250.

In addition, at fractal dimension, be less than 1.020 and surpass at 1.400 o'clock, Copper Foil is poor to the adhesion of base material.

Below, box dimension is described in detail.

So-called box dimension, is the size (box size) of fixing when cutting apart fixing region and observing, by inquiry fractal figure by which kind of degree comprise, and infer the method for fractal dimension.

" fractal dimension (box-counting dimension) " means the complexity of shape, the index of the concavo-convex degree on surface etc., and it is concavo-convex more complicated that the value of fractal dimension more represents, defines in the following manner.By take the number that square case (box) that the size on a limit is δ covers the needed box of certain figure F, be made as N _δ(F), time, fractal dimension defines according to following formula.

$D_B=-\underset{\mathrm{\δ}\→0}{\lim }\frac{\log N_{\mathrm{\δ}}\left(F\right)}{\log \mathrm{\δ}}$

; in the present invention; the section of Copper Foil is divided into the clathrate region of δ uniformly-spaced (the foursquare zonule that the size by a limit is δ is cut apart); change on one side the size of δ, on one side the number of the size on a limit of a part of surperficial outline line of the counting side that is attached at base material that the comprises Copper Foil square box (unit) that is δ.Then, the number of the box of counting is made as to the longitudinal axis, the size of δ is now made as to transverse axis, plot two logarithm charts, according to the slope of this chart, obtain fractal dimension.

In addition, the scope that in the present invention, δ is 1nm～10nm.

In addition, in the present invention, measuring area is 1 μ m * 1 μ m.

And the fractal dimension in the present invention is to measure region (1 μ m * 1 μ m) according to sections more than at least 5 positions to calculate respectively fractal dimension, and these values are carried out to arithmetic average and value.

More specifically, fractal dimension of the present invention is that cross-section structure photo (photo of the face parallel with the thickness direction of Copper Foil) according to Copper Foil is calculated.First, use two-beam focused ion beam (Dual-Beam FIB) device (FEI manufactures, two-beam promise bar 200 how Nola Pu (Dual Beam Nova200Nanolab), accelerating voltage 30kV), Copper Foil is processed into sample, and cuts out section.Then, by cluster ion beam device (manufacture of Seiko electronics (Seiko Instruments) company, SMI9200), observe its section, and obtain view data.Then, by image, process, extract the coarse surface portion (line segment) of Copper Foil.According to this cross sectional photograph, use above-mentioned box dimension, according to the mensuration region at least 5 positions (1 μ m * 1 μ m), calculate respectively the fractal dimension (box-counting dimension) of outline line, these values are carried out to arithmetic average and obtain fractal dimension of the present invention (average fractal dimension).

There is no particular restriction for the surperficial surface roughness Ra of the side that is attached at base material of Copper Foil, with regard to can forming efficiently the aspect of Wiring pattern of fine, is preferably below 0.200 μ m, more preferably below 0.100 μ m.In addition, there is no particular restriction for the lower limit of surface roughness Ra, most preferably is 0 μ m, but with regard to industrial productive aspect, more than being mostly 0.010 μ m.

In addition, so-called surface roughness Ra, by JIS B0601 (calendar year 2001) defined, can be by known surface-profile measuring instrument (such as exabyte: Ai Fake, device name: Dektak150) etc. measure.

There is no particular restriction for the thickness of Copper Foil, can suitably adjust according to application target.With regard to regard to the more excellent aspect of the fine of the adhesion of base material and pattern, thickness is preferably 2 μ m～30 μ m, more preferably 5 μ m～20 μ m.

Copper Foil comprises copper conventionally, but also can comprise the metal (such as silver, tin, palladium, gold, nickel, chromium etc.) beyond a part of copper.

In addition, as mentioned above, the face with base material attaching of Copper Foil needs only the important document of the specific surface roughness Rz of performance and fractal dimension, and only an interarea (one side) meets this important document.And two interareas (two sides) that also can Copper Foil meet this important document.

In addition, when only an interarea meets this important document, there is no particular restriction for the shape of another interarea.Conventionally be mostly smooth glassy surface.

In addition, Copper Foil can be used for various forms (purposes).Such as enumerating: printed wiring board, electromagnetic shielding material, material, lithium ion battery etc. for conducting (ground connection).

And as required, this Copper Foil can for example, form pattern-like by known method (engraving method of recording in etching work procedure described later).

[manufacture method of Copper Foil]

There is no particular restriction for the manufacture method of above-mentioned Copper Foil, if the method that surface roughness Rz and fractal dimension are particular range also can be used method arbitrarily.

Fig. 2 means the flow chart of each operation in the preferred configuration of manufacture method of Copper Foil, and this form comprises: by plating layer form operation S102, catalyst provides operation S104, plating operation S106, supporter to remove operation S108, by plating layer, removed operation S110.If this form, the surface roughness Rz of the Copper Foil of gained and fractal dimension are easily adjusted, and productivity is also more excellent.

Below, each operation of this preferred configuration is described in detail.

(by plating layer, being formed operation S102)

This operation S102 forms the layer that comprises polymer on supporter, then to the layer that comprises polymer, provide energy, and on supporter, form by the operation of plating layer, wherein above-mentioned polymer has with plating coating catalyst or its predecessor and forms interactional functional group (being suitably called below interaction base) and polymerism base.

What by this operation S102, form is according to the function of interaction base contained in polymer by plating layer, and provides absorption (adhering to) plating coating catalyst or its predecessor in operation S104 at catalyst described later.That is, by plating layer, given play to the function as the good receiving layer of plating coating catalyst or its predecessor.In addition, polymerism base is by the cure process utilizing energy and provide and for polymer combination each other, and can obtain stiffness excellence by plating layer.

More specifically, as shown in Fig. 3 (A), in this operation S102, on supporter 12, form by plating layer 14.

First, the material using in this operation S102 (supporter, polymer, formed with composition by plating layer etc.) is described in detail, then the order of this operation S102 is described in detail.

(supporter)

Supporter is the member that supports each layer of aftermentioned, also can use existing known any supporting substrate (such as resin substrate, ceramic substrate, glass substrate, metal substrate etc.Be preferably insulating properties substrate).

Wherein, with regard at supporter described later, remove in operation S108, can more easily remove supporter aspect with regard to, be preferably and use fissility supporter, described fissility supporter has the surface of the easy fissility of performance.In addition, the easy fissility that the surface of so-called fissility supporter has, refer to when the laminate with Copper Foil described later is applied to the external force in order to fissility supporter is peeled off, Copper Foil with by the interface of plating layer, can not peeled off, and fissility supporter with by the character of the interface peel of plating layer.

With regard to fissility supporter and by the interface of plating layer, more easily peeled off aspect with regard to, the surperficial water contact angle of the easy fissility of performance of fissility supporter is preferably more than 70 °, more preferably 70 °～110 °, is especially preferably 80 °～100 °.

The assay method of water contact angle is to use to utilize the summit of water and the tangential method of this contact of 2 of supporter dripping.

In addition, there is no particular restriction for the size of supporter and thickness, suitably selects most preferred size and thickness.

In addition, there is no particular restriction for the shape of supporter, is generally tabular.

(polymer)

The polymer using has polymerism base and interaction base.

Polymerism base is provided and can be formed each other at polymer the functional group of chemical bond by energy, such as enumerating: free-radical polymerised base, cationically polymerizable base etc.Wherein, with regard to the more excellent aspect of reactivity, be preferably free-radical polymerised base.Free-radical polymerised base is such as enumerating: unsaturated carboxylic acid ester group, styryl, vinyl, acrylamido, the methacryl amidos etc. such as acrylate-based (acryloxy), methacrylate based (methacryloxy), itaconic acid ester group, butenoic acid ester group, methacrylate ester group, maleic acid ester group.Wherein, be preferably methacryloxy, acryloxy, vinyl, styryl, acrylamido, methacryl amido, be particularly preferably methacryloxy, acryloxy, styryl.

Interaction base is and plating coating catalyst or the interactional functional group of its predecessor, can uses: can form with plating coating catalyst or its predecessor the functional group of electrostatic interaction; Or can form the nitrogenous functional group, sulfur-bearing functional group of coordination with plating coating catalyst or its predecessor, containing oxygen functional group etc.

Interaction base is such as also enumerating: non-dissociating property functional group (not producing protogenic functional group by dissociating) etc.

Interaction base more specifically, can enumerate: amino, amide groups, imide, urea groups, tertiary amine base, ammonium, carbonamidine base (amidino group), triazine ring, triazole ring, BTA base, imidazole radicals, benzimidazolyl, quinolyl, pyridine radicals, pyrimidine radicals, pyrazinyl, azoles quinoline base (nazoline group), quinoxaline base (quinoxaline group), purine radicals, triazine radical, piperidyl, piperazinyl, pyrrolidinyl, pyrazolyl, anilino-, the group that comprises alkylamine structure, the group that comprises fulminuric acid structure, nitro, nitroso, azo group, diazo, azido, cyano group, nitrogenous functional groups such as cyanate ester based (R-O-CN), ether, hydroxyl, phenol hydroxyl, carboxyl, carbonate group, carbonyl, ester group, the group that comprises N-oxide structure, the group that comprises S-oxide structure, the groups that comprise N-hydroxyl structure etc. are containing oxygen functional group, thienyl, mercapto, ghiourea group, trithiocyanuric acid base, benzothiazolyl, mercapto-triazine base, thioether group, sulphur oxygen base, sulfoxide group, sulfuryl, sulfinyl group, the group that comprises sulphur acyloxy imines (sulfoxyimine) structure, the group that comprises sulfonium salt structure, sulfonic group, the sulfur-bearing functional groups such as group that comprise sulphonic acid ester structure, phosphate-based, phosphinylidyne amido, phosphino-, the phosphorous functional groups such as group that comprise phosphate ester structure, the groups that comprise the halogen atoms such as chlorine, bromine etc., in can forming the functional group of salt structure, also can be used the salt of these groups.

Wherein, high with regard to polarity, to regard to the high aspect of the energy of adsorption of plating coating catalyst or its predecessor etc., be particularly preferably carboxyl, sulfonic group, phosphate and boronate isoiony polar group or ether or cyano group, be especially preferably carboxyl or cyano group.

These functional groups as interaction base can comprise two or more in polymer.

There is no particular restriction for the weight average molecular weight of polymer, is preferably more than 1000, below 700,000, more preferably more than 2000, below 200,000.Particularly, with regard to the viewpoint of polymerization sensitivity, be preferably more than 20000.

In addition, there is no particular restriction for the degree of polymerization of polymer, more than being preferably ten polymers, more preferably more than 20 polymers.And, be preferably below 7,000 polymers, more preferably, below 3,000 polymers, be especially preferably below 2,000 polymers, be particularly preferably below 1,000 polymers.

The preferred configuration of polymer can be enumerated: the copolymer that comprises the unit with interaction base (being also suitably called below interaction base unit) shown in the unit with polymerism base shown in following formula (a) (being also suitably called below polymerism base unit) and following formula (b).In addition, unit refers to repetitive.

In above-mentioned formula (a) and formula (b), R ¹～R ⁵the alkyl that represents independently hydrogen atom respectively or be substituted or be unsubstituted (such as methyl, ethyl, propyl group, butyl etc.).In addition, there is no particular restriction for substituting group, can enumerate: methoxyl group, chlorine atom, bromine atoms or fluorine atom etc.

In addition, R ¹the methyl that is preferably hydrogen atom, methyl or replaces through bromine atoms.R ²the methyl that is preferably hydrogen atom, methyl or replaces through bromine atoms.R ³be preferably hydrogen atom.R ⁴be preferably hydrogen atom.R ⁵the methyl that is preferably hydrogen atom, methyl or replaces through bromine atoms.

In above-mentioned formula (a) and formula (b), X, Y and Z represent respectively singly-bound or the divalent organic base that is substituted or is unsubstituted independently.Divalent organic base can be enumerated: the divalence aliphatic alkyl that is substituted or is unsubstituted (is preferably carbon number 1～8.Alkylidenes such as methylene, ethylidene, propylidene), the divalence aromatic hydrocarbyl that is substituted or is unsubstituted (is preferably carbon number 6～12.Phenylene for example) ,-O-,-S-,-SO ₂-, alkyl), the group (such as alkylene oxide group, alkylene oxide carbonyl, alkylidene carbonyl oxygen base etc.) that forms of-CO-,-NH--,-COO-,-CONH-or these moiety combinations etc.-N (R)-(R:.

With regard to described later by plating layer, removed operation in by plating layer remove efficiency more excellent aspect with regard to, X, Y and Z are preferably ester group (COO-).

In above-mentioned formula (a) and formula (b), L ¹and L ²represent independently respectively singly-bound or the divalent organic base that is substituted or is unsubstituted.The definition of divalent organic base is identical with the definition of the divalent organic base described in above-mentioned X, Y and Z.

Synthetic easily and by with regard to the aspect of the catalyst adsorptivity excellence of plating layer with regard to polymer, L ¹be preferably aliphatic alkyl or have amino-formate bond or the divalent organic base of urea key (for example aliphatic alkyl), being wherein preferably total carbon number is 1～9.In addition, L herein ¹total carbon number refer to L ¹the shown contained total carbon atom number of the divalent organic base that is substituted or is unsubstituted.

In addition, synthetic easily and by with regard to the aspect of the catalyst adsorptivity excellence of plating layer with regard to polymer, L ²be preferably the group that singly-bound, divalence aliphatic alkyl, divalence aromatic hydrocarbyl or these moiety combinations form.Wherein, L ²be preferably the aliphatic alkyl that singly-bound or total carbon number are 1～15, be particularly preferably and be unsubstituted.In addition, L herein ²total carbon number refer to L ²the shown contained total carbon atom number of the divalent organic base that is substituted or is unsubstituted.

In above-mentioned formula (b), W represents and plating coating catalyst or the interactional functional group of its predecessor.This functional group's definition is identical with the definition of above-mentioned interaction base.

With respect to all unit in polymer, the content of above-mentioned polymerism base unit is preferably 5 % by mole～50 % by mole, more preferably 5 % by mole～40 % by mole.When the content in polymerism base unit is less than 5 % by mole, the situation that responding property (hardening, polymerism) reduces, when the content in polymerism base unit surpasses 50 % by mole, easy gelation when synthetic and be difficult to synthesize.

In addition, with regard to regard to the viewpoint of the adsorptivity of plating coating catalyst or its predecessor, with respect to all unit in polymer, the content of above-mentioned interaction base unit is preferably 5 % by mole～95 % by mole, more preferably 10 % by mole～95 % by mole, be especially preferably 60 % by mole～95 % by mole.

In addition, polymerism base unit and interaction base unit also can comprise the unit of two or more mutually different kind.

In addition, in polymer, also can comprise polymerism base unit and interaction base unit unit in addition.

The concrete example of above-mentioned polymer is such as enumerating: the polymer that the polymer that paragraph [the 0065]～paragraph [0070] of the polymer that the paragraph of Japanese Patent Laid-Open 2009-007540 communique [0106]～paragraph [0112] is recorded, Japanese Patent Laid-Open 2006-135271 communique is recorded, paragraph [the 0030]～paragraph [0108] of No. US2010-080964 are recorded etc.

This polymer can for example, be manufactured by known method (method in the above-mentioned document of enumerating).

(order of operation S102)

First, there is no particular restriction for the method for the layer (by plating layer precursor layer) that formation comprises above-mentioned polymer on supporter, can use known method.For example also can enumerate: by comprising being formed by plating layer with composition of above-mentioned polymer, coat method (rubbing method) on supporter or the method on supporter by polymer contact laminating.Wherein, with regard to easy control, by with regard to the aspect of the thickness of plating layer, be preferably rubbing method.Below to being formed and narrate by the form of composition by plating layer.

During for rubbing method, by being formed by plating layer, with composition, be coated on method on supporter there is no particular restriction, can use known method (such as spin coating, mould painting, dip-coating etc.).

With regard to the viewpoint of operability or manufacture efficiency, be preferably following form: will be formed with composition and coat on supporter by plating layer, be dried as required processing and remaining solvent is removed, and forming the layer (by plating layer formation composition layer) that comprises polymer.

In addition, there is no particular restriction for the dry condition of processing, and with regard to the more excellent aspect of productivity, is preferably with room temperature～220 ℃ (being preferably 50 ℃～120 ℃), implements 1 minute～30 minutes (being preferably 1 minute～10 minutes).

Then there is no particular restriction, to the layer (by plating layer formation composition layer) that comprises polymer on supporter, to provide the method for energy.Such as being preferably, use heat treated or exposure-processed etc., with regard to the aspect of end process in the short time, be preferably exposure-processed.By providing energy to the layer that comprises polymer, and can make the polymerism base activation in polymer, and produce between polymer, be cross-linked, thereby carry out the sclerosis of layer.

Exposure-processed can be used the irradiation of utilization ultraviolet ray (ultraviolet, UV) lamp, luminous ray etc. etc.Light source is such as having mercury vapor lamp, metal halide lamp, xenon lamp, chemical lamp, carbon arc lamp etc.Radioactive ray also have electron beam, X ray, ion beam, far infrared etc.Concrete form can preferably be enumerated: the high illumination flash exposure of the scan exposure of infrared laser, xenon discharge lamp etc. or infrared lamp exposure etc.

Time for exposure is different because of reactivity and the light source of polymer, be generally 10 seconds～and between 5 hours.Exposure energy, as long as be 10mJ～8000mJ left and right, is preferably the scope of 50mJ～3000mJ.

In addition, when using heat treated that energy is provided, can use fan drying machine, baking oven, infrared drier, heated roller etc.

By the thickness of plating layer, there is no particular restriction, with regard to productive aspect, is preferably 0.01 μ m～10 μ m, and more preferably 0.2 μ m～5 μ m, is particularly preferably 0.3 μ m～1.0 μ m.

In addition, by the surface roughness Rz of the surface of plating layer (with supporting the surface that side is opposite side), there is no particular restriction, with regard to the further aspect reducing of surface roughness Rz of Copper Foil, is preferably below 0.2 μ m, more preferably O.1 below μ m.There is no particular restriction for the lower limit of surface roughness Rz, with regard to the restriction on manufacturing, more than being mostly 0.01 μ m.

(by plating layer formation composition)

By plating layer, formed with containing above-mentioned polymer in composition.

By the content of the polymer in plating layer formation use composition, there is no particular restriction, with respect to total composition, is preferably 2 quality %～50 quality %, more preferably 3 quality %～20 quality %.If the content of polymer is in above-mentioned scope, the operability of composition is excellent, and easily controls by the bed thickness of plating layer.

By plating layer, formed and also can contain solvent with composition.By containing solvent, and operability improves.

Spendable solvent is not particularly limited, for example can enumerate: water, methyl alcohol, ethanol, propyl alcohol, ethylene glycol, glycerine, the alcohol series solvents such as propylene glycol monomethyl ether, the acid such as acetic acid, acetone, methyl ethyl ketone, the ketone series solvents such as cyclohexanone, formamide, dimethylacetylamide, the acid amides series solvents such as 1-METHYLPYRROLIDONE, acetonitrile, the nitrile series solvents such as propionitrile, methyl acetate, the ester series solvents such as ethyl acetate, dimethyl carbonate, the carbonic ester series solvents such as diethyl carbonate, can enumerate in addition: ether series solvent, glycol series solvent, amine series solvent, mercaptan series solvent, halogen series solvent etc.

Wherein, be preferably acid amides series solvent, ketone series solvent, nitrile series solvent, carbonic ester series solvent, particularly, be preferably acetone, dimethylacetylamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, 1-METHYLPYRROLIDONE, dimethyl carbonate.

By the content of the solvent in plating layer formation use composition, there is no particular restriction, with respect to total composition, is preferably 50 quality %～98 quality %, more preferably 90 quality %～97 quality %.If the content of solvent is in above-mentioned scope, the operability of composition is excellent, and easily carry out by the control of the bed thickness of plating layer etc.

[catalyst provides operation S104]

Catalyst provides operation S104 by plating layer, to be provided the operation of plating coating catalyst or its predecessor to what formed gained in operation S102 by plating layer.

In this operation S104, the interaction base that is derived from polymer adheres to according to its function plating coating catalyst or its predecessor that (absorption) provides.More specifically, in by plating layer and by plating layer Adsorption on Surface plating coating catalyst or its predecessor.

First, the material using in this operation S104 (plating coating catalyst or its predecessor etc.) is described in detail, then the order of this operation S104 is described in detail.

(plating coating catalyst or its predecessor)

Plating coating catalyst or its predecessor have been given play to the function as catalyst or the electrode of copper plating treatment in plating operation S106 described later.Therefore, the plating coating catalyst using or the kind of its predecessor, suitably determine according to the kind of plating processing.

Below, plating coating catalyst or its predecessor are mainly electroless plating or its predecessor etc. to be described in detail.

The plating coating catalyst of active nucleus when if electroless plating catalyst becomes electroless plating, also can use plating coating catalyst arbitrarily, particularly, can enumerate: there is metal (as the metal of ionization tendency the carried out electroless plating lower than Ni and known metal) of the catalyst function of autocatalysis agent reduction reaction etc.More specifically, can enumerate Pd, Ag, Cu, Ni, Al, Fe, Co etc.Wherein, with regard to high catalyst function, be particularly preferably Ag, Pd.

Electroless plating catalyst also can be used metallic colloid (metallic).Conventionally, metallic colloid can be made in the following manner: in the solution that charged interfacial agent or charged protective agent exist, metal ion is reduced.

If electroless plating catalyst precursors can become the plating coating catalyst predecessor of electroless plating catalyst by chemical reaction, can use with no particular limitation.The metal ion of the metal that mainly can be used as above-mentioned electroless plating catalyst and enumerate.Metal ion as electroless plating catalyst precursors becomes electroless plating catalyst by reduction reaction, i.e. 0 valency metal.Metal ion as electroless plating catalyst precursors can be after offering by plating layer, before in impregnated in electroless plating liquid, by other reduction reaction, become 0 valency metal, thereby can be made into electroless plating catalyst, can also impregnated in the state of electroless plating catalyst precursors in electroless plating liquid, by the reducing agent in electroless plating liquid, become metal (electroless plating catalyst).

Metal ion as electroless plating catalyst precursors is preferably use slaine and offers by plating layer.The slaine that is dissociated into metal ion and alkali (anion) if the slaine using is dissolved in suitable solvent, there is no particular restriction, can enumerate: M (NO ₃) _n, MCl _n, M _2/n(SO ₄), M _3/n(PO ₄) (M represents n valency metallic atom) etc.The metal ion that metal ion can preferably be used above-mentioned slaine to dissociate and form.Concrete example can be enumerated: Ag ion, Cu ion, Al ion, Ni ion, Co ion, Fe ion, Pd ion, wherein be preferably can polydonita coordination metal ion, particularly, with regard to complexible functional group's species number and the aspect of catalyst function, be preferably Ag ion, Pd ion.

In this operation, as the catalyst of directly electroplating for not carrying out electroless plating, also can use above-mentioned 0 valency metal in addition.

The form of the plating coating catalyst liquid (making plating coating catalyst or its predecessor be dispersed or dissolved in dispersion liquid or the solution forming in solvent) that above-mentioned plating coating catalyst or its predecessor are preferably to comprise these compositions is used.

The solvent using in plating coating catalyst liquid can be with an organic solvent and/or water.By plating coating catalyst liquid, contain organic solvent, and plating coating catalyst liquid is to being improved by the permeability of plating layer, and can makes plating coating catalyst or its predecessor be adsorbed in efficiently on interaction base.

If organic solvent used is permeable to by the solvent in plating layer in plating coating catalyst liquid; there is no particular restriction; particularly, can use: acetone, methyl acetoacetate, ethyl acetoacetate, ethylene acetate, cyclohexanone, pentanedione, acetophenone, 2-(1-cyclohexenyl group) cyclohexanone, propylene-glycol diacetate, glyceryl triacetate (triacetin), diethylene glycol diacetate esters, dioxanes, 1-METHYLPYRROLIDONE, dimethyl carbonate, ethylene glycol dimethyl ether etc.

(order of operation S104)

Plating coating catalyst or its predecessor are offered to there is no particular restriction by the method for plating layer.

For example can enumerate: prepare above-mentioned plating coating catalyst liquid (metal is scattered in to the dispersion liquid forming in suitable decentralized medium or the solution that comprises the metal ion through dissociating with suitable dissolution with solvents slaine), plating coating catalyst liquid is coated by the method on plating layer; Or dipping has formed by the method for the supporter of plating layer etc. in plating coating catalyst liquid.

Be preferably 30 seconds the time of contact by plating layer and plating coating catalyst liquid～about 10 minutes, about more preferably 1 minute～5 minutes.

The temperature of plating coating catalyst liquid during contact is preferably 20 ℃～60 ℃ left and right, more preferably 30 ℃～50 ℃ left and right.

[plating operation S106]

Plating operation S106 be to catalyst provide plating coating catalyst or its predecessor be provided in operation S104 by plating layer, carried out copper plating treatment, on by plating layer, form Copper Foil (being equivalent to copper facing), and obtain sequentially there is supporter, by the operation of the laminate of plating layer and Copper Foil.More specifically, as shown in Fig. 3 (B), in this operation S106, on by plating layer 14, form Copper Foil 10, and obtain laminate 16.

The kind of the copper plating treatment of carrying out in this operation S106 can be enumerated: electroless plating copper, electrolytic copper plating etc., in above-mentioned operation S104, can select according to the function offering by the plating coating catalyst of plating layer or its predecessor.

Wherein, with regard to obtaining with regard to the aspect of the Copper Foil of the better adhesion of base material performance, be preferably and carry out electroless plating copper.In addition, in order to obtain the Copper Foil of desired bed thickness, preferred form is after electroless plating copper, further to carry out electrolytic copper plating.

Below, the copper plating treatment of preferably carrying out in this operation S106 is described.

(electroless plating copper)

Electroless plating copper refers to and uses the solution that is dissolved with copper ion, the operation that copper is separated out by chemical reaction.

Electroless plating copper in this operation S106, for example, will provide being washed by plating layer of electroless plating catalyst and after unnecessary electroless plating catalyst (metal) is removed, and impregnated in electroless plating copper and carry out in bathing.The electroless plating copper using is bathed and can be used known electroless plating copper to bathe.In addition, with regard to the aspect of easy acquisition, electroless plating copper is bathed to be preferably and is used alkaline electroless plating copper to bathe the situation of (pH value is preferably 9～14 left and right).

In addition, at electroless plating catalyst precursors with absorption or be impregnated in by the state of plating layer, be impregnated in electroless plating copper bathe in time, will be washed by plating layer and after unnecessary predecessor (slaine etc.) is removed, impregnated in during electroless plating copper bathes.In such cases, in electroless plating copper is bathed, carry out the reduction of plating coating catalyst predecessor and follow-up electroless plating copper.Electroless plating copper as used herein is bathed same as described above, also can use known electroless plating copper to bathe.

In addition, the reduction of electroless plating catalyst precursors is different from the form of use electroless plating copper liquid as above, also can prepare catalyst activation liquid (reducing solution), as other operations before electroless plating copper, carries out.Catalyst activation liquid is to be dissolved with electroless plating catalyst precursors (being mainly metal ion) to be reduced into the solution of the reducing agent of 0 valency metal, the concentration of this reducing agent in whole solution is preferably 0.1 quality %～50 quality %, more preferably 1 quality %～30 quality %.Reducing agent can be used known reducing agent (boron such as sodium borohydride or dimethyamine borane is reducing agent, formaldehyde, low phosphoric acid (hypophosphoric acid) etc.).

During dipping, be preferably electroless plating catalyst or its predecessor are contacted by the concentration of the electroless plating catalyst of plating layer near surface or its predecessor, kept fixing, on one side and apply stirring or shake and flood.

The composition that common electroless plating copper is bathed for example for example,, except solvent (water), mainly comprises: 1. copper ion plating for, 2. reducing agent, the 3. additive (stabilizer) of the stability of raising copper ion.

Electroless plating copper is bathed organic solvent used and is preferably the solvent that is dissolvable in water water, with regard in this respect, can preferably use the alcohols such as the ketones such as acetone, methyl alcohol, ethanol, isopropyl alcohol.

Electroless plating copper is bathed the kind of metal used can use copper, as required also can be also for example, with other metals (copper, tin, lead, nickel, gold, silver, palladium, rhodium).

The temperature that the thickness of the Copper Foil obtaining by electroless plating copper can be bathed by copper ion concentration, dip time in electroless plating copper is bathed or electroless plating copper etc. is controlled, using the Copper Foil by electroless plating copper gained when conductting layer carries out electrolytic copper plating described later, the Copper Foil providing equably more than at least 0.1 μ m is provided.In addition, with regard to the viewpoint of conductivity, when not carrying out electrolytic copper plating described later, more than being preferably 0.1 μ m, more preferably more than 1 μ m, most preferably be 3 μ m～10 μ m.

In addition, the dip time in electroless plating copper is bathed be preferably 1 minute～about 10 hours, about more preferably 10 minutes～3 hours.

(electrolytic copper plating (electro-coppering))

In this operation S106, when the plating coating catalyst providing or its predecessor have as the function of electrode, can by plating layer, be carried out electrolytic copper plating to what this plating coating catalyst or its predecessor be provided in above-mentioned operation S104.

In addition, after aforesaid electroless plating copper, using formed Copper Foil as electrode, then also can carry out electrolytic copper plating.Whereby, can easily form the new Copper Foil with any thickness.

Process for electrolytically plating copper can be used existing known method.In addition, electrolysis plating metal used can be used copper, as required also can and with the metal (such as chromium, lead, nickel, gold, silver, tin, zinc etc.) beyond copper.

The thickness of the Copper Foil obtaining by electrolytic copper plating in addition, can be controlled by adjusting copper ion concentration contained in electrolytic copper plating bath or current density etc.

In addition, when being applied to common electric wiring etc., with regard to the viewpoint of conductivity, more than the thickness of Copper Foil is preferably 1 μ m, 3 μ m～30 μ m more preferably.

In addition, between electroless plating copper and electrolytic copper plating, can implement as required processing that acid solution (for example aqueous sulfuric acid) is contacted with electroless plating copper, to remove the cupric oxide on electroless plating copper.

[supporter is removed operation]

It is the operation that the laminate of gained in above-mentioned plating operation S106 is removed supporter that supporter is removed operation S108.More specifically, as shown in Fig. 3 (C), the laminate 16 of recording from Fig. 3 (B) is removed supporter 12, and obtain, comprises having by the Copper Foil 18 of plating layer by plating layer 14 and Copper Foil 10.

There is no particular restriction to remove the method for supporter, can suitably select best method according to the kind of used supporter.

For example can enumerate: the solution that only dissolves the supporter in laminate is contacted with laminate, and supporter is dissolved to the method for removing; In laminate, supporter is carried out to the method that physical property is peeled off; The method of supporter in laminate being implemented to the oxidation processes such as plasma treatment or ozone treatment and being removed etc.

As mentioned above, when using fissility supporter as supporter, can by the generation of interfaces of plating layer and supporter, peeled off by physical property effect, thereby can easily the separation of fissility supporter removed.

[by plating layer, being removed operation]

By plating layer remove operation S110 be from above-mentioned supporter remove gained in operation S108 by the laminate of plating layer and Copper Foil, remove by the operation of plating layer.More specifically, as shown in Fig. 3 (D), having of recording from Fig. 3 (C) removed by plating layer 14 by the Copper Foil 18 of plating layer, and obtains Copper Foil 10.

Remove that there is no particular restriction by the method for plating layer, can by the kind of the material of plating layer, suitably be selected best method according to forming.

For example can enumerate: make only to dissolve by the solution of plating layer (for example alkaline aqueous solution) with being contacted by the Copper Foil of plating layer, and will by plating layer, be dissolved the method for removing; From will be carried out the method that physical property is peeled off by plating layer in by the Copper Foil of plating layer; The method of removing being implemented the oxidation processes such as plasma treatment or ozone treatment by plating layer etc.

In addition, by above-mentioned, by plating layer, dissolved in the method remove, as required can and by ultrasonic treatment etc.By also using ultrasonic treatment, and make to be improved by the efficiency of removing of plating layer.In addition, also can apply fixing pressure will dissolve by the solution spray attachment of plating layer extremely by plating layer.

In addition, supporter is removed operation S108 and by plating layer, is removed operation S110 and can separate as mentioned above and implement, and also can implement simultaneously.

That is the laminate that, can implement gained in above-mentioned plating operation S106 is removed supporter and by plating layer, is obtained the operation of Copper Foil.In such cases, for example, can enumerate: make to dissolve supporter and contacted with laminate by the solution of plating layer, and by supporter and the method for being removed by plating layer dissolving; In laminate, by having, by the supporter of plating layer, carried out the method that physical property is peeled off; The method of implementing the oxidation processes such as plasma treatment or ozone treatment to supporter and by plating layer and removing etc.

Through above-mentioned operation S102～S110 and Copper Foil and surface that contacted by plating layer, meet specific surface roughness Rz and fractal dimension as mentioned above.

[laminate (laminate that contains Copper Foil) with Copper Foil]

So that the mode that the surface of the specific surface roughness Rz of the performance of above-mentioned Copper Foil and fractal dimension contacts with substrate surface, by Copper Foil and base material laminating, obtains the laminate with base material and Copper Foil whereby.

In this laminate, due on the face with micro concavo-convex structure of copper foil surface in abutting connection with base material, so the adhesion of base material and Copper Foil is excellent.

First, below used base material is described in detail, then to obtaining the order of laminate, is described in detail.

(base material)

There is no particular restriction to be pasted with the kind of base material of Copper Foil, can use known base material.Such as enumerating: resin base material, glass baseplate, ceramic base material, paper base material etc.Wherein, aspect, the application in printed wiring board excellent with regard to adhesion with Copper Foil with regard to, be preferably use resin base material.

There is no particular restriction for the kind of the material of formation resin base material, can enumerate thermoplastic resin or thermosetting resin.

Thermosetting resin is such as enumerating: epoxy resin, phenol resin, polyimide resin, mylar, two maleimide resin, vistanex, isocyanate resin etc.

Thermoplastic resin for example can be enumerated: phenoxy resin, polyether sulfone, polysulfones, PPSU, polyphenylene sulfide, polyphenylene oxide, Polyetherimide, acrylonitrile-butadiene-styrene (ABS) (Acrylonitrile Butadiene Styrene, ABS) resin, polyethylene terephthalate, Polyethylene Naphthalate, Merlon, polystyrene, polymethyl methacrylate, polyether-ether-ketone, polyamide, PLA, cyclic olefine copolymer (Cyclo Olefin Polymer, COP), liquid crystal polymer (Liquid Crystal Polymer, LCP) etc.

In addition, resin base material can comprise: the fillers such as glass woven fabric (glass cloth), glass adhesive-bonded fabric, aromatic polyamides (aramid) are weaved cotton cloth, aromatic polyamides adhesive-bonded fabric.

In addition, there is no particular restriction for the shape of base material, with regard to the better aspect of adhesion, is preferably tabular.

(manufacture method of laminate)

There is no particular restriction on base material, to attach the method for Copper Foil, can use known method.For example Copper Foil and base material (particularly resin base material) are fitted and lamination, suppress (press) etc. and exert pressure and crimping, thereby obtain desired laminate.

During crimping, can implement in the lump as required heat treated.

Temperature while adding thermo-compressed can suitably be selected optimal conditions according to the material of used base material, when using common used epoxy to be resin base material, adhesion with regard to Copper Foil is more excellent, with regard to the aspect of mobility of resin base material, thermosetting, pyrolytic etc., be preferably 150 ℃～200 ℃, more preferably 165 ℃～185 ℃.In addition, with regard to the aspect that adhesion is more excellent, productivity is more excellent of Copper Foil, the time that adds thermo-compressed is preferably 0.5 hour～and 4 hours, more preferably 1 hour～2 hours.

In addition, when manufacturing laminate, Copper Foil both can only be attached at the one side of tabular base material, also can be attached at two sides.

(purposes)

The laminate of gained can be used for various uses.For example can be applicable to semiconductor packages, motherboard, flexible print circuit (Flexible Printed Circuit, FPC), cover brilliant film (Chip On Film, COF), coil type engages the various uses such as (Tape Automated Bonding, TAB), antenna automatically.

[etching work procedure]

As required, the Copper Foil in the laminate that comprises above-mentioned base material and Copper Foil is etched into pattern-like, thereby can manufactures the laminate that surface has pattern-like Copper Foil.

Below this etching work procedure is described in detail.

Etching work procedure is the Copper Foil in laminate to be etched into the operation of pattern-like.That is,, in this operation, by etching, remove the unwanted part of formed Copper Foil, and can form desired copper foil pattern.

The formation of this copper foil pattern also can be used method arbitrarily, particularly, can use known subtractive process (subtractive method), semi-additive process (semi-additive method) conventionally.

Subtractive process is that dry film photoresist layer is set on formed Copper Foil, by pattern exposure, development, forms the pattern identical with copper foil pattern portion, using dry film photoresist pattern as shade and utilize etching solution to remove Copper Foil, and forms the method for copper foil pattern.Dry film photoresist also can be used material arbitrarily, can use minus, eurymeric, aqueous, membranaceous resist.And engraving method also can be used any means of using when the manufacture of printed wiring board, can use Wet-type etching, dry-etching etc., select arbitrarily.In the operation of operation, device etc. simplicity aspect, Wet-type etching is preferred.Etching solution is such as using: the aqueous solution of copper chloride, iron chloride etc.

In addition, semi-additive process is that dry film photoresist layer is set on Copper Foil, by pattern exposure, development, form the pattern identical with non-copper foil pattern portion, using dry film photoresist pattern as shade, electroplate, dry film photoresist pattern is removed to rear enforcement fast-etching, and remove Copper Foil with pattern-like, thereby form the method for copper foil pattern.Dry film photoresist, etching solution etc. can be used the material identical with subtractive process.In addition, electro-plating method can be used the method for above-mentioned record.

[embodiment]

Below, by embodiment, the present invention is described in more detail, but the present invention is not limited to these embodiment.

First, the synthetic method of the polymer using in embodiment is described in detail.

(synthesis example 1: polymer A synthetic)

In the there-necked flask of 1000ml, drop into 1-METHYLPYRROLIDONE (35g), at nitrogen, flow down and be heated to 75 ℃.Last within 2.5 hours, drip wherein acrylic acid 2-hydroxy methacrylate (Tokyo changes into manufacture) (6.60g), 2 cyanoethyl acrylate (28.4g) and 1-METHYLPYRROLIDONE (35g) solution that comprises V-60l (with the pure medicine manufacture of light) 0.65g.After dropping finishes, reaction solution is heated to 80 ℃, then stirs 3 hours.Then reaction solution is cooled to room temperature.

In above-mentioned reaction solution, add two tributyl hydroquinones (0.29g), dibutyl tin laurate (dibutyltin dilaurate) (0.29g), good haze hereby AOI (Karenz AOI) (clear and electrician's (thigh) manufacture) (18.56g) and 1-METHYLPYRROLIDONE (19g), at 55 ℃, react 6 hours.Then in reactant liquor, add methyl alcohol (3.6g), then react 1.5 hours.After reaction finishes, water precipitates again, takes out solid constituent and obtains polymer A (25g).

(evaluation of structure)

Make polymer A be dissolved in deuterate dimethyl sulfoxide (DMSO) (dimethyl sulfoxide, DMSO) in, utilize the nulcear magnetic resonance (NMR) (nuclear magnetic resonance, NMR) of the 300MHz of Brooker (Bruker) manufacture (AV-300) to measure.Known: to be equivalent to the peak value of unit of cyano-containing at 4.3ppm-4.05ppm (2H divides), 2.9ppm-2.8ppm (2H divides), 2.5ppm-1.3ppm (3H divides) is observed wider, be equivalent to peak value containing the unit of polymerism base at 7.3ppm-7.2ppm (1H divides), 6.4ppm-6.3ppm (1H divides), 6.2ppm-6.1ppm (1H divides), 6.0ppm-5.9ppm (1H divides), 4.3ppm-4.05ppm (6H divides), 3.3 ppm-3.2ppm (2H divides), 2.5ppm-1.3ppm (3H divides) is observed wider, unit containing polymerism base: unit=22 of cyano-containing: 78 (mol%).

(mensuration of molecular weight)

Make polymer A be dissolved in oxolane (tetrahydrofuran, THF), the high speed gel permeation chromatograph (Gel Permeation Chromatography, GPC) that uses eastern Cao (Tosoh) to manufacture (HLC-8220GPC) carries out the mensuration of molecular weight.Its result is known, occurs peak value at 23.75 minutes, by polystyrene conversion, counts Mw=5300 (Mw/Mn=1.54).

In addition, each unit of numeric representation in the chemical formula of following polymer A % by mole.

< embodiment 1>

[by plating layer, being formed operation]

By spin-coating method by the acetonitrile solution of the polymer A that comprises 10 % by weight (being formed layer composition A by plating layer) coating (condition: the mode that to take by thickness after plating layer dry be 0.5 μ m is coated with) in supporter (exabyte: all nanograms (PANAC), trade name: TP05, with the contact angle of water: 95 °) on, after being dried 10 minutes with 80 ℃, use UV exposure machine (manufacture of San Yong motor manufacturing company, model: UVF-502S, lamp: UXM-501MD), with the exposure energy of 1000mJ, expose.

By exposure after supporter at 1 quality %NaHCO ₃in the aqueous solution, flood 10 minutes, then utilize distilled water to clean, and obtain supporter A.In addition, that gained is 0.01 μ m by the surface roughness Rz of the exposing surface of plating layer.

[catalyst provides operation]

Prepare the 0.5 quality % acid chloride aqueous solution, using it as plating coating catalyst liquid.In this plating coating catalyst liquid (liquid temperature: room temperature), supporter A dipping, after 5 minutes, is cleaned with pure water.

[plating operation]

Then, supporter A is carried out to electroless plating copper.Electroless plating copper is to use the electroless plating copper of the following composition that utilizes another name for Sichuan Province Lu Kapu PGT (Through-Copper PGT) (industry of upper village is manufactured) to bathe, at 30 ℃ of bath temperatures, by supporter A dipping 15 minutes, the plating of take was separated out the mode that thickness is 0.5 μ m and is formed Copper Foil.

The tune liquid order of electroless plating copper liquid and raw material are as described below.

Formalin liquid * 2.3 volume %

Finally, take total amount utilizes distilled water as the mode of 100 volume % and carries out liquid level adjustment.

* Formalin used herein is the formalin (superfine) with the pure medicine of light.

Then, the supporter A with Copper Foil of gained is flooded to 15 seconds in 1 quality % aqueous sulfuric acid, and the oxide scale film on Copper Foil is removed.

Then, using the Copper Foil of above-mentioned gained as power supply layer, use the following electrolytic copper plating forming to bathe, the thick mode as 12 μ m of the copper of take is implemented electrolytic copper plating (2.5A/dm ²: 20 minutes), and obtain the laminate A with Copper Foil.

(composition that electrolytic copper plating is bathed)

[supporter is removed operation]

Then, with hand, peel off the supporter in the laminate A of gained, and obtain, there is having by the Copper Foil A of plating layer by plating layer and Copper Foil.

[by plating layer, being removed operation]

Then, with the spraying of 0.2MPa press to by the Copper Foil A of plating layer by the plating layer spray attachment 4 quality %NaOH aqueous solution, will be removed by plating layer and obtain Copper Foil.

[manufacture of the laminate that contains Copper Foil]

Then, the mode contacting with Copper Foil and face that contacted by plating layer and the prepreg of gained (Hitachi changes into, GEA-67N, 0.2mm), spreads on Copper Foil on the two sides of prepreg, engages, and obtain two sides copper-clad plate by vacuum pressing.

< embodiment 2>

Carry out plasma treatment (day clear (Nissin), microwave downward stream mode) implement by plating layer remove replace spraying that utilizes the 4%NaOH aqueous solution of implementing in above-mentioned [being removed operation by plating layer] to remove, in addition, according to the order identical with embodiment 1, obtain two sides copper-clad plate.

< embodiment 3>

In above-mentioned [being formed operation by plating layer], utilize identical UV exposure machine, with the exposure energy of 500mJ, expose, in addition, according to the order identical with embodiment 1, obtain two sides copper-clad plate.

< embodiment 4>

In above-mentioned [catalyst provides operation], prepare the 0.2 quality % acid chloride aqueous solution, using it as plating coating catalyst liquid, in this plating coating catalyst liquid (liquid temperature: room temperature), supporter A was flooded after 2 minutes, with pure water, clean, in addition, according to the order identical with embodiment 1, obtain two sides copper-clad plate.

< comparative example 1>

Use low level electrolytic copper foil (FUKUDA METAL's manufacture, name of an article SV, Rz=1.840 μ m, the thick 12 μ m of copper), the order identical according to [manufacture of the laminate that contains Copper Foil] with implementing in embodiment 1, obtains two sides copper-clad plate.

< comparative example 2>

The condition of the electrolytic copper plating in above-mentioned [plating operation] is made as to 8A/dm ², 7 minutes, specially by the exposing surface of plating (with the surface that to have by the side of plating layer be opposition side) alligatoring, and the plating surface (copper is thick is 12 μ m) of acquisition Rz=0.135 μ m in addition, obtains Copper Foil according to the order identical with embodiment 1.Then,, using the exposing surface of specially roughened Copper Foil as the face that connects airtight with prepreg, the order identical according to [manufacture of the laminate that contains Copper Foil] with implementing in embodiment 1, obtains two sides copper-clad plate.

< comparative example 3>

The condition of the electrolytic copper plating in above-mentioned [plating operation] is made as to 13A/dm ², 4.5 minutes, specially by the exposing surface of plating (with the surface that to have by the side of plating layer be opposition side) alligatoring, and the plating surface (copper is thick is 12 μ m) of acquisition Rz=0.310 μ m in addition, obtains Copper Foil according to the order identical with embodiment 1.Then,, using the exposing surface of specially roughened Copper Foil as the face that connects airtight with prepreg, the order identical according to [manufacture of the laminate that contains Copper Foil] with implementing in embodiment 1, obtains two sides copper-clad plate.

< comparative example 4>

After [being formed operation by plating layer] and [catalyst provides operation] of embodiment 1, [being formed operation by plating layer] of again implementing EXAMPLE l, forms by plating layer to have the formation of catalyst distribution.Form: be positioned at lower floor by plating layer on carry catalyst, but by plating layer, be there is not the state of catalyst on upper strata.In addition, that gained is 0.014 μ m by the surface roughness Rz of the exposing surface of plating layer.

Then, the dip time in electroless plating copper is bathed in [plating operation] was changed to 80 minutes from 30 minutes, and take plating and separate out the mode that thickness is 0.5 μ m and form Copper Foil, in addition, according to the order identical with embodiment 1, obtain two sides copper-clad plate.

The various evaluation of < >

(mensuration of peel strength)

According to JIS C6481:1996, the Copper Foil of the two sides copper-clad plate of gained in embodiment 1～embodiment 4 and comparative example 1～comparative example 4 is carried out to 90 ℃ of peeling strength tests.Result is gathered and is shown in table 1.

(mensuration of surface roughness Rz and Ra)

According to JIS B060l:2001, surperficial surface roughness Rz and the Ra of the side of connecting airtight with prepreg of Copper Foil and surface that contacted by plating layer of gained in embodiment 1～embodiment 4 [being removed operation by plating layer] and the Copper Foil of comparative example l～comparative example 4 are measured.In addition, during mensuration, use surface-profile measuring instrument (exabyte: Ai Fake (ULVAC), device name: Dektakl50).Result is gathered and is shown in table 1.

(mensuration of fractal dimension)

Use two-beam focused ion beam apparatus (FEI manufacture, Dual Beam Nova200Nanolab, accelerating voltage 30kV), the Copper Foil being used in the Copper Foil of gained in embodiment 1～embodiment 4 [being removed operation by plating layer] and comparative example 1～comparative example 4 is processed into sample, and cuts out section.Then, by cluster ion beam device (manufacture of Seiko electronics corporation, SMI9200), observe its section, and obtain view data.Then by image, process the coarse surface portion (line segment) of the side of connecting airtight with prepreg of extracting Copper Foil, according to this cross sectional photograph, by the mensuration region (1 μ m * 1 μ m) at 5 positions, calculate respectively the fractal dimension of outline line, these values are carried out to arithmetic average and obtain the fractal dimension that table 1 records (average fractal dimension).In addition, the box size in box dimension (size on a limit of square box) is 1nm～10nm.

(forming pattern distribution (L/S=25 μ m/25 μ m))

In embodiment 1～embodiment 4 and comparative example 1～comparative example 4 on the Copper Foil of the two sides copper-clad plate of gained, laminating film resist (Dry Film Resist, DFR) (Hitachi changes into, RY3310).Then, have on the substrate of dry type resist film at lamination, connect airtight the glass shade of the formed comb type distribution (according to JPCA-BU01-2007) of JPCA-ET01 defined, the exposure machine by centre wavelength 405nm irradiates the light energy of 70mJ to resist.Spraying with 0.2MPa is pressed the substrate spray attachment 1%Na after exposure ₂cO ₃the aqueous solution, and develop.Then substrate is washed, is dried, and on Copper Foil, form the resist pattern that subtractive process is used.

By the substrate that has formed resist pattern being impregnated in to FeCl at 40 ℃ of temperature ₃in/HCl the aqueous solution (etching solution) and carry out etching, and the existing Copper Foil in non-formation region of resist pattern is removed.Then, with the spraying of 0.2MPa, press 3%NaOH aqueous solution spray attachment to substrate, and the swelling of resist pattern is peeled off, utilize 10% aqueous sulfuric acid to carry out neutralisation treatment, and wash, and obtain comb type distribution (pattern-like Copper Foil).The distribution of gained is L/S=25 μ m/25 μ m.

Then, in order to estimate the inequality of live width, and measure the distribution width (minimum) of 50 of any parts, and calculate standard deviation.Result is gathered and is shown in table 1.

In addition, about comparative example 2～comparative example 4, because Copper Foil is low to the adhesion of prepreg, therefore when above-mentioned etching, cause Copper Foil to be peeled off, and cannot form distribution.

[table 1]

As shown in table 1, confirm in the Copper Foil (embodiment 1～embodiment 4) at this example, although surface roughness Rz is very little, show excellent peel strength.The inequality that also confirms in addition distribution width is also little, and can form the Wiring pattern of fine.

On the other hand, as shown in comparative example 1, in existing known Copper Foil, due to surface roughness, Rz is large, so peel strength is excellent, but the inequality of distribution width is large, and cannot obtain the Wiring pattern of fine.

In addition, as shown in comparative example 2～comparative example 4, in the time of outside fractal dimension is particular range, the peel strength of Copper Foil is poor, and cannot form distribution.

The explanation of symbol

10: Copper Foil

12: supporter

14: by plating layer

16: laminate

18: have by the Copper Foil of plating layer.

Claims (4)

1. an attaching Copper Foil, it is in order to be attached on base material,

The surperficial surface roughness (Rz) that is attached at the side of described base material is below 0.500 μ m,

The fractal dimension of surperficial outline line that is attached at the side of described base material in the section of described Copper Foil is 1.020～1.400, and described fractal dimension is that application is set as the size on a limit of square box the box dimension of 1nm～10nm and calculates.

2. a laminate, it comprises:

Base material; And

Be attached at the attaching Copper Foil according to claim 1 on described base material.

3. a printed wiring board, it contains laminate according to claim 2.

4. attach the manufacture method with Copper Foil, it,, for the manufacture of attaching Copper Foil according to claim 1, comprising:

On supporter, the layer that formation comprises polymer, then to the layer that comprises described polymer, provide energy, and on described supporter, form by the operation of plating layer, wherein said polymer has and forms interactional functional group and polymerism base with plating coating catalyst or its predecessor;

To the described operation that described plating coating catalyst or its predecessor are provided by plating layer;

To providing the described of described plating coating catalyst or its predecessor to be carried out copper plating treatment by plating layer, described, form Copper Foil on by plating layer, and obtain, sequentially there is described supporter, described by the operation of the laminate of plating layer and described Copper Foil;

From described laminate, remove described supporter and the described operation that is obtained described Copper Foil by plating layer.