WO2013047056A1

WO2013047056A1 - Copper foil for lamination

Info

Publication number: WO2013047056A1
Application number: PCT/JP2012/071684
Authority: WO
Inventors: 植木　志貴
Original assignee: 富士フイルム株式会社
Priority date: 2011-09-30
Filing date: 2012-08-28
Publication date: 2013-04-04
Also published as: JP5651564B2; JP2013077702A; CN104025722B; CN104025722A; KR101569040B1; KR20140071333A; TW201313952A

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 0.500μm 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

Copper foil for pasting

The present invention relates to a copper foil for pasting.

Copper metal is widely used as a basic material for printed wiring boards and the like because metallic copper is a good conductor of electricity and is relatively inexpensive and easy to handle.
When manufacturing a printed wiring board, usually, a copper foil and a predetermined base material are laminated together and heat-pressed to obtain a copper-clad laminate. In general, the surface of the copper foil to be bonded to the base material is subjected to a roughening treatment in order to improve adhesion with the base material (Patent Document 1).

On the other hand, in recent years, high density, high reliability, and reduction in size and weight of printed wiring boards have been strongly demanded, and accordingly, it is required to form a narrow and high-definition wiring pattern.
However, when a wiring pattern is formed using a copper foil that has been subjected to a conventional roughening treatment, the wiring pattern wiring obtained is affected by the unevenness of the surface that has been subjected to the roughening treatment of the copper foil. There was a problem that the variation in width was large.

In order to form a high-definition wiring pattern, there is a way to lower the profile of the rough surface of the copper foil. However, in this method, since the adhesiveness between the copper foil and the substrate is lowered, problems such as peeling, floating, and delamination of the copper foil circuit occur.
Thus, conventionally, high adhesion to the substrate and high definition of the wiring pattern are in a trade-off relationship with each other, and it has been difficult to satisfy both.

Japanese Patent No. 3476264

An object of this invention is to provide the copper foil for bonding which can form a high-definition wiring pattern, showing the favorable adhesiveness with a base material in view of the said situation.
Another object of the present invention is to provide a laminate and a printed wiring board obtained by using the above-mentioned bonding copper foil.

As a result of intensive studies, the present inventor has found that the above-mentioned problem can be solved by having a predetermined structure on the surface to be bonded to the base of the bonding copper foil.
That is, it has been found that the above object can be achieved by the following means.

(1) A copper foil for pasting used for pasting on a substrate,
The surface roughness (Rz) of the surface to be attached to the substrate is 0.500 μm or less,
The fractal dimension of the contour line of the surface on the side to be attached to the substrate in the cross section of the copper foil calculated by applying the box count method in which the size of one side of the square box is set to 1 nm to 10 nm is 1.020 to 1 400, a copper foil for attachment.

(2) A laminate having a base material and the attaching copper foil according to (1) attached on the base material.

(3) A printed wiring board containing the laminate according to (2).
(4) A method for producing a bonding copper foil according to (1),
A layer containing a polymer having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor is formed on the support, and then energy is applied to the layer containing the polymer to Forming a layer to be plated on,
Providing a plating catalyst or a precursor thereof to the layer to be plated;
The laminated body which performs a copper plating process with respect to the to-be-plated layer provided with the plating catalyst or its precursor, forms copper foil on a to-be-plated layer, and has a support body, to-be-plated layer, and copper foil in this order Obtaining
The manufacturing method of the copper foil for adhesion | attachment which has a process of removing a support body and a to-be-plated layer from a laminated body, and obtaining copper foil.

ADVANTAGE OF THE INVENTION According to this invention, the copper foil for affixing which can form a high-definition wiring pattern can be provided, showing favorable adhesiveness with a base material.
Moreover, according to this invention, the laminated body and printed wiring board using the said copper foil for affixing can also be provided.

(A) It is a typical perspective view of the copper foil for affixing of this invention. (B) It is an enlarged view of the surface side of the AA line cross section. It is the flowchart which showed the manufacturing process of one Embodiment of the manufacturing method of the copper foil for affixing of this invention. (A)-(D) are typical sectional drawings which show in order each manufacturing process of one embodiment of a manufacturing method of a pasting copper foil of the present invention.

Below, the copper foil for adhesion of this embodiment is demonstrated.
The bonding copper foil of the present embodiment has a predetermined surface roughness Rz and the fractal dimension of the outline of the bonding surface in the cross section calculated by the box count method has a predetermined value. Show. When the affixed surface shows a predetermined surface roughness Rz, there are few macro unevenness on the affixed surface (low profile), and as a result, a high-definition wiring pattern can be formed during pattern formation. Further, when the cross-sectional contour line of the pasting surface shows a predetermined fractal dimension, it has a micro and complicated surface property. That is, even if the surface roughness Rz of the pasting surface is small, it has a sufficient surface area due to its complicated surface shape, and as a result, it exhibits a sufficient anchoring effect on the base material. Excellent adhesion to the material. That is, it is possible to achieve both the improvement in adhesion and the high definition of the wiring pattern, which have been a trade-off relationship.
First, the aspect of the copper foil for sticking is explained in full detail below, and the manufacturing method of this copper foil is explained in full detail after that.

[Copper foil for pasting (copper foil for pasting)]
The attaching copper foil of the present embodiment (hereinafter, also simply referred to as “copper foil”) is used for attaching to the substrate surface. The base material used will be described later.
FIG. 1A is a schematic perspective view of the copper foil 10 for attachment, and FIG. 1B is an enlarged view of the vicinity of the surface in the section AA in FIG. 1A. In addition, in FIG.1 (B), the upper side of the copper foil 10 for affixing corresponds to the outline of the surface of the side affixed on a base material. As shown in the figure, the surface of the bonding copper foil 10 on the base and the side to be bonded is a small surface roughness Rz and a macroscopically flat surface, but a microscopically complicated surface shape. have.

The surface roughness Rz of the surface to be attached to the copper foil base material is 0.500 μm or less. If it is in the said range, a high-definition wiring pattern can be formed efficiently. Among these, 0.300 μm or less is preferable and 0.200 μm or less is more preferable because a wiring pattern with a narrower gap can be formed with high definition. The lower limit is not particularly limited, and is most preferably 0 μm. However, from the viewpoint of industrial productivity, it is often 0.050 μm or more.
When Rz is more than 0.500 μm, the variation in wiring width becomes large, and a high-definition wiring pattern cannot be obtained.

The surface roughness Rz is the maximum height roughness specified in JIS B 0601 (2001), which is a known surface shape measuring device (for example, company name: ULVAC, device name: Dektak 150), etc. Can be measured.

In the cross section of copper foil, the contour line (cross-sectional contour line) of the surface to be attached to the copper foil base material is fractal, and the box count method is used in which the size of one side of the square box is set to 1 nm to 10 nm. The fractal dimension of the surface contour calculated in this way is 1.020 to 1.400. When the fractal dimension is within the above range, the copper foil exhibits excellent adhesion to the substrate. Of these, the fractal dimension is preferably 1.050 to 1.400, more preferably 1.100 to 1.300, and even more preferably 1.150 to 1.250 in terms of better adhesion to the substrate.
In addition, when the fractal dimension is less than 1.020 and more than 1.400, the adhesion of the copper foil to the base material is inferior.

The box count method will be described in detail below.
The box count method is a method of estimating the fractal dimension by examining how much a fractal figure is included when a certain area is divided into a certain size (box size). is there.
“Fractal dimension (box count dimension)” is an index that represents the complexity of the shape, the degree of surface irregularities, etc., and the larger the fractal dimension value, the more complex the irregularities are defined as follows: Is done. Assuming that the number of boxes necessary for covering a certain figure F with a square box (box) having a side size δ is N _δ (F), the fractal dimension is defined by the following equation.

In other words, in the present invention, the cross section of the copper foil is divided into grid-like regions with equal intervals δ (divided into small square regions with one side of δ), and the copper is changed while changing the size of δ. The number of square boxes (cells) having a side size of δ including a part of the contour line on the surface of the foil attached to the substrate is counted. Next, the number of counted boxes is plotted on the log-log graph with the vertical axis representing the number of boxes and the horizontal axis representing the magnitude of δ, and the fractal dimension is obtained from the slope of the graph.
In the present invention, δ is in the range of 1 to 10 nm.

In the present invention, the measurement area is 1 μm × 1 μm.
Furthermore, the fractal dimension in the present invention is a value obtained by calculating the fractal dimension from at least five cross-sectional measurement regions (1 μm × 1 μm) and arithmetically averaging them.

More specifically, the fractal dimension of the present invention is calculated from a cross-sectional structure photograph of a copper foil (a photograph of a plane parallel to the thickness direction of the copper foil). First, using a Dual-Beam FIB apparatus (manufactured by FEI, Dual Beam Nova200 Nanolab, acceleration voltage 30 kV), a copper foil is sampled and a cross-section is obtained. Next, the cross section is observed with a focused ion beam apparatus (SMI 9200, manufactured by Seiko Instruments Inc.) to obtain image data. Thereafter, the roughened surface portion (line segment) of the copper foil is extracted by image processing. Based on this cross-sectional photograph, the above-mentioned box count method is used to calculate the fractal dimension (box count dimension) of the contour line in at least five measurement areas (1 μm × 1 μm), respectively, and arithmetically average them. The fractal dimension (average fractal dimension) of the present invention is determined.

The surface roughness Ra of the surface of the copper foil attached to the base material is not particularly limited, but is preferably 0.200 μm or less, and preferably 0.100 μm or less in that a high-definition wiring pattern can be efficiently formed. More preferred. The lower limit is not particularly limited, and is most preferably 0 μm. However, from the viewpoint of industrial productivity, it is often 0.010 μm or more.
The surface roughness Ra is defined in JIS B 0601 (2001), which can be measured with a known surface shape measuring device (for example, company name: ULVAC, device name: Dektak 150).

The thickness of the copper foil is not particularly limited and can be appropriately adjusted according to the purpose of use. From the viewpoint of excellent adhesion to the substrate and high definition of the pattern, it is preferably 2 to 30 μm, more preferably 5 to 20 μm.

The copper foil is usually made of copper, but may contain a part of metals other than copper (for example, silver, tin, palladium, gold, nickel, chromium, etc.).

Note that, as described above, the surface of the copper foil substrate and the surface to be bonded need only indicate the requirements for the predetermined surface roughness Rz and fractal dimension, and only one main surface (one surface) may satisfy the requirements. . Moreover, both the main surfaces (both surfaces) of copper foil may satisfy | fill this requirement.
In addition, when only one main surface satisfies the requirement, the shape of the other main surface is not particularly limited. Usually, it is often a flat glossy surface.

Moreover, copper foil can be used for various aspects (applications). For example, a printed wiring board, an electromagnetic wave shielding material, a continuity (earth) material, a lithium ion battery, and the like can be given.
Furthermore, if necessary, the copper foil may be formed in a pattern by a known method (for example, an etching method described in an etching step described later).

[Manufacturing method of copper foil]
The method for producing the copper foil is not particularly limited, and any method can be used as long as the surface roughness Rz and the fractal dimension are within a predetermined range.
FIG. 2 is a flowchart showing each step in a preferred embodiment of the method for producing a copper foil, which includes a plated layer forming step S102, a catalyst applying step S104, a plating step S106, a support removing step S108, and a plated layer. A removal step S110 is provided. If it is this aspect, adjustment of the surface roughness Rz and fractal dimension of the copper foil obtained is easy, and it is excellent also in productivity.
Below, each process of this suitable aspect is explained in full detail.

(Plating layer forming step S102)
In this step S102, a layer containing a polymer having a functional group that interacts with the plating catalyst or its precursor (hereinafter referred to as an interactive group as appropriate) and a polymerizable group is formed on the support, In this step, energy is applied to the layer containing the polymer to form a layer to be plated on the support.
The to-be-plated layer formed by this process S102 adsorbs (attaches) a plating catalyst or its precursor in the catalyst provision process S104 mentioned later according to the function of the interactive group contained in a polymer. That is, the layer to be plated functions as a good receiving layer for the plating catalyst or its precursor. Moreover, a polymeric group is utilized for the coupling | bonding of polymers by the hardening process by energy provision, and can obtain the to-be-plated layer excellent in hardness and hardness.
More specifically, as shown in FIG. 3A, a layer 14 to be plated is formed on the support 12 in step S102.
First, the materials (support, polymer, composition for forming a layer to be plated, etc.) used in this step S102 will be described in detail, and then the procedure of this step S102 will be described in detail.

(Support)
The support is a member for supporting each layer described below, and any conventionally known support substrate (for example, a resin substrate, a ceramic substrate, a glass substrate, a metal substrate, etc., preferably an insulating substrate) is used. Can be used.

Especially, it is preferable to use the peelable support body which has the surface which shows easy peelability from the point which can remove a support body more easily in support body removal process S108 mentioned later. In addition, the easy peelability which the surface of a peelable support body has is peeling at the interface of copper foil and a to-be-plated layer, when the external force for peeling a peelable support body is applied to the laminated body which has a copper foil mentioned later It means the property of peeling at the interface between the peelable support and the layer to be plated without being done.
The water contact angle of the surface showing the easy peelability of the peelable support is preferably 70 ° or more from the viewpoint that the peeling at the interface between the peelable support and the layer to be plated proceeds more easily. 110 ° is more preferable, and 80 to 100 ° is even more preferable.
As a method for measuring the water contact angle, a tangent method using two points of contact between the top of the dropped water and the support is used.

In addition, the magnitude | size and thickness in particular of a support body are not restrict | limited, The optimal magnitude | size and thickness are selected suitably.
The shape of the support is not particularly limited, but is usually a flat plate shape.

(polymer)
The polymer used has a polymerizable group and an interactive group.
The polymerizable group is a functional group capable of forming a chemical bond between polymers by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among these, a radical polymerizable group is preferable from the viewpoint of more excellent reactivity. Examples of radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like. Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups. Of these, a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are particularly preferable.

An interactive group is a functional group that interacts with a plating catalyst or a precursor thereof, a functional group that can form an electrostatic interaction with the plating catalyst or a precursor thereof, or a coordination group with a plating catalyst or a precursor thereof. Nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups and the like that can be formed can be used.
Examples of interactive groups include non-dissociable functional groups (functional groups that do not generate protons by dissociation).

More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazine ring, triazole ring, benzotriazole group, imidazole group, benzimidazole Group, quinoline group, pyridine group, pyrimidine group, pyrazine group, nazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanuric structure Nitrogen-containing functional groups such as nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group (R—O—CN); ether group, hydroxyl group, phenolic hydroxyl group, carboxyl group, Carbonate group, carbonyl group, ester group, group containing N-oxide structure, S An oxygen-containing functional group such as a group containing an oxide structure or a group containing an N-hydroxy structure; a thiophene group, a thiol group, a thiourea group, a thiocyanuric acid group, a benzthiazole group, a mercaptotriazine group, a thioether group, a thioxy group, a sulfoxide group, Sulfur-containing functional groups such as sulfone group, sulfite group, group containing sulfoxyimine structure, group containing sulfoxynium salt structure, sulfonic acid group, group containing sulfonic acid ester structure; Phosphate group, phosphoramide group, phosphine group And a phosphorus-containing functional group such as a group containing a phosphate ester structure; a group containing a halogen atom such as chlorine and bromine, and the like. In a functional group capable of taking a salt structure, a salt thereof can also be used.
Among them, since the polarity is high and the adsorption ability to a plating catalyst or a precursor thereof is high, an ionic polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, an ether group, or A cyano group is particularly preferable, and a carboxyl group or a cyano group is more preferable.
Two or more of these functional groups as interactive groups may be contained in the polymer.

The weight average molecular weight of the polymer is not particularly limited, but is preferably 1000 or more and 700,000 or less, more preferably 2000 or more and 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
The degree of polymerization of the polymer is not particularly limited, but is preferably a 10-mer or more, and more preferably a 20-mer or more. Moreover, 7000-mer or less is preferable, 3000-mer or less is more preferable, 2000-mer or less is still more preferable, 1000-mer or less is especially preferable.

As a preferred embodiment of the polymer, it has a unit having a polymerizable group represented by the following formula (a) (hereinafter also referred to as a polymerizable group unit as appropriate) and an interactive group represented by the following formula (b). Examples thereof include a copolymer containing a unit (hereinafter also referred to as an interactive group unit as appropriate). In addition, a unit means a repeating unit.

In the above formulas (a) and (b), R ¹ to R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc. ). The substituent is not particularly limited, and examples thereof include a methoxy group, a chlorine atom, a bromine atom, or a fluorine atom.
R ¹ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom. R ² is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom. R ³ is preferably a hydrogen atom. R ⁴ is preferably a hydrogen atom. R ⁵ is preferably a hydrogen atom, a methyl group, or a methyl group substituted with a bromine atom.

In the above formulas (a) and (b), X, Y, and Z each independently represent a single bond or a substituted or unsubstituted divalent organic group. Examples of the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a substituted or unsubstituted group. A divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO ₂ —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).

X, Y, and Z are preferably ester groups (—COO—) from the viewpoint that the removal efficiency of the plated layer is more excellent in the plated layer removal step described later.

In the above formulas (a) and (b), L ¹ and L ² each independently represent a single bond or a substituted or unsubstituted divalent organic group. As a definition of a divalent organic group, it is synonymous with the divalent organic group described by X, Y, and Z mentioned above.
L ¹ is an aliphatic hydrocarbon group or a divalent organic group having a urethane bond or a urea bond (for example, aliphatic carbonization) because the polymer can be easily synthesized and the catalyst adsorbability of the plated layer is excellent. Hydrogen group), and those having a total carbon number of 1 to 9 are preferred. Incidentally, the total number of carbon atoms of L ^1, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^1.

L ² is a single bond, a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination thereof in that the polymer is easily synthesized and the catalyst adsorption property of the plated layer is excellent. The groups are preferred. Among these, L ² is preferably a single bond or an aliphatic hydrocarbon group having 1 to 15 total carbon atoms, and particularly preferably unsubstituted. Incidentally, the total number of carbon atoms of L ^2, means the total number of carbon atoms contained in the substituted or unsubstituted divalent organic group represented by L ^2.

In the above formula (b), W represents a functional group that interacts with the plating catalyst or its precursor. The definition of the functional group is the same as the definition of the interactive group described above.

The content of the polymerizable group unit is preferably from 5 to 50 mol%, more preferably from 5 to 40 mol%, based on all units in the polymer. If it is less than 5 mol%, the reactivity (curability, polymerizability) may be lowered, and if it exceeds 50 mol%, gelation tends to occur during synthesis and synthesis is difficult.
In addition, the content of the interactive group unit is preferably 5 to 95 mol%, more preferably 10 to 95 mol%, based on the total unit in the polymer, from the viewpoint of adsorptivity to the plating catalyst or its precursor. 60 to 95 mol% is more preferable.
The polymerizable group unit and the interactive group unit may contain two or more different types of units.
The polymer may contain units other than the polymerizable group unit and the interactive group unit.

Specific examples of the polymer include, for example, polymers described in paragraphs [0106] to [0112] of JP-A-2009-007540, and paragraphs [0065] to [0070] of JP-A-2006-135271. Examples thereof include polymers described in paragraphs [0030] to [0108] of US2010-080964.
The polymer can be produced by known methods (eg, the methods in the literature listed above).

(Procedure of step S102)
First, the method for forming a layer containing the polymer (plated layer precursor layer) on the support is not particularly limited, and a known method can be used. For example, a method (coating method) of applying the composition for forming a layer to be plated containing the polymer on a support, or a method of directly laminating the polymer on the support is also included. Of these, the coating method is preferable because the film thickness of the layer to be plated can be easily controlled. About the aspect of the composition for to-be-plated layer forming, it mentions later.

In the case of the coating method, the method for coating the composition for forming a layer to be plated on the support is not particularly limited, and known methods (for example, spin coating, die coating, dip coating, etc.) can be used.
From the viewpoint of handleability and production efficiency, the composition for forming a layer to be plated is applied on a support, and if necessary, a drying treatment is performed to remove the remaining solvent, and a layer containing a polymer (layer to be plated) A mode of forming the forming composition layer) is preferred.
The conditions for the drying treatment are not particularly limited, but are preferably carried out at room temperature to 220 ° C. (preferably 50 to 120 ° C.) for 1 to 30 minutes (preferably 1 to 10 minutes) from the viewpoint of better productivity. .

Next, the method for applying energy to the layer containing the polymer on the support (composition layer forming composition layer) is not particularly limited. For example, it is preferable to use a heat treatment or an exposure process, and the exposure process is preferable from the viewpoint that the process is completed in a short time. By applying energy to the layer containing the polymer, the polymerizable group in the polymer is activated, crosslinking between the polymers occurs, and the curing of the layer proceeds.
For the exposure process, light irradiation with a UV lamp, visible light, or the like is used. Examples of the light source include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp. Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays. Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure.
The exposure time varies depending on the reactivity of the polymer and the light source, but is usually between 10 seconds and 5 hours. The exposure energy may be about 10 to 8000 mJ, preferably 50 to 3000 mJ.

In addition, when using heat processing as energy provision, a ventilation dryer, oven, an infrared dryer, a heating drum, etc. can be used.

The thickness of the layer to be plated is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.3 to 1.0 μm from the viewpoint of productivity.
Further, the surface roughness Rz of the surface of the layer to be plated (the surface opposite to the support side) is not particularly limited, but is preferably 0.2 μm or less in that the surface roughness Rz of the copper foil is further reduced. More preferably, it is 1 μm or less. The lower limit is not particularly limited, but is often 0.01 μm or more due to manufacturing restrictions.

(Composition for plating layer formation)
The composition for forming a layer to be plated contains the polymer.
The content of the polymer in the composition for forming a layer to be plated is not particularly limited, but is preferably 2 to 50% by mass and more preferably 3 to 20% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

The composition for forming a layer to be plated may contain a solvent. By containing the solvent, the handleability is improved.
Solvents that can be used are not particularly limited, for example, alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, propylene glycol monomethyl ether, acids such as acetic acid, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, Amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, ester solvents such as methyl acetate and ethyl acetate, carbonate solvents such as dimethyl carbonate and diethyl carbonate, and others In addition, ether solvents, glycol solvents, amine solvents, thiol solvents, halogen solvents and the like can be mentioned.
Among these, amide solvents, ketone solvents, nitrile solvents, and carbonate solvents are preferable. Specifically, acetone, dimethylacetamide, methyl ethyl ketone, cyclohexanone, acetonitrile, propionitrile, N-methylpyrrolidone, and dimethyl carbonate are preferable. .

The content of the solvent in the composition for forming a layer to be plated is not particularly limited, but is preferably 50 to 98% by mass, more preferably 90 to 97% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.

[Catalyst imparting step S104]
The catalyst applying step S104 is a step of applying a plating catalyst or a precursor thereof to the layer to be plated obtained in the layer to be plated forming step S102.
In this step S104, the polymer-derived interactive group adheres (adsorbs) the applied plating catalyst or its precursor depending on its function. More specifically, the plating catalyst or its precursor is adsorbed in the layer to be plated and on the surface of the layer to be plated.
First, the materials (plating catalyst or its precursor etc.) used at this process S104 are explained in full detail, and the procedure of this process S104 is explained in full detail after that.

(Plating catalyst or its precursor)
The plating catalyst or its precursor functions as a catalyst or electrode for copper plating treatment in the plating step S106 described later. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment.
Hereinafter, mainly electroless plating or a precursor thereof will be described in detail as a plating catalyst or a precursor thereof.

As the electroless plating catalyst, any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating. Specifically, a metal having a catalytic ability for autocatalytic reduction reaction (which tends to be more ionized than Ni). And those known as metals capable of low electroless plating). More specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, etc. are mentioned. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
As the electroless plating catalyst, metal colloid (metal particles) may be used. Generally, a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent.

The electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction. The metal ions of the metals mentioned as the electroless plating catalyst are mainly used. The metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction. The metal ion that is an electroless plating catalyst precursor may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating solution, by separately changing to a zero-valent metal by a reduction reaction. The electroless plating catalyst precursor may be immersed in an electroless plating solution and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.

The metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt. The metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO ₃ ) _n , MCl _n , M _{2 / n} (SO ₄ ), M _{3 / n} (PO ₄ ) (M represents an n-valent metal atom), and the like. As a metal ion, the thing which said metal salt dissociated can be used suitably. Specific examples include Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferred, and in particular, functional groups capable of coordination. In view of the number of types and catalytic ability, Ag ions and Pd ions are preferred.

In this step, zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.

It is preferable that the said plating catalyst or its precursor is used with the form of the plating catalyst liquid (The dispersion or solution which disperse | distributed or dissolved the plating catalyst or its precursor in the solvent) containing these.
As the solvent used in the plating catalyst solution, an organic solvent and / or water is used. When the plating catalyst solution contains an organic solvent, the permeability of the plating catalyst solution to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the interactive group.

The organic solvent used in the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the layer to be plated. Specifically, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, Acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve and the like can be used.

(Procedure of step S104)
The method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
For example, the above plating catalyst solution (a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a metal salt dissolved in an appropriate solvent and dissociated metal ions) is prepared, and the plating catalyst solution is applied to the layer to be plated. The method of apply | coating on the top or the method of immersing the support body in which the to-be-plated layer was formed in a plating catalyst liquid are mentioned.
The contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 10 minutes, and more preferably about 1 minute to 5 minutes.
The temperature of the plating catalyst solution at the time of contact is preferably about 20 to 60 ° C., more preferably about 30 to 50 ° C.

[Plating step S106]
In the plating step S106, the plating layer to which the plating catalyst or its precursor is applied in the catalyst application step S104 is subjected to copper plating, and a copper foil (corresponding to copper plating) is formed on the layer to be plated. This is a step of obtaining a laminate having a body, a layer to be plated, and a copper foil in this order. More specifically, as shown in FIG. 3B, in this step S106, the copper foil 10 is formed on the layer 14 to be plated, and the laminate 16 is obtained.

Examples of the copper plating treatment performed in this step S106 include electroless copper plating, electrolytic copper plating, and the like, and are selected depending on the function of the plating catalyst or its precursor applied to the layer to be plated in the above step S104. be able to.
Especially, it is preferable to perform electroless copper plating from the point from which the copper foil which shows better adhesiveness with respect to a base material is obtained. Moreover, in order to obtain the copper foil of desired layer thickness, it is a more preferable aspect to perform electrolytic copper plating after electroless copper plating.
Hereinafter, the copper plating process suitably performed in this process S106 is demonstrated.

(Electroless copper plating)
Electroless copper plating refers to an operation of depositing copper by a chemical reaction using a solution in which copper ions are dissolved.
The electroless copper plating in this step S106 is performed by, for example, washing the layer to be plated with the electroless plating catalyst with water to remove excess electroless plating catalyst (metal) and then immersing it in an electroless copper plating bath. Do it. As the electroless copper plating bath used, a known electroless copper plating bath can be used. The electroless copper plating bath is preferably an alkaline electroless copper plating bath (preferably having a pH of about 9 to 14) from the viewpoint of availability.
In addition, when the electroless plating catalyst precursor is immersed in the electroless copper plating bath while adsorbed or impregnated on the layer to be plated, the layer to be plated is washed with water to remove excess precursor (metal salt, etc.). Then, it is immersed in an electroless copper plating bath. In this case, reduction of the plating catalyst precursor and subsequent electroless copper plating are performed in the electroless copper plating bath. As the electroless copper plating bath used here, a known electroless copper plating bath can be used as described above.

In addition, the reduction of the electroless plating catalyst precursor is performed as a separate step before electroless copper plating by preparing a catalyst activation liquid (reducing liquid) separately from the above-described embodiment using the electroless copper plating liquid. It is also possible. The catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1 to 30% by mass is more preferable. As the reducing agent, known reducing agents (for example, boron-based reducing agents such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid, etc.) can be used.
When dipping, keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.

As a composition of a general electroless copper plating bath, for example, in addition to a solvent (for example, water), 1. 1. copper ion for plating, 2. reducing agent; Additives (stabilizers) that improve the stability of copper ions are mainly included.

The organic solvent used in the electroless copper plating bath is preferably a water-soluble solvent, and from this point, ketones such as acetone and alcohols such as methanol, ethanol and isopropanol are preferably used.

Copper is used as the type of metal used in the electroless copper plating bath, but other metals (for example, copper, tin, lead, nickel, gold, silver, palladium, rhodium) are used in combination as required. May be.

The thickness of the copper foil obtained by electroless copper plating can be controlled by the copper ion concentration, the immersion time in the electroless copper plating bath, or the temperature of the electroless copper plating bath. When performing copper electroplating to be described later using the copper foil as a conductive layer, it is preferable that a copper foil of at least 0.1 μm or more is uniformly applied. From the viewpoint of conductivity, when not performing electrolytic copper plating described later, it is preferably 0.1 μm or more, more preferably 1 μm or more, and most preferably 3 to 10 μm.
In addition, the immersion time in the electroless copper plating bath is preferably about 1 minute to 10 hours, and more preferably about 10 minutes to 3 hours.

(Electrolytic copper plating (electro copper plating))
In this step S106, when the plating catalyst or precursor thereof applied in step S104 has a function as an electrode, electrolytic copper plating is applied to the layer to be plated to which the plating catalyst or precursor is applied. It can be carried out.
Further, after the above-described electroless copper plating, the formed copper foil may be used as an electrode, and electrolytic copper plating may be further performed. Thereby, a copper foil having an arbitrary thickness can be easily formed.

As a method of electrolytic copper plating, a conventionally known method can be used. In addition, although copper is used as a metal used for electrolytic plating, a metal other than copper (for example, chromium, lead, nickel, gold, silver, tin, zinc, etc.) may be used in combination as necessary. .

Moreover, the thickness of the copper foil obtained by electrolytic copper plating can be controlled by adjusting the copper ion concentration or current density contained in the electrolytic copper plating bath.
When applied to general electric wiring, the thickness of the copper foil is preferably 1 μm or more, more preferably 3 to 30 μm from the viewpoint of conductivity.
In addition, in order to remove the copper oxide on the electroless copper plating, contact an acidic solution (for example, sulfuric acid aqueous solution) and the electroless copper plating between the electroless copper plating and the electrolytic copper plating, if necessary. You may perform the process to make.

[Support removal step]
The support removing step S108 is a step of removing the support from the laminate obtained in the plating step S106. More specifically, as shown in FIG. 3C, the support 12 is removed from the laminate 16 shown in FIG. 3B, and the layer to be plated including the layer 14 and the copper foil 10 is included. The attached copper foil 18 is obtained.

The method for removing the support is not particularly limited, and an optimal method is appropriately selected according to the type of support used.
For example, a method in which a solution in which only the support in the laminate is dissolved is brought into contact with the laminate and the support is dissolved and removed, a method in which the support is physically separated from the laminate, and a support in the laminate For example, a method of removing by performing oxidation treatment such as plasma treatment or ozone treatment.

As described above, when a peelable support is used as the support, it is possible to cause separation at the interface between the layer to be plated and the support by a physical action, and to easily separate and remove the peelable support. it can.

[Plating layer removal process]
The to-be-plated layer removing step S110 is a step for removing the to-be-plated layer from the laminate of the to-be-plated layer and the copper foil obtained in the support removing step S108. More specifically, as shown in FIG. 3D, the plated layer 14 is removed from the plated foil 14 with the plated layer shown in FIG.

The method for removing the layer to be plated is not particularly limited, and an optimum method is appropriately selected according to the type of material constituting the layer to be plated.
For example, a solution in which only the layer to be plated dissolves (for example, an alkaline aqueous solution) and the copper foil with the layer to be plated are brought into contact with each other, and the layer to be plated is dissolved and removed. And a method of removing the target layer by subjecting the layer to be plated to oxidation treatment such as plasma treatment or ozone treatment.

In addition, in the method for dissolving and removing the plated layer, ultrasonic treatment or the like may be used in combination as necessary. By using ultrasonic treatment in combination, the removal efficiency of the layer to be plated is improved. Alternatively, a solution for dissolving the layer to be plated may be sprayed onto the layer to be plated under a certain pressure.

The support removing step S108 and the plated layer removing step S110 may be performed separately as described above, or may be performed simultaneously.
That is, you may implement the process of removing a support body and a to-be-plated layer from the laminated body obtained by said plating process S106, and obtaining copper foil. In this case, for example, a solution in which the support and the layer to be plated are dissolved is brought into contact with the laminate, and the support and the layer to be plated are dissolved and removed. Examples of the peeling method include a method of removing the support and the layer to be plated by performing an oxidation treatment such as plasma treatment or ozone treatment.

The surface in contact with the plated layer of the copper foil obtained through the above steps S102 to S110 satisfies the predetermined surface roughness Rz and the fractal dimension as described above.

[Laminated body having copper foil (laminated body containing copper foil)]
The laminated body which has a base material and copper foil is obtained by bonding a copper foil and a base material so that the surface which shows predetermined surface roughness Rz and fractal dimension of the copper foil mentioned above may contact | connect a base material surface. .
In this laminated body, since a base material adjoins on the surface which has a fine uneven structure on the surface of copper foil, the adhesiveness of a base material and copper foil is excellent.
First, the base material used is explained in full detail below, and the procedure for obtaining a laminated body is explained in full detail after that.

(Base material)
The kind in particular of base material with which copper foil is affixed is not restrict | limited, A well-known base material can be used. For example, a resin base material, a glass base material, a ceramic base material, a paper base material, etc. are mentioned. Especially, it is excellent in adhesiveness with copper foil, and it is preferable to use a resin base material from the point of application to a printed wiring board.

Although the kind of material which comprises a resin base material is not restrict | limited in particular, A thermoplastic resin or a thermosetting resin is mentioned.
Examples of the thermosetting resin include an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, a polyolefin resin, and an isocyanate resin.
Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, ABS resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, and polymethyl methacrylate. , Polyether ether ketone, polyamide, polylactic acid, cycloolefin copolymer (COP), liquid crystal polymer (LCP), and the like.

The resin base material may contain fillers such as glass woven fabric (glass cloth), glass nonwoven fabric, aramid woven fabric, and aramid nonwoven fabric.

The shape of the substrate is not particularly limited, but is preferably a flat plate from the viewpoint of better adhesion.

(Laminate manufacturing method)
The method for attaching the copper foil to the substrate is not particularly limited, and a known method can be used. For example, a desired laminate can be obtained by laminating and laminating a copper foil and a substrate (particularly a resin substrate), and applying pressure such as pressing.

When crimping, heat treatment may be performed as necessary.
Optimum conditions are appropriately selected depending on the base material used for thermocompression bonding, but when using a general epoxy resin base material, the adhesiveness of the copper foil is better. In view of fluidity, thermosetting property, and thermal decomposability of the resin substrate, 150 to 200 ° C. is preferable, and 165 to 185 ° C. is more preferable. In addition, the time for performing the thermocompression bonding is preferably 0.5 to 4 hours, and more preferably 1 to 2 hours from the viewpoint that the adhesiveness of the copper foil is more excellent and the productivity is more excellent.

In addition, when manufacturing a laminated body, you may affix a copper foil only to the single side | surface of a flat base material, or may affix it on both surfaces.

(Use)
The obtained laminate can be used for various applications. For example, the present invention can be applied to various uses such as a semiconductor package, a motherboard, an FPC, a COF, a TAB, and an antenna.

[Etching process]
As needed, the laminated body which equips the surface with a patterned copper foil can be manufactured by etching the copper foil in the laminated body containing the said base material and copper foil in a pattern shape.
This etching process will be described in detail below.

An etching process is a process of etching the copper foil in a laminated body in pattern shape. That is, in this step, a desired copper foil pattern can be formed by removing unnecessary portions of the formed copper foil by etching.
Any method can be used to form the copper foil pattern, and specifically, a generally known subtractive method or semi-additive method is used.

In the subtractive method, a dry film resist layer is provided on the formed copper foil, the same pattern as the copper foil pattern part is formed by pattern exposure and development, and the copper foil is removed with an etching solution using the dry film resist pattern as a mask. This is a method for forming a copper foil pattern. Any material can be used as the dry film resist, and negative, positive, liquid, and film-like ones can be used. Moreover, as an etching method, any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus. As an etching solution, for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.

The semi-additive method is to provide a dry film resist layer on the copper foil, form the same pattern as the non-copper foil pattern part by pattern exposure and development, perform electroplating using the dry film resist pattern as a mask, and dry film In this method, quick etching is performed after removing the resist pattern, and the copper foil is removed in a pattern to form a copper foil pattern. The dry film resist, the etching solution, etc. can use the same material as the subtractive method. Moreover, the above-mentioned method can be used as the electroplating method.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
First, the synthesis method of the polymer used in the examples will be described in detail.

(Synthesis Example 1: Synthesis of Polymer A)
N-methylpyrrolidone (35 g) was placed in a 1000 ml three-necked flask and heated to 75 ° C. under a nitrogen stream. Thereto, N-methylpyrrolidone (35 g) containing 2-hydroxyethyl acrylate (Tokyo Kasei) (6.60 g), 2-cyanoethyl acrylate (28.4 g), and V-601 (Wako Pure Chemical Industries) 0.65 g. ) The solution was added dropwise over 2.5 hours. After completion of dropping, the reaction solution was heated to 80 ° C. and further stirred for 3 hours. Thereafter, the reaction solution was cooled to room temperature.
Ditertiary butyl hydroquinone (0.29 g), dibutyltin dilaurate (0.29 g), Karenz AOI (manufactured by Showa Denko KK) (18.56 g), and N-methylpyrrolidone (19 g) were added to the above reaction solution. In addition, the reaction was carried out at 55 ° C. for 6 hours. Thereafter, methanol (3.6 g) was added to the reaction solution, and the reaction was further performed for 1.5 hours. After completion of the reaction, reprecipitation was performed with water, and the solid matter was taken out to obtain polymer A (25 g).

(Identification of structure)
Polymer A was dissolved in heavy DMSO and measured by Bruker 300 MHz NMR (AV-300). Peaks corresponding to cyano group-containing units are broadly observed at 4.3-4.05 ppm (2H min), 2.9-2.8 ppm (2H min), 2.5-1.3 ppm (3H min), Peaks corresponding to the polymerizable group-containing unit are 7.3 to 7.2 ppm (1 H min), 6.4 to 6.3 ppm (1 H min), 6.2 to 6.1 ppm (1 H min), 6.0 to 5.9 ppm (1H min), 4.3-4.05 ppm (6H min), 3.3-3.2 ppm (2H min), 2.5-1.3 ppm (3H min) broadly observed and polymerized It was found that the sex group-containing unit: cyano group-containing unit = 22: 78 (mol%).

(Measurement of molecular weight)
Polymer A was dissolved in THF, and the molecular weight was measured using a high-speed GPC (HLC-8220GPC) manufactured by Tosoh Corporation. As a result, a peak appeared at 23.75 minutes, and it was found that Mw = 5300 (Mw / Mn = 1.54) in terms of polystyrene.
In addition, the numerical value in the chemical formula of the following polymer A represents the mol% of each unit.

<Example 1>
[Plating layer forming process]
An acetonitrile solution containing 10% by weight of polymer A (a composition to be plated layer-forming composition A) is applied onto a support (company name: PANAC, product name: TP05, contact angle with water: 95 °) by spin coating. (Condition: Coating is applied so that the film thickness after drying of the layer to be plated is 0.5 μm) and dried at 80 ° C. for 10 minutes, and then UV exposure machine (manufactured by Mitsunaga Electric Co., Ltd., model number: UVF-502S, Using a lamp: UXM-501MD), exposure was performed with an exposure energy of 1000 mJ.
The support after the exposure was immersed in a 1% by mass aqueous NaHCO ₃ solution for 10 minutes, and then washed with distilled water to obtain a support A. In addition, the surface roughness Rz of the exposed surface of the obtained layer to be plated was 0.01 μm.

[Catalyst application process]
A 0.5 mass% palladium acetate aqueous solution was prepared and used as a plating catalyst solution. The support A was immersed in the plating catalyst solution (liquid temperature: room temperature) for 5 minutes and then washed with pure water.

[Plating process]
Next, electroless copper plating was performed on the support A. Electroless copper plating uses an electroless copper plating bath of the following composition using Sulcup PGT (manufactured by Uemura Kogyo Co., Ltd.), and the support A is immersed for 15 minutes at a bath temperature of 30 ° C., resulting in a plating deposition thickness of 0.5 μm. Thus, a copper foil was formed.
The preparation order and raw materials of the electroless copper plating solution are as follows.
Approximately 60% by volume of distilled water
PGT-A 9.0% by volume
PGT-B 6.0% by volume
PGT-C 3.5% by volume
Formalin solution * 2.3% by volume
Finally, the liquid level was adjusted with distilled water so that the total amount would be 100% by volume.
* The formalin used here is a Wako Pure Chemical formaldehyde solution (special grade).

Next, the obtained support A with copper foil was immersed in a 1% by mass sulfuric acid aqueous solution for 15 seconds to remove the oxide film on the copper foil.
Next, electrolytic copper plating (2.5 A / dm ² : 20 minutes) is performed using the copper foil obtained above as a power feeding layer so that the copper thickness becomes 12 μm using an electrolytic copper plating bath having the following composition. A laminate A having a copper foil was obtained.
(Composition of electrolytic copper plating bath)
-Water 1000 parts by weight-Copper sulfate pentahydrate 110 parts by weight-298 parts by weight of 98% sulfuric acid-0.2 parts by weight of 35% hydrochloric acid-Made by Meltex, 30 parts by weight of Capper Gream ST-901M

[Support removal step]
Next, the support body in the obtained laminated body A was peeled by hand, and the copper foil A with a to-be-plated layer which has a to-be-plated layer and copper foil was obtained.

[Plating layer removal process]
Furthermore, 4 mass% NaOH aqueous solution was sprayed with the spray pressure of 0.2 MPa with respect to the to-be-plated layer in the copper foil A with a to-be-plated layer, the to-be-plated layer was removed, and copper foil was obtained.

[Production of copper foil-containing laminate]
Next, lay the copper foil on both sides of the prepreg so that the surface of the obtained copper foil in contact with the layer to be plated is in contact with the prepreg (Hitachi Kasei, GEA-67N, 0.2 mm). To obtain a double-sided copper-clad plate.

<Example 2>
Example 1 except that the plating layer was removed by performing plasma treatment (Nissin, microwave downflow method) instead of spray removal with 4% NaOH aqueous solution performed in [Plating layer removal step]. A double-sided copper-clad plate was obtained according to the same procedure as described above.

<Example 3>
A double-sided copper-clad plate was obtained according to the same procedure as in Example 1 except that the exposure was performed with the same UV exposure machine at an exposure energy of 500 mJ in the above [plated layer forming step].

<Example 4>
In the above [catalyst application step], a 0.2 mass% palladium acetate aqueous solution was prepared, and this was used as a plating catalyst solution. After immersing the support A in the plating catalyst solution (liquid temperature: room temperature) for 2 minutes, A double-sided copper-clad plate was obtained according to the same procedure as in Example 1 except that it was washed with water.

<Comparative Example 1>
Using a low profile electrolytic copper foil (made by Fukuda Metals, product name SV, Rz = 1.840 μm, copper thickness 12 μm), following the same procedure as in [Production of copper foil-containing laminate] carried out in Example 1, both sides A copper-clad plate was obtained.

<Comparative example 2>
The condition of electrolytic copper plating in the above [plating step] is 8 A / dm ² for 7 minutes, and the exposed surface of the plating (the surface opposite to the side where the layer to be plated is present) is intentionally roughened, and Rz = 0 A copper foil was obtained by the same procedure as in Example 1 except that a plating surface of 135 μm was obtained (copper thickness was 12 μm). Next, a double-sided copper-clad board is obtained according to the same procedure as in [Manufacture of a copper foil-containing laminate] carried out in Example 1 with the exposed surface of the intentionally roughened copper foil as the adhesive surface with the prepreg. It was.

<Comparative Example 3>
The condition of electrolytic copper plating in the above [plating step] is 13 A / dm ² , 4.5 minutes, and the exposed surface of the plating (the surface opposite to the side where the layer to be plated is present) is intentionally roughened to obtain Rz = A copper foil was obtained by the same procedure as in Example 1 except that a plating surface of 0.310 µm was obtained (copper thickness was 12 µm). Next, a double-sided copper-clad board is obtained according to the same procedure as in [Manufacture of a copper foil-containing laminate] carried out in Example 1 with the exposed surface of the intentionally roughened copper foil as the adhesive surface with the prepreg. It was.

<Comparative Example 4>
After [Plating layer forming step] and [Catalyst applying step] in Example 1, [Plating layer forming step] in Example 1 was again performed to form a plated layer with a configuration having a catalyst distribution. . That is, the catalyst was supported on the layer to be plated located in the lower layer, but the catalyst was not present in the upper layer to be plated. The surface roughness Rz of the exposed surface of the obtained layer to be plated was 0.014 μm.
Thereafter, the immersion time in the electroless copper plating bath in the [plating step] was changed from 30 minutes to 80 minutes, and the copper foil was formed so that the plating deposition thickness became 0.5 μm. According to the same procedure, a double-sided copper-clad plate was obtained.

<Various evaluations>
(Measurement of peel strength)
Based on JIS C 6481: 1996, a 90 ° C. peel strength test was performed on the copper foils of the double-sided copper-clad plates obtained in Examples 1 to 4 and Comparative Examples 1 to 4. The results are summarized in Table 1.

(Measurement of surface roughness Rz and Ra)
Surface roughness of the surface of the copper foil obtained in Examples 1 to 4 in contact with the layer to be plated and the surface of the copper foil of Comparative Examples 1 to 4 in contact with the prepreg The thickness Rz and Ra were measured based on JIS B 0601: 2001. In the measurement, a surface shape measuring device (company name: ULVAC, device name: Dektak 150) was used. The results are summarized in Table 1.

(Measurement of fractal dimension)
Dual-Beam FIB apparatus (manufactured by FEI, Dual Beam Nova200 Nanolab) for the copper foils obtained in [Plating layer removal step] of Examples 1 to 4 and the copper foils used in Comparative Examples 1 to 4 The sample was processed using an acceleration voltage of 30 kV, and a cross-section was obtained. Next, the cross section was observed with a focused ion beam apparatus (SMI 9200, manufactured by Seiko Instruments Inc.) and obtained as image data. Thereafter, the roughened surface portion (line segment) on the side to be brought into close contact with the prepreg of the copper foil is extracted by image processing, and the contour line is drawn in five measurement regions (1 μm × 1 μm) based on this cross-sectional photograph. The fractal dimensions were calculated and arithmetically averaged to obtain the fractal dimensions (average fractal dimensions) shown in Table 1. In the box count method, the box size (the size of one side of the square box) was 1 nm to 10 nm.

(Pattern wiring formation (L / S = 25μm / 25μm))
DFR (Hitachi Chemical Co., Ltd., RY3310) was laminated on the copper foils of the double-sided copper-clad plates obtained in Examples 1 to 4 and Comparative Examples 1 to 4. Next, a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) defined in JPCA-ET01 is closely attached to the substrate on which the dry resist film is laminated, and the resist is 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with light energy. Development was performed by spraying a 1% Na ₂ CO ₃ aqueous solution onto the exposed substrate at a spray pressure of 0.2 MPa. Thereafter, the substrate was washed with water and dried to form a subtractive resist pattern on the copper foil.
Etching was performed by immersing the substrate on which the resist pattern was formed in an FeCl ₃ / HCl aqueous solution (etching solution) at a temperature of 40 ° C. to remove the copper foil present in the region where the resist pattern was not formed. Thereafter, the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the substrate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a comb-like wiring (pattern shape). Copper foil) was obtained. The obtained wiring was L / S = 25 μm / 25 μm.
Thereafter, in order to estimate the variation in the line width, the wiring width (bottom value) at 50 arbitrary points was measured, and the standard deviation was calculated. The results are summarized in Table 1.
In Comparative Examples 2 to 4, since the adhesion of the copper foil to the prepreg was low, the copper foil was peeled off during the etching, and wiring could not be formed.

As shown in Table 1, it was confirmed that the copper foils of the present embodiment (Examples 1 to 4) exhibited excellent peel strength even though the surface roughness Rz was very small. It was also confirmed that the wiring width variation was small and a high-definition wiring pattern could be formed.
On the other hand, as shown in Comparative Example 1, a conventionally known copper foil has a high surface roughness Rz and thus has excellent peel strength, but has a wide wiring width variation and a high-definition wiring pattern. I could not.
Further, as shown in Comparative Examples 2 to 4, when the fractal dimension was outside the predetermined range, the peel strength of the copper foil was inferior and wiring could not be formed.

DESCRIPTION OF SYMBOLS 10 Copper foil 12 Support body 14 Layer to be plated 16 Laminated body 18 Copper foil with a layer to be plated

Claims

A copper foil for pasting used for pasting to a substrate,
The surface roughness (Rz) of the surface to be attached to the substrate is 0.500 μm or less,
The fractal dimension of the contour line of the surface on the side to be attached to the substrate in the cross section of the copper foil, calculated by applying the box count method in which the size of one side of the square box is set to 1 nm to 10 nm, is 1.020. A copper foil for pasting which is ˜1.400.
The laminated body which has a base material and the copper foil for affixing of Claim 1 affixed on the said base material.
A printed wiring board containing the laminate according to claim 2.
It is a manufacturing method of the copper foil for pasting of Claim 1,
On the support, a layer containing a polymer having a functional group and a polymerizable group that interacts with the plating catalyst or its precursor is formed, and then energy is applied to the layer containing the polymer, and the support Forming a layer to be plated on;
Adding a plating catalyst or a precursor thereof to the layer to be plated;
A copper plating process is performed on the layer to be plated to which the plating catalyst or its precursor is applied, a copper foil is formed on the layer to be plated, and the support, the layer to be plated, and the copper foil are combined with each other. Obtaining a laminate having in order;
The manufacturing method of the copper foil for adhesion | attachment which has the process of removing the said support body and the said to-be-plated layer from the said laminated body, and obtaining the said copper foil.