PH12015500529B1 - Carrier-attached copper foil - Google Patents

Abstract

A carrier-attached copper foil suitable for fine pitching is provided. The carrier-attached copper foil includes a copper foil carrier, a release layer laminated onto the copper foil carrier, and an ultra-thin copper layer laminated on the release layer. The ultra-thin copper layer is roughened, and the Rz of the surface of the ultra-thin copper layer is 1.6 mm or less when measured using a non-contact roughness meter.

Description

' 4 v

After the treatments such as roughening have been performed, the surface of the ultra-thin copper layer (the “roughened surface”) preferably has an Rz (ten-point average roughness) of 1.6 um or less when measured using a non-contact roughness meter. This is especially advantageous from the standpoint of fine pitching. The Rz is preferably 1.5 ym or less, more preferably 1.4 um or less, more preferably 1.35 um or less, more preferably 1.3 um or less, more preferably 1.2 um or less, more preferably 1.0 um or less, more preferably 0.8 um or less, and more preferably 0.6 ym or less.

Because adhesion to the resin declines when the Rz is too low, the Rz is preferably 0.01 um or higher, more preferably 0.1 pum or higher, and even more preferably 0.2 pm or higher.

After the treatments such as roughening have been performed, the surface of the ultra-thin copper layer (the “roughened surface”) preferably has an Ra (calculated average roughness) of 0.30 um or less when measured using a non-contact roughness meter. This is especially advantageous from the standpoint of fine pitching. The Ra is preferably 0.27 um or less, more preferably 0.26 um or less, more preferably 0.25 um or less, more preferably 0.24 um or less, more preferably 0.23 pm or less, more preferably 0.20 um or less, more preferably 0.18 um or less, more preferably 0.16 um or less, more preferably 0.15 um or less, and more preferably 0.13 pum or less.

Because adhesion to the resin declines when the Ra is too low, the Ra is preferably 0.005 pm or higher, more preferably 0.009 um or higher, more preferably 0.01 um or higher, more preferably 0.02 pm or higher, more preferably 0.05 um or higher, and more preferably 0.10 ym or higher.

After the treatments such as roughening have been performed, the surface of the ultra-thin copper layer (the “roughened surface”) preferably has an Rt of 2.3 um or less when measured using a non-contact roughness meter. This is especially advantageous from the standpoint of fine pitching. The Rt is preferably 2.2 um or less, more preferably 2.1 um or less, more preferably 2.07 um or less, more preferably 2.0 um or less, more preferably 1.9 um or less, more preferably 1.8 um or less, more preferably 1.5 um or less, more preferably 1.2 um or less, and more preferably 1.0 um or less. Because adhesion to the resin declines when the value is too low, the Rt is preferably 0.01 um or higher, more preferably 0.1 um or higher, more preferably 0.3 pm or higher, and more preferably 0.5 pm or higher.

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After the treatments such as roughening have been performed, the surface of the ultra-thin copper layer preferably has an Ssk (skewness) of from -0.3 to 0.3 when measured using a non-contact roughness meter. This is especially advantageous from the standpoint of fine pitching. The lower limit for the Ssk is preferably -0.2 or more, more preferably -0.1 or more, more preferably -0.070 or more, more preferably -0.065 or more, more preferably -0.060 or more, more preferably -0.058 or more, and more preferably 0 or more. The upper limit for Ssk is preferably 0.2 or less.

After the treatments such as roughening have been performed, the surface of the ultra-thin copper layer preferably has a Sku (kurtosis) of 2.7 to 3.3 when measured using a non-contact roughness meter. This is especially advantageous from the standpoint of fine pitching. The lower limit for the Sku is preferably 2.8 or more, more preferably 2.9 or more, and more preferably 3.0 or more. The upper limit for

Sku is preferably 3.2 or less.

In the present invention, the Ra and Rz roughness parameters for the surface of the ultra-thin copper layer are in accordance with JIS B0601-1994, the Rt roughness parameters are in accordance with JIS B0601-2001, and the Ssk and Sku roughness parameters are in accordance with the ISO25178 draft standards when measured using a non-contact roughness meter.

In the case of a printed wiring board or copper-clad laminate, when an insulating substrate of resin is attached to the surface of the ultra-thin copper layer, the insulating substrate is dissolved and removed so that the surface roughness (Ra, Rt, Rz) of the copper circuits or copper foil can be measured.

In fine pitching, it is important to control the volume of the roughened surface to reduce the amount of etching performed on the roughened particle layer. Here, “volume” is a value measured using a laser microscope, and is an indicator used to evaluate the volume of the roughened particles present on the roughened surface.

When the volume of the roughened surface is higher, the adhesion of the ultra-thin copper layer to the resin is stronger. When the adhesion of the ultra-thin copper layer to the resin is stronger, the anti-migration properties tend to be better. More specifically, the volume is measured using a laser microscope, and is preferably 300,000 um’ or more, and more preferably 350,000 pm’ or more per 66,524 pm’ area i , ' of the roughened surface. When the volume is too high, the amount of etching increases, and fine pitching cannot be performed. Therefore, the volume is preferably 500,000 pm’ or less, and more preferably 450,000 pm?’ or less.

Furthermore, in fine pitching, it is important to control the surface area ratio of the roughened surface to ensure adhesion of the fine roughening particles to the resin.

Here, “surface area ratio” is a value measured using a laser microscope, and is the quotient of the actual area divided by the area when the area and actual area are measured. Here, “area” is the measurement reference area, and the “actual area” is the surface area in the measurement reference area. When the surface area ratio is too high, the adhesion strength increases. However, the amount of etching increases and fine pitching cannot be performed. When the surface area ratio is too low, sufficient adhesion strength cannot be ensured. Therefore, a value from 1.05 to 1.5 is preferred, a value from 1.07 to 1.47 is more preferred, a value from 1.09 to 1.4 is more preferred, and a value from 1.1 to 1.3 is more preferred. <5. Resin Layer >

In the carrier-attached copper foil of the present invention, a resin layer may be provided on the surface of the ultra-thin copper layer after each of the surface treatments, such as roughening, has been completed. For example, a resin layer may be provided on top of the roughening layer, heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer. The resin layer may be an insulating resin layer.

The resin layer may be an adhesive resin, that is, an adhesive, or an adhesive insulating resin layer in a semicured state (B stage). When a resin in a semicured state (B stage), the surface is not tacky to the touch and the insulating resin layer can be laminated and then stored. The curing reaction then is completed by subjecting the resin to heat treatment.

The resin layer may include a thermosetting resin, or the resin may be a thermoplastic resin. The resin layer may also include a thermoplastic resin. The resin layer may include any resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, or skeletal material common in the art. Examples of materials (resins, resin curing agents, compounds,

f \ v curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, and skeletal materials) used in the resin layer and/or resin layer forming methods and forming devices are described in the following documents: WO 2008/004399 Al, WO 2008/053878 Al, WO 2009/084533 Al, JP11-5828A, JP11- 140281A, JP3184485B, WO 97/02728 Al, JP3676375B, JP2000-43188A,

JP3612594B, JP2002-179772A, JP2002-359444A, JP2003-304068A, JP3992225B,

JP2003-249739A, JP4136509B, JP2004-82687A, JP4025177B, JP2004-349654A,

JP4286060B, JP2005-262506A, JP4570070B, JP2005-53218A, JP3949676B,

JP4178415B, WO 2004/005588 Al, JP2006-257153A, JP2007-326923A, JP2008- 111169A, JP5024930B, WO 2006/028207 Al, JP4828427B, JP2009-67029A, WO 2006/134868 Al, JP5046927B, JP2009-173017A, WO 2007/105635 Al, JP51808135B,

WO 2008/114858 Al, WO 2009/008471 Al, JP 2011-14727A, WO 2009/001850 Al,

WO 2009/145179 A1, WO 2011/068157 Al, and JP2013-19056A.

There are no particular restrictions on the type of resin used in the resin layer.

Preferred examples include one or more resins selected from among epoxy resins, polyimide resins, polyfunctional cyanate ester compounds, maleimide compounds, poly maleimide compounds, maleimide resins, aromatic maleimide resins, polyvinyl acetal resins, urethane resins, polyether sulfone resins, aromatic polyamide resins, aromatic polyamide resin polymers, rubber resins, polyamines, aromatic polyamines, polyamide-imide resins, rubber modified epoxy resins, phenoxy resins, carboxyl group-modified acrylonitrile-butadiene resins, polyphenylene oxides, bismaleimide triazine resins, thermosetting polyphenylene oxide resins, cyanate ester resins, carboxylic acid anhydrides, polycarboxylic acid anhydrides, linear polymers with a crosslinkable functional group, polyphenylene ether resins, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenol compounds, manganese naphthenates, 2,2-bis (4-glycidyl phenyl) propane, polyphenylene ether-cyanate resins, siloxane-modified polyamide-imide resins, cyano ester resins, phosphazene-based resins, rubber- modified polyamides-imide resins, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxys, polymer epoxys, aromatic polyamides, fluorine resins, bisphenols, block copolymer polyimide resins, and cyano ester resins.

Said epoxy resins can be used without any problems if they have two or more epoxy groups per molecule and can be used in electrical or electronic applications.

Epoxy resins epoxidized using a compound having two or more glycidyl groups per f y ’ molecule are especially preferred. Examples include those selected from among bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AD epoxy resins, novolac epoxy resins, cresol novolac epoxy resins, alicyclic epoxy resins, brominated epoxy resins, phenol novolac epoxy resins, naphthalene epoxy resins, brominated bisphenol A epoxy resins, ortho-cresol novolac epoxy resins, rubber-modified bisphenol A epoxy resins, glycidyl amine epoxy resins, triglycidylisocyanurate, N,N-diglycidylaniline and other glycidyl amine compounds, tetrahydrophthalic acid diglycidyl ester and other glycidyl ester compounds, phosphorus-containing epoxy resins, biphenyl epoxy resins, biphenyl novolac epoxy resins, trishydroxyphenylmethane epoxy resins, and tetraphenylethane epoxy resins.

These resins can be used alone or in mixtures of two or more. Hydrogenated and halogenated epoxy resins can also be used. Any phosphorus-containing epoxy resin common in the art can be used as the phosphorus-containing epoxy resin. A preferred example of a phosphorus-containing epoxy resin is an epoxy resin obtained as a derivative of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide which has two or more epoxy groups per molecule.

This epoxy resin obtained as a derivative of 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide can be a phosphorus-containing epoxy resin obtained by reacting naphthoquinone or hydroquinone with 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide to obtain a compound in Formula 1 (HCA-NQ) or a compound in Formula 2 (HCA-HQ), and then reacting an epoxy resin with some of the OH groups. [Formula 1] 0=pP—0

HO

" Y, ’ [Formula 2] 0=P—0 or

HO

A phosphorus-containing epoxy resin, or Component E in which the compound above is used as a raw material, is preferably used in a mixture of one or two compounds having a structure according to Formula 3 through Formula 5 below.

These resins have superior stability in a semicured state and a good flame-retardant effect. [Formula 3] 0=p—0 0H ~~ 0_ 0!

CE A A SE

~~ ~~ ? 0l_ | ;

Spo SNe ew rrr 0 (

PE

U Ci + Yo

CIE

! , , t [Formula 4]

I=p-0 a a aa

OL, tH—~C: oH 4 dra L , V

N/T ™ Tp 0 > [Formula 5] 0=p—0 — v=o po —0—{ a oe \ ~~ th ~~ tH 0

Er fr th fe 0 0

HCE

The brominated epoxy resins can be any brominated epoxy resins common in the art. For example, the brominated expoxy resin is preferably used in a mixture of one or two of brominated epoxy resins having a structure expressed by Formula 6 which are derived from a tetrabromobisphenol A having two or more epoxy groups per molecule, and brominated epoxy resins having a structure expressed by Formula 7. [Formula 6]

A Tk Ok Br Cup 8 [3] CHa OH cv pn-sgo{OHi-Do-ch reco BiG etff-0 Dee

CAH sr CH . CH} ' 1 "og : Cr) O a I-Qpocssci,

Chl

[Formula 7] ol)" ol! ol" ch. ch, cH. 5 5

CO CH <r CH +Q

Br Br Br 5 The maleimide resin, aromatic maleimide resin, maleimide compound, or polymaleimide compound can be any maleimide resin, aromatic maleimide resin, maleimide compound, or polymaleimide compound common in the art. Examples of maleimide resins, aromatic maleimide resins, maleimide compounds, and polymaleimide = compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4- methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, 1,3-bis (3-maleimide phenoxy) benzene, 1,3-bis (4-maleimide phenoxy) benzene, and polymers obtained by polymerizing any of these compounds with another compound. The maleimide resin can be an aromatic resin having two or more maleimide groups per molecule, or a polymerization adduct obtained by polymerizing an aromatic resin having two or more maleimide groups per molecule with a polyamine or aromatic polyamine. The polyamine or aromatic polyamine can be any polyamine or aromatic polyamine commonly used in the art. Specific examples of polyamines and aromatic polyamines include m-phenylenediamine, p- phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6- diaminopyridine, 4,4'-diaminodiphenyl methane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3-methyldiphenylether, 4,4'- diaminodiphenyl sulfide, 4,4'-aminobenzophenone, 4,4'-diaminodiphenyl sulfone, bis (4-aminophenyl) phenyl amine, m-xylene diamine, p-xylene diamine, 1,3-bis [4- aminophenoxy] benzene, 3-methyl-4,4'-diaminodiphenyl methane, 3,3'-diethyl-4,4'- diaminodiphenyl methane, 3,3'-dichloro-4,4'-diaminodiphenyl methane, 2,2'5,5'- tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis (3-methyl-4-amino-phenyl) propane, 2,2-bis (3-ethyl-4-amino-phenyl) propane, 2,2-bis (2,3-dichloro-4-amino-phenyl)

propane, bis (2,3-dimethyl-4-amino-phenyl) phenyl ethane, ethylenediamine, hexamethylene diamine, 2,2-bis (4-(4-aminophenoxy) phenyl) propane, and polymers obtained by polymerizing any of these compounds with another compound.

These polyamines and/or aromatic polyamines common in the art can be used alone or in combinations of two or more.

The phenoxy resins can be any phenoxy resin common in the art.

The phenoxy resin can be synthesized by reacting a bisphenol with a divalent epoxy resin.

The epoxy resin can be any epoxy resin common in the art and/or any one of the epoxy resins listed above.

The bisphenol can be any bisphenol common in the art.

Examples include bisphenol A, bisphenol F, bisphenol S,

tetrabromobisphenol A, or a bisphenol obtained from 4,4'-dihydroxybiphenyl, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), and quinones such as hydroquinone and naphthoquinone as adducts.

The linear polymers with a crosslinkable functional group can be any linear polymers with a crosslinkable functional group common in the art.

The linear polymers with a crosslinkable functional group preferably include a functional group contributing to the curing reaction of the epoxy resin such as a hydroxyl group or carboxyl group.

The linear polymers with a crosslinkable functional group are preferably soluble in organic solvents with a boiling point from 50°C to 200°C.

Specific examples of linear polymers with a crosslinkable functional group include polyvinyl acetal resins,

phenoxy resins, polyether sulfone resins, and polyamide-imide resins.

The crosslinking agent can be any crosslinking agent common in the art.

For example, a urethane resin can be used as a crosslinking agent.

The rubber resin can be any rubber resin common in the art.

Rubber resins as a concept contain a natural rubber and synthetic resin.

Examples of synthetic resins include styrene-butadiene rubbers,

butadiene rubbers, butyl rubbers, ethylene-propylene rubbers, acrylonitrile-butadiene rubbers, acrylic rubbers (acrylic acid ester copolymers), polybutadiene rubbers, and isoprene rubbers.

When the heat-resistance of the resin layer is to be ensured, the use of a synthetic resin having heat-resistant properties, such as a nitrile rubber, chloroprene rubber, silicon rubber, or urethane rubber is advantageous.

These rubber resins preferably include different functional groups on both ends in order to manufacture a copolymer from a reaction with an aromatic polyamide resin or a polyamide-imide resin.

The use of CTBN (carboxy group-terminated butadiene nitrile) is especially advantageous.

A carboxyl-modified acrylonitrile-butadiene rubber can form a crosslinked structure with an epoxy resin to improve the flexibility of the cured resin layer.

Examples of carboxyl-modified materials that can be used

' . , include carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), and carboxy-modified nitrile butadiene rubber (C-NBR). The polyamide-imide resin can be any polyamide-imide resin common in the art. Examples of polyamide-imide resins include resins obtained by heating trimellitic anhydride, benzophenone tetracarboxylic anhydride and bicycloalkenyl tolylenediisocyanate in a solvent such as N-methyl-2-pyrrolidone and/or N,N-dimethylacetamide; and resins obtained by heating trimellitic anhydride, diphenylmethane diisocyanate and butadiene rubber-carboxyl group-terminated acrylonitrile in a solvent such as N-methyl-2-pyrrolidone and/or N,N- dimethylacetamide. The rubber-modified polyamide-imide resins can be any rubber- modified polyamide-imide resins common in the art. A rubber-modified polyamide- imide resin can be obtained by reacting a polyamide-imide resin with a rubber resin.

Reacting a polyamide-imide resin with a rubber resin improves the flexibility of the polyamide-imide resin. In other words, reacting a polyamide-imide resin with a rubber resin partially substitutes the acid component of the polyamide-imide resin (such as cyclohexanedicarboxylic acid) with a rubber component. The polyamide-imide resin can be any polyamide-imide resin common in the art. The rubber resin can be any rubber resin common in the art or any rubber resin listed above. When a rubber- modified polyamide-imide resin is polymerized, the solvent used to dissolve the polyamide-imide resin and the rubbery resin can be dimethyl formamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, and y- butyrolactone. These solvents can be used alone or in mixtures of two or more. The phosphazene resin can be any phosphazene resin common in the art. A phosphazene resin is a resin containing a phosphazene having a double bond between the constituent elements phosphorus and nitrogen. A phosphazene resin can significantly improve flame retardancy due to the multiplier effect of the nitrogen and the phosphorus in the molecule. Unlike 9,10-dihydro-9-oxa-10-phospha phenanthrene-10- oxide derivatives, this remains stable in the resin and prevents migration. The fluororesin can be any fluororesin common in the art. Examples of fluororesins include PTFE (polytetrafluoroethylene (tetrafluorinated), PFA (tetrafluoroethylene- perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (4.6 fluorinated), ETFE tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (bifluorinated)), PCTFE (polychlorotrifluoroethylene (trifluorinated)), polyallyl sulfone, aromatic polysulfide, aromatic polyether, and

3 po “

CARRIER-ATTACHED COPPER FOIL

Technical Field

The present invention relates to carrier-attached copper foil. More specifically, the present invention relates to carrier-attached copper foil used as a material in printed wiring boards. . 5

Ci

A printed wiring board is usually manufactured by bonding an insulating” Ze substrate onto copper foil to obtain a copper-clad laminate, and then forming, a ee conductive pattern on the surface of the copper foil using etching. However, as electronic devices become smaller and demand for higher performance increases, components have been mounted more densely and higher frequency sigHals are more commonly used. As a result, a printed wiring board able to acdommodate finer conductive patterning (fine pitching), higher frequency signals and the like is required.

Copper foil able to accommodate fine pitching currently has a thickness of 9 pum or less, and further 5 um or less. However, such an ultra-thin copper foil has low mechanical strength and tends to tear and wrinkle when printed wiring boards are manufactured. Therefore, carrier-attached copper foil has been developed in which thick metal foil is used as a carrier, and an ultra-thin copper layer has been electrodeposited on the metal foil via a release layer. The surface of the ultra-thin copper layer is affixed to an insulating substrate, thermocompression bonding is performed, and the carrier is peeled off via the release layer. After a circuit pattern has been formed on the exposed ultra-thin copper layer using a resist, the ultra-thin copper layer is etched off using a sulfuric acid-hydrogen peroxide etchant to form a microcircuit (MSAP: modified semi-additive process).

This technique mainly requires the surface of the ultra-thin copper layer of the carrier-attached copper foil, which is the surface that is bonded to the resin, to have sufficient peeling strength between the ultra-thin copper layer and the resin substrate.

This peeling strength must be sufficiently maintained after high-temperature heating, wet processing, soldering, and chemical treatment and the like. One typical method of increasing the peeling strength between the ultra-thin copper layer and the resin substrate is to attach a large amount of roughening particles onto the surface of an fluororesins composed of at least one type of thermoplastic resin and a fluororesin mentioned above. The resin layer may also include a resin curing agent. The resin curing agent can be any resin curing agent common in the art. Specific examples of resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolac resins such as phenol novolac resins and cresol novolac resins, acid anhydrides such as phthalic anhydride, biphenyl phenol resins, and phenol alkyl resins. The resin layer can contain one or more type of resin curing agent. These curing resins are especially effective on epoxy resins. A specific example of a phenyl phenol resin is expressed by Formula 8. [Formula 8]

H H

© Oo

Ny ( Hy A \ :

A specific example of a phenol aralkyl-type phenol resin is expressed by

Formula 9. [Formula 9]

H H oO oO

Lf. A

G0 +0)

Js

The imidazoles can be any one common in the art. Examples include 2- undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl-4- methyl imidazole, 1-cyanoethyl-2-undecyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 2-phenyl-4,5-dihydroxy methyl imidazole, and 2-phenyl-4-methyl-5-hydroxymethyl imidazole. These can be used alone or in mixtures of two or more. Among these, imidazoles having a structure expressed by Formula 10 are especially preferred. Imidazoles having a structure expressed by Formula 10 produce a resin layer in a semicured state which has significantly better moisture resistance and long-term storage stability. Imidazoles have a catalytic action when epoxy resins are cured. In the initial stage of the curing process, it functions as a reaction initiator causing the epoxy resin to self-polymerize. [Formula 10]

H,C CH,OH

J

The amine resin curing agent can be any amine common in the art. Examples of amine resin curing agents include the polyamines and aromatic polyamines mentioned above, and amine adducts obtained by polycondensation of an aromatic polyamine or polyamide with an epoxy resin and polyvalent carboxylic acid. These can be used alone or in combinations of two or more. Preferred examples of amine curing agents include one or more compounds selected from among 4,4- diaminophenylene sulfone, 3,3'-diaminophenylene sulfone, 4,4-diaminodiphenyl, 2,2- bis [4-(4-aminophenoxy) phenyl] propane, and [4-(4-aminophenoxy) phenyl] sulfone.

The resin layer may contain a curing accelerator. The curing accelerator can be any curing accelerator common in the art. Examples of curing accelerators include tertiary amines, imidazoles, and urea-based curing accelerators. The resin layer may also include a reaction catalyst. The reaction catalyst may be any reaction catalyst common in the art. Examples of reaction catalysts include finely pulverized silica and antimony trioxide.

Polyvalent carboxylic anhydrides are preferably components contributing as a curing agent for epoxy resins. Preferred examples of polyvalent carboxylic anhydrides include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadic anhydride, and methyl nadic anhydride.

The thermoplastic resins may be thermoplastic resins having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin. The polyvinyl acetal resins may have a functional group polymerizable with an epoxy resin or maleimide compound other than an acid group or hydroxyl group. The polyvinyl acetal resins may include a carboxyl group, amino group, or unsaturated double bond introduced to the molecule. The aromatic polyamide resin polymers include those obtained by reacting an aromatic polyamide resin with a rubber resin.

Here, the aromatic polyamide resins include those obtained by polycondensation of an aromatic diamine and dicarboxylic acid. Examples of aromatic diamines include 4,4'- diaminodiphenyl methane, 3,3'-diaminodiphenyl sulfone, m-xylene diamine, and 3,3'- oxydianiline. Examples of dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and fumaric acid. The rubber resin reacted with the aromatic polyamide resin can be any rubber resin common in the art or any rubber resin listed above. The aromatic polyamide resin polymer is used to prevent damage caused by underetching using the etchant when the copper foil is etched after lamination on a copper-clad laminate.

The resin layer may be a resin layer obtained by successively forming a cured resin layer (that is, a resin layer that has been completely cured) and a semicured resin layer on the copper foil side (that is, the ultra-thin copper layer side of the carrier- attached copper foil). The cured resin layer can be composed of any resin component having a coefficient of thermal expansion from 0 ppm/°C to 25 ppm/°C, such as a polyimide resin, polyamide-imide resin, or a composite resin of these.

A semicured resin layer having a coefficient of thermal expansion from 0 ppm/°C to 50 ppm/°C after curing may be provided on top of the cured resin layer.

The coefficient of thermal expansion of the entire resin layer after the cured resin layer and semicured resin layer have been cured should be 40 ppm/°C or less. The cured resin layer should have a glass transition temperature of 300°C or more. The semicured resin layer may be formed using a maleimide resin or aromatic maleimide resin. The resin composition used to form the semicured resin layer preferably includes a maleimide resin, epoxy resin, and linear polymer with a crosslinkable functional group. The epoxy resin can be any epoxy resin common in the art or mentioned in the present specification. The maleimide resin, aromatic maleimide resin and linear polymer with a crosslinkable functional group can be any maleimide resin,

' . ‘ aromatic maleimide resin and linear polymer with a crosslinkable functional group common in the art, or any maleimide resin, aromatic maleimide resin and linear polymer with a crosslinkable functional group mentioned above.

When carrier-attached copper foil having a resin layer is provided for use in the manufacture of a three-dimensional molded printed wiring board, the cured resin layer is preferably a cured flexible macromolecular polymer layer. This macromolecular polymer layer is preferably made of a resin having a glass transition temperature of 150°C or more in order to withstand the solder mounting step.

Preferred examples of macromolecular polymers include polyamide resins, polyether sulfone resins, aramid resins, phenoxy resins, polyimide resins, polyvinyl acetal resins, and polyamide-imide resin. These can be used alone or in mixed resins of two or more.

The thickness of the macromolecular polymer layer is preferably from 3 ym to 10 um.

The macromolecular polymer layer preferably includes one or more type of resin selected from among epoxy resins, maleimide resins, phenol resins, and urethane resins. The semicured resin layer is preferably an epoxy resin composition with a thickness from 10 ym to 50 ym.

The epoxy resin composition preferably contains Component A through

Component E below.

Component A: One or more epoxy resins that have an epoxy equivalent of 200 or less and that are in liquid form at room temperature, selected from among bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol AD epoxy resins.

Component B: A highly heat-resistant epoxy resin.

Component C: A phosphorus-containing flame-retardant resin such as a phosphorus-containing epoxy resin, or a phosphazene resin. These can be used alone or in mixtures of two or more.

Component D: A rubber-modified polyamide-imide resin in which a liquid rubber component soluble in a solvent with a boiling point from 50°C to 200°C has been modified.

‘ .\ .

Component E: A resin curing agent.

Component B is a highly heat-resistant epoxy resin with a high glass transition point Tg. Preferred examples of highly heat-resistant epoxy resins include polyfunctional epoxy resins such as novolac epoxy resins, cresol novolac epoxy resins, phenol novolac epoxy resins, and naphthalene epoxy resins. The phosphorus- containing resin in Component C can be any phosphorus-containing resin mentioned above. The phosphazene resin in Component C can be any phosphazene resin mentioned above. The rubber-modified polyamide-imide resin in Component D can be any rubber-modified polyamide-imide resin mentioned above. The resin curing agent in Component E can be any resin curing agent mentioned above.

A solvent is added to the resin compositions mentioned above and used as a resin varnish to form a thermosetting resin layer that is the adhesive layer of the printed wiring board. The resin varnish can be prepared by adding a solvent to the resin composition to obtain a resin solid content from 30 wt% to 70 wt%, and the semicured resin film can be formed at a resin flow from 5% to 35% as measured in accordance with MIL-P-13949G in the MIL standards. The solvent can be any solvent common in the art or any solvent mentioned above.

In a resin layer having a first thermosetting resin layer from the copper foil side and a second thermosetting resin layer on the surface of the first thermosetting resin layer, the first thermosetting resin layer may be formed using a resin component that does not dissolve in the chemicals during the desmear step in the wiring board production process, and the second thermosetting resin layer may be formed using a resin component that does dissolve in the chemicals during the desmear step in the wiring board production process and can be removed in the washing step. The first thermosetting resin layer can be formed using a resin component made of a polyimide resin, polyether sulfone, polyphenylene oxide, or a mixture of two or more of these.

The second thermosetting resin layer can be formed using an epoxy resin component.

This resin layer is preferably of a thickness satisfying the condition Rz< t1< t2, where tl (um) is the thickness of the first thermosetting resin layer, Rz (um) is the surface roughness of the roughened surface of the carrier-attached copper foil, and t2 (um) is the thickness of the second thermosetting resin.

’, oy '

The resin layer may be a prepreg in which a skeleton material is impregnated with a resin. The resin impregnating the skeleton material is preferably a thermosetting resin. The prepreg may be any prepreg common in the art, or any prepreg used in the manufacture of printed wiring boards.

The skeleton material can be made of amide fibers, glass fibers, or wholly aromatic polyester fibers. The skeleton material is preferably unwoven cloth or woven cloth made of amide fibers, glass fibers, or wholly aromatic polyester fibers. The wholly aromatic polyester fibers are preferably wholly aromatic polyester fibers having a melting point of 300°C or higher. Wholly aromatic polyester fibers having a melting point of 300°C or higher are fibers manufactured using a so-called liquid crystal polymer. The main component of these liquid crystal polymers is a polymer of 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid. Because wholly aromatic polyester fibers have a low dielectric constant and a low dielectric loss tangent, they have superior performance as a constituent element of an electrical insulating layer, and can be used in the same way as glass fibers and aramid fibers. The fibers constituting the unwoven cloth or woven cloth are preferably subjected to treatment with a silane coupling agent to improve the wettability with the resin on the surface.

The silane coupling agent used here depends on the intended use, but can be any amino or epoxy-based silane coupling agent common in the art or any silane coupling agent mentioned above.

The prepreg may also be a prepreg in which a skeleton material such as unwoven cloth made of aramid fibers or glass fibers having a nominal thickness of 70 pm or less, or glass cloth having a nominal thickness of 30 ym or less is impregnated with a thermosetting resin. (For a Resin Layer Including a Dielectric (Dielectric Filler))

The resin layer may include a dielectric (dielectric filler). When one of the resin layers or resin compositions includes a dielectric (dielectric filler), it is used to form a capacitor layer and to increase the capacitance of the capacitor circuit.

Examples of dielectrics (dielectric fillers) include dielectric powders of a composite oxide with a Perovskite structure such as BaTiO; SrTiO;, Pb (Zr-Ti)O; (PZT),

PbLaTiO; PbLaZrO (PLZT), or SrBi;Ta,Oy (SBT).

The dielectric (dielectric filler) can be a powder. When the dielectric (dielectric filler) is a powder, the particle size of the dielectric (dielectric filler) has to be within a range from 0.01 ym to 3.0 ym, and preferably within a range from 0.02 pm to 2.0 um. Because a certain secondary aggregate is formed between powder particles, the particle size cannot be measured using indirect measuring methods in which the average particle size is inferred from measurements, such as the laser diffraction scattering particle size distribution measuring method or the BET method, because these methods are inaccurate. Instead, the average particle size is obtained by directly observing the dielectric (dielectric filler) under a scanning electron microscope (SEM), and analyzing SEM images. In the present specification, this average particle size is indicated by DIA. In the present specification, image analysis is performed on a dielectric (dielectric filler) powder observed under a scanning electron microscope (SEM) using an Asahi Engineering IP-1000PC, and the average particle size DIA is determined by a round particle analysis using an end threshold of 10, and a degree of overlap of 20. In the present embodiment, a carrier-attached copper foil can be provided which has a resin layer containing a dielectric to form a capacitor circuit layer having a low dielectric loss tangent in which the adhesion of the resin layer containing the dielectric to the inner layer circuit surface of the inner layer core material has been improved.

The resin, resin composition and/or compound in the resin layer described above can be a resin solution (resin varnish) in which the resin, resin composition and/or compound has been dissolved in a solvent such as methyl ethyl ketone (MEK), cyclopentanone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethyl formamide, dimethyl acetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N,N- dimethyl acetamide, or N,N-dimethyl formamide. This is applied to the ultra-thin copper layer, heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling agent layer using the roll coating method. If necessary, the resin varnish can be heated and dried to remove the solvent and produce a Stage B resin.

The drying process may be performed in a hot air drying furnace, and the drying temperate may be from 100 to 250°C, preferably from 130 to 200°C. The composition of the resin layer may be dissolved in a solvent to obtain a resin liquid with a resin solid content from 3 wt% to 70 wt%, preferably from 3 wt% to 60 wt%, more preferably from 10 wt% to 40 wt%, and more preferably from 25 wt% to 40 wt%. The composition may be dissolved using a mixed solvent of methyl ethyl ketone and cyclopentanone. At this stage, this is most preferred from an environmental standpoint.

The solvent is preferably a solvent having a boiling point in a range from 50°C to 200°C. A semicured resin film can be formed at a resin flow from 5% to 35% as measured in accordance with MIL-P-13949G in the MIL standards. In the present specification, the resin flow is obtained in accordance with MIL-P-13949G in the MIL standards by taking four 10 cm x 10 cm samples from resin-attached copper foil having a resin thickness of 55 um, stacking the four samples (to make a laminate), bonding the laminate at a press temperature of 171°C, press pressure of 14 kgf/cm? and press time of 10 minutes. The resin flow is the value calculated from the outflow resin weight measurement using Equation 1. [Equation 1]

Resin Flow (%) = __ Outflow Resin Wt X100 (Laminate Wt) - (Copper Foil Wt)

The carrier-attached copper foil including a resin layer (the resin-coated carrier-attached copper foil) can be used by applying the resin layer to the substrate, subjecting the laminate to thermocompression bonding to thermocure the resin layer, peeling off the carrier to expose the ultra-thin copper layer (the surface on the intermediate layer side of the ultra-thin copper layer is naturally exposed), and forming the desired wiring pattern in the ultra-thin copper layer.

When resin-coated carrier-attached copper foil is used, the number of prepregs used in the manufacture of a multiple layer printed wiring board can be reduced. In addition, a copper-clad laminate can even be manufactured without using any prepregs at all because the thickness of the resin layer is sufficient to ensure interlayer insulation. At this time, the surface of the substrate can be undercoated using an insulating resin to further improve the smoothness of the surface.

When prepregs are not used, material costs associated with the prepregs can be reduced, and the lamination step can be simplified. This confers definite economic advantages. In addition, multilayer printed wiring boards manufactured without prepregs are thinner, and ultra-thin multilayer printed wiring boards can be manufactured with a per layer thickness of 100 ym or less. The thickness of the resin layer is preferably from 0.1 to 120 um.

When the thickness of the resin layer is less than 0.1 um, the adhesive strength of the resin layer may become lower, and interlayer insulation between inner layer circuits may not be ensured when resin-coated carrier-attached copper foil is laminated in inner layers without interposed prepregs. When the thickness of the resin layer is greater than 120 um, it may be difficult to form a resin layer with the intended thickness in a single application, and extra material and manufacturing steps have to be used. This is not advantageous from an economic standpoint. When carrier- attached copper foil with a resin layer is used in the manufacture of an ultra-thin multilayer printed wiring board, the thickness of the resin layer is from 0.1 ym to 5 pm, preferably from 0.5 um to 5 pm, and more preferably from 1 ym to 5 um.

However, a multilayer printed wiring board on the thinner side is preferred. When the resin layer includes a dielectric, the thickness of the resin layer is from 0.1 ym to 50 pm, preferably from 0.5 ym to 25 um, and more preferably from 1.0 ym to 15 um.

The overall thickness of the cured resin layer and semicured resin layer is preferably from 0.1 gum to 120 um, more preferably from 5 um to 120 ym, more preferably from 10 um to 120 um, and more preferably from 10 um to 60 pm. The thickness of the cured resin layer is preferably from 2 yum to 30 um, more preferably from 3 um to 30 pm, and even more preferably from 5 to 20 um. The thickness of the semicured resin layer is preferably from 3 pum to 55 pm, more preferably from 7 pm to 55 pm, and even more preferably from 15 to 115 um. When the overall thickness of the resin layer exceeds 120 um, it may be difficult to manufacture an ultra-thin multilayer printed wiring board. When the overall thickness is less than 5 um, an ultra-thin multilayer printed wiring board is easy to manufacture, but the resin layers forming the insulating layers between inner layer circuits is too thin, and the insulating properties between inner layer circuits may tend to be unstable. When the thickness of the cured resin layer is less than 2 um, the surface roughness of the copper foil may have to be carefully taken into account. When the thickness of the cured resin layer is greater than 20 um, the effect of the cured resin layer may not increase any further, and the overall thickness of the insulating layers becomes larger.

When the thickness of the resin layer is from 0.1 ym to 5 um, a heat-resistant layer, anticorrosive layer, chromate treatment layer, and/or silane coupling treatment layer is formed on top of the ultra-thin copper layer, and the resin layer is preferably formed on top of the heat-resistant layer, anticorrosive layer, chromate treatment layer, and/or silane coupling treatment layer in order to improve adhesion between the resin layer and the carrier-attached copper foil. The thickness of the resin layer is the average value of thickness measurements made at ten points in a cross-section of the layer.

In another embodiment of resin-coated carrier-attached copper foil, the ultra- thin copper foil, heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer is coated with a resin layer, and the carrier is peeled off in a semicured state to obtain carrier-free resin-coated copper foil. < 6. Carrier-Attached Copper Foil >

The carrier-attached copper foil manufactured in the manner described above includes a copper foil carrier, a release layer laminated on the copper foil carrier, an ultra-thin copper layer laminated on the release layer, and an optional resin layer. The uses of carrier-attached copper foil per se are well known in the art. For example, a printed wiring board can be manufactured by thermocompression-bonding the surface of the ultra-thin copper layer on an insulating substrate made of a paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth/paper composite substrate epoxy resin, glass cloth/glass non-woven composite substrate epoxy resin, glass cloth substrate epoxy resin, polyester film or polyimide film, peeling off the carrier to obtain a copper-clad laminate, and then etching the ultra-thin copper layer bonded to the insulating substrate to obtain the desired conductive pattern. Electric components can then be mounted on the printed wiring board to obtain a printed circuit board. The following are various examples of the manufacture of printed wiring boards using the carrier-attached copper foil of the present invention.

One embodiment of the method for manufacturing a printed wiring board of the present invention includes the steps of: preparing a carrier-attached copper foil according to the present invention and an insulating substrate; laminating the carrier- attached copper foil and the insulating substrate; peeling off the carrier of the carrier- attached copper foil, after the carrier-attached copper foil and insulating substrate have been laminated so that the ultra-thin copper layer faces the insulating substrate,

ultra-thin copper layer whose surface profile (unevenness, roughness) has been increased.

However, when such an ultra-thin copper layer whose surface profile (unevenness, roughness) has been increased is used for manufacturing a semiconductor package board which requires finer circuit patterning than other printed wiring boards, some of the copper particles left over from the circuit etching process cause problems such as defective insulation between circuit patterns.

Therefore, in WO 2004/005588 (Patent Document 1), an attempt has been made to use carrier-attached copper foil whose surface on the ultra-thin copper layer side has not been roughened as a carrier-attached copper foil for microcircuitry such as in semiconductor package boards. However, the adhesion (peeling strength) between the ultra-thin copper layer without roughening and the resin tends to be poorer than that of ordinary printed wiring board copper foil because of its low profile (unevenness, coarseness, roughness). Therefore, further improvements to carrier- attached copper foil are required.

JP2007-007937A (Patent Document 2) and JP2010-006071A (Patent

Document 3) describe the application of a Ni layer and/or Ni alloy layer, the application of a chromate treatment layer, the application of a Cr layer and/or Cr alloy layer, the application of a Ni layer and a chromate treatment layer, and the application of a Ni layer and a Cr layer on the surface of carrier-attached ultra-thin copper foil to bebrought into contact with (and bonded to) a polyimide resin board. These surface- treatment layers provide the desired bonding strength between a polyimide resin board and carrier-attached ultra-thin copper foil while either eliminating or reducing (miniaturizing) the extent of roughening treatment. These documents also describe a surface treatment using a silane coupling agent, and anticorrosive treatment.

Prior Art Literature

Patent Literature

Patent Document 1: WO 2004/005588

Patent Document 2: JP2007-007937A

Patent Document 3: JP2010-006071A to form a copper-clad laminate; and then forming a circuit using the semi-additive method, modified semi-additive method, partly additive method, or subtractive method. The insulating substrate can include inner layer circuits.

In the present invention, the semi-additive method is a method used to form a conductive pattern by performing thin electroless plating on the insulating substrate or copper foil seed layer, forming a pattern, and then electroplating and etching the pattern.

Therefore, one embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier- attached copper foil and insulating substrate have been laminated; entirely removing the ultra-thin copper layer exposed by peeling off the carrier using a method such as etching with acid or other corrosive solutions or plasma; providing a through-hole and/or blind via in the insulating substrate and also in the resin layer if present exposed by the removal of the ultra-thin copper layer by etching; performing desmear treatment on the region including the through-hole and/or blind via; providing an electroless plating layer on the resin and in the region including the through-hole and/or blind via; providing a plating resist on top of the electroless plating layer; exposing the plating resist and removing the plating resist in the region where a circuit is to be formed; providing an electroplated layer in the region where the plating resist has been removed and the circuit is to be formed; removing the plating resist; and removing the electroless plating layer using flush etching in the regions other than the region where the circuit is to be formed.

Another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier-attached copper foil and insulating substrate have been laminated; entirely removing the ultra-thin copper layer exposed by peeling off the carrier using a method such as etching with acid or other corrosive solutions or plasma; providing an electroless plating layer on the surface of the insulating substrate or the resin layer if present exposed by removing the ultra-thin copper layer by etching; providing a plating resist on top of the electroless plating layer; exposing the plating resist and removing the plating resist in the region where the circuit is to be formed; providing an electroplated layer in the region where the plating resist has been removed and the circuit is to be formed, removing the plating resist; and removing the electroless plating layer and the ultra- thin copper layer using flush etching in the regions other than the region where the circuit is formed.

In the present invention, the modified semi-additive method is a method used to form a circuit on an insulating layer by laminating metal foil on the insulating layer, protecting the non-circuit portions with a plating resist, thickening the copper on the circuit portions using electroplating before removing the resist, and then removing the metal foil outside of the circuit portions using (flush) etching.

Therefore, one embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier- attached copper foil and insulating substrate have been laminated; providing a through-hole and/or blind via in the ultra-thin copper layer exposed peeling off the carrier and in the insulating substrate; performing desmear treatment on the region including the through-hole and/or blind via; providing an electroless plating layer in the region including the through-hole and/or blind via; providing a plating resist on the surface of the ultra-thin copper layer exposed by peeling off the carrier; forming a circuit using electroplating after the plating resist has been provided; removing the plating resist; and removing by flush etching the ultra-thin copper layer exposed by the removal of the plating resist.

Another embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier- attached copper foil and insulating substrate have been laminated; providing a plating resist on the ultra-thin copper layer exposed by peeling off the carrier; exposing the plating resist and then removing the plating resist in the region where the circuit is to be formed; providing an electroplating layer in the region where the plating resist has been removed and the circuit is to be formed; removing the plating resist; and removing by flush etching the ultra-thin copper layer in the regions other than the region where the circuit is formed.

In the present invention, the partly additive method is a method used to manufacture a printed wiring board by applying a catalytic core to a substrate including a conductive layer and, if necessary, to a substrate in which a through-hole or via hole has been formed, etching the board to form a conductive circuit, and performing electroless plating for thickening on the conductive circuit, the through- hole or via hole after a solder resist or plating resist has been provided as necessary.

Therefore, one embodiment of the method for manufacturing a printed wiring board according to the present invention using the partly semi-additive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier- attached copper foil and insulating substrate have been laminated; providing a through-hole and/or blind via in the ultra-thin copper layer exposed by peeling off the carrier and in the insulating substrate; performing desmear treatment on the region including the through-hole and/or blind via; providing a catalytic core in the region including the through-hole and/or blind via; providing an etching resist on the surface of the ultra-thin copper layer exposed by peeling off the carrier; exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the catalytic core using a method such as etching with acid or other corrosive solutions or plasma to form a circuit; removing the etching resist; providing a solder resist or plating resist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalytic core using a method such as etching with acid or other corrosive solutions or plasma; and providing an electroless plating layer in the regions not provided with the solder resist or plating resist.

In the present invention, the subtractive method is a method used to form a conductive pattern by selectively removing unneeded portions of the copper foil on a copper-clad laminate by etching.

Therefore, one embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier- attached copper foil and insulating substrate have been laminated; providing a through-hole and/or blind via in the ultra-thin copper layer exposed by peeling off the carrier and in the insulating substrate; performing desmear treatment on the region including the through-hole and/or blind via; providing an electroless plating layer in the region including the through-hole and/or blind via; providing an electroplating layer on the surface of the electroless plating layer; providing an etching resist on the surface of the electroplating layer and/or ultra-thin copper layer; exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer, the electroless plating layer, and the electroplating layer using a method such as etching with acid or other corrosive solutions or plasma to form a circuit; and removing the etching resist.

Another embodiment of the method for manufacturing a printed wiring board according to the present invention using the subtractive method includes the steps of: preparing a carrier-attached copper foil of the present invention and an insulating substrate; laminating the carrier-attached copper foil and insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier-attached copper foil and insulating substrate have been laminated; providing a through-hole and/or blind via in the ultra-thin copper layer exposed by peeling off the carrier and in the insulating substrate; performing desmear treatment on the region including the through-hole and/or blind via; providing an electroless plating layer in the region including the through-hole and/or blind via; providing a mask on the surface of the electroless plating layer; providing an electroplating layer on the surface of the electroless layer not including the formed mask; providing an etching resist on the surface of the electroplating layer and/or the ultra-thin copper layer; exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the electroless plating layer using a method such as etching with acid or another corrosive solution or plasma to form a circuit; and removing the etching resist.

The steps of providing a through-hole and/or blind via, and conducting the subsequent desmear treatment do not have to be performed.

The following is a detailed description with reference to the drawings of a specific example of a method for manufacturing a printed wiring board using carrier- attached copper foil according to the present invention. In this example, the carrier- attached copper foil has an ultra-thin copper layer whose surface has been roughened.

The present invention, however, is not limited to this example. For example, the following method for manufacturing a printed wiring board can use carrier-attached copper foil having an ultra-thin copper layer whose surface has not been roughened.

First, as shown in FIG. 2 (A), carrier-attached copper foil (the first layer) having an ultra-thin copper layer whose surface has a roughening layer is prepared. Next, as shown in FIG. 2 (B), a resist is applied to the roughening layer of the ultra-thin copper layer, the resist is exposed and developed, and the resist is etched to the desired shape.

Next, as shown in FIG. 2 (C), plating for a circuit is formed, and the resist is removed to form a circuit plating with the desired shape. Next, as shown in FIG. 3 (D), embedding resin is provided on the ultra-thin copper layer to cover the circuit plating (so as to embed the circuit plating) so that a resin layer is formed, and another sheet of carrier-attached copper foil (the second layer) is bonded to the ultra-thin copper layer side. Next, as shown in FIG. 3 (E), the carrier is peeled off the second carrier-attached copper foil. Next, as shown in FIG. 3 (F), a laser hole is formed at a predetermined location in the resin layer to expose the circuit plating and form a blind via. Next, as shown in FIG. 4 (G), the blind via is filled with copper to form a via fill. Next, as shown in FIG. 4 (H), a circuit plating is formed on the via fill in the same manner as

FIG. 2 (B) and FIG. 2 (C). Next, as shown in FIG. 4 (I), the carrier is peeled off the first carrier-attached copper foil. Next, as shown in FIG. 5 (J), the ultra-thin copper layer is removed from both surfaces using flush etching to expose the surface of the circuit plating inside the resin layer. Next, as shown in FIG. 5 (K), a bump is formed on the circuit plating inside the resin layer, and a copper pillar is formed on top of the solder. In this way, a printed wiring board is created using carrier-attached copper foil of the present invention.

The other sheet of carrier-attached copper foil (the second layer) can be carrier-attached copper foil of the present invention, carrier-attached copper foil of the prior art, or ordinary copper foil. One or more layers of circuitry can be formed on the second layer circuitry shown in FIG. 4-H using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

The carrier-attached copper foil used in the first layer may have a substrate on the carrier side of the carrier-attached copper foil. The use of a substrate or resin layer supports the carrier-attached copper foil used in the first layer and prevents wrinkling.

This improves productivity. Any kind of substrate can be used as long as it is effective to support the carrier-attached copper foil used in the first layer. This substrate can be a carrier, prepreg or resin layer described in the present specification, or any carrier, prepreg, resin layer, metal sheet, metal foil, inorganic compound sheet, inorganic compound foil, organic compound sheet, or organic compound foil common in the art.

There are no particular restrictions on the time at which the substrate is formed on the carrier surface. However, it has to be formed before the carrier is peeled off.

Preferably, it is formed before the resin layer is formed on the ultra-thin copper layer side of the carrier-attached copper foil. More preferably, it is formed before a circuit is formed on the ultra-thin copper layer side of the carrier-attached copper foil.

The carrier-attached copper foil of the present invention is preferably controlled so that the color difference on the surface of the ultra-thin copper layer satisfies (1) below. In the present invention, the “the color difference on the surface of the ultra-thin copper layer” means the color difference of the surface of the ultra-thin copper layer, or the color difference of the surface of a surface-treated layer subjected to various surface treatments such as roughening. In other words, the carrier-attached copper foil of the present invention is preferably controlled so that the color difference of the surface of the ultra-thin copper layer, roughening layer, heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling layer satisfies (1) below. (1) The color difference AE*ab of the surface of the ultra-thin copper layer, roughening layer, heat-resistant layer, anticorrosive layer, chromate treatment layer, orsilane coupling layer is equal to or greater than 45 in accordance with JIS Z 8730.

Here, color differences AL, Aa, Ab are comprehensive indices expressed using the L*a*b color system based on JIS Z 8730. Each measurement is taken using a color-difference meter and takes black/white, red/green, and yellow/blue into account.

AL indicates black/white, Aa indicates red/green, and Ab indicates yellow/blue.

AE*ab is represented by the following equation using these color differences. [Equation 2]

AE*ab=V/A L*+ A a*+ A b?

The color difference can be adjusted by increasing the current density during ultra-thin copper layer formation, reducing the copper concentration in the plating bath, and increasing the linear flow rate of the plating bath. The color difference can also be adjusted by roughening the surface of the ultra-thin copper layer to form a roughening layer. When a roughening layer is provided, the adjustment may be made by using an electrolytic solution containing at least one element selected from among copper, nickel, cobalt, tungsten, and molybdenum, increasing the current density (for example, 40-60 A/dm?), and shortening the treatment time (for example, 0.1-1.3 seconds). When a roughening layer is not provided on the surface of the ultra-thin copper layer, the adjustment may be achieved by forming a Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the ultra-thin copper layer, heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer using a plating bath containing Ni and other elements in which Ni concentration is at least twice as high as the concentration of the other elements at a lower current density (0.1-1.3 A/dm?) for alonger time (20-40 seconds) than conventional processes.

If the color difference AE*ab of the surface of the ultra-thin copper layer is equal to or greater than 45 in accordance with JIS Z 8730, the contrast between the ultra-thin copper layer and the circuity is clearer, resulting in better visibility and more precise circuit alignment when a circuit is formed on the surface of the ultra-thin copper layer of the carrier-attached copper foil, for example. The color difference

AE*ab of the surface of the ultra-thin copper layer is preferably equal to or greater than 50, more preferably equal to or greater than 55, and even more preferably equal to or greater than 60 in accordance with JIS Z 8730.

‘ ,

When the color difference on the surface of the ultra-thin copper layer, heat- resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer is controlled in the manner described above, the contrast with the circuit plating is clearer, and visibility is better. As a result, the circuit plating can be formed at the desired locations more precisely in the manufacturing step for the printed wiring board shown in FIG. 2 (C) for instance. Furthermore, because the circuit plating is embedded in the resin layer in the manufacturing method for a printed wiring board described above, the circuit plating is protected by the resin layer during removal of the ultra-thin copper layer using flush etching as shown in FIG. 5 (J) for instance, its shape is retained, and thus microcircuitry is more easily formed.

Furthermore, because the circuit plating is protected by the resin layer, anti-migration properties are also improved, and conduction between wiring in the circuitry is favorably suppressed. In this way, microcircuitry is more easily formed. When the ultra-thin copper layer is removed using flush etching as shown in FIG. 5 (J) and FIG. 5 (K), the exposed surface of the circuit plating is recessed in the resin layer.

Therefore, a bump on the circuit plating and a copper pillar on the bump are more easily formed, respectively. This improves manufacturing efficiency.

The embedding resin can be any resin or prepreg common in the art. Examples include BT (bismaleimide triazine) resins, prepregs of glass cloth impregnated with

BT resins, or ABF or ABF film from Ajinomoto Fine-Techno Co., Ltd. The embedding resin can also be any resin layer, resin, and/or prepreg mentioned in the present specification.

Examples

The following is a more detailed example of the present invention with reference to examples of the present invention. However, the present invention is not in any way limited to these examples. 1. Manufacture of Carrier-Attached Copper Foil < Example 1 >

The copper foil carrier was prepared using long, 35 pm-thick electrolytic copper foil (JTC from JX Nippon Mining & Metals Corporation.). An Ni layer was formed by electroplating 4,000 pig/dm’ of nickel on the shiny surface of the copper foil on a continuous roll-to-roll plating line under the following conditions.

* Ni Layer

Nickel Sulfate: 250-300 g/L

Nickel Chloride: 35-45 g/L

Nickel Acetate: 10-20 g/L

Trisodium Citrate: 15-30 g/L

Brightener: Saccharin, butynediol, etc.

Sodium Dodecyl Sulfate: 30-100 ppm pH: 4-6

Bath Temperature: 50-70°C

Current Density: 3-15 A/dm”

After washing the foil with water and acid, electrolytic chromate treatment was performed on the continuous roll-to-roll plating line to form a 11 pg/dm? Cr layer on the Ni layer under the following conditions. - Electrolytic Chromate Treatment

Liquid Composition: Potassium Dichromate 1-10 g/L, Zinc 0-5 g/L pH: 3-4

Liquid Temperature: 50-60°C

Current Density: 0.1-2.6 A/dm?

Coulombs: 0.5-30 As/dm’

Next, a 3 um-thick ultra-thin copper layer was electroplated on top of the Cr layer on the continuous roll-to-roll plating line under the following conditions to complete the carrier-attached copper foil. In this example, carrier-attached copper foils were also manufactured with ultra-thin copper layers of 2, 5, and 10 um, and these were evaluated in the same manner as the example having an ultra-thin copper layer of 3 um. The results were the same regardless of the thickness. - Ultra-Thin Copper Layer

Copper Concentration: 30-120 g/L

H,SO4 Concentration: 20-120 g/L

Electrolyte Temperature: 20-80°C

Current Density: 10-100 A/dm?

Next, the first roughening treatment, the second roughening treatment, the anticorrosive treatment, the chromate treatment, and the silane coupling treatment described below were performed in this order. - Roughening Treatment 1 (Liquid Composition 1)

Cu: 10-30 g/L

H,SO4: 10-150 g/L

W: 0-50 mg/L.

Sodium Dodecyl Sulfate: 0-50 mg/L

As: 0-200 mg/L (Electroplating Conditions 1)

Temperature: 30-70°C

Current Density: 25-110 A/dm?

Roughening Coulombs: 50-500 As/dm’

Plating Time: 0.5-20 seconds - Roughening Treatment 2 (Liquid Composition 2)

Cu: 20-80 g/L

H,S04: 50-200 g/L (Electroplating Conditions 2)

Temperature: 30-70°C

Current Density: 5-50 A/dm”

Roughening Coulombs: 50-300 As/dm’

Plating Time: 1-60 seconds + Anticorrosive Treatment (Liquid Composition)

NaOH: 40-200 g/L

NaCN: 70-250 g/L

CuCN: 50-200 g/L

Zn(CN),: 2-100 g/L

As03: 0.01-1 g/L (Liquid Temperature)

{ x v

Summary of the Invention

Problem to be Solved by the Invention

In the development of carrier-attached copper foil, emphasis has been placed on maintaining sufficient peeling strength between the ultra-thin copper layer and the resin substrate. As a result, not enough research has been conducted on fine pitching, and there is still room for improvement. Therefore, it is an object of the present invention to provide carrier-attached copper foil suitable for fine pitching. More specifically, it is an object of the present invention to provide carrier-attached copper foil with which wiring can be formed which is finer than L/S = 20 pm/20 um, which is considered to be the upper limit for the formation of wiring using MSAP.

Means for Solving the Problem

The present inventors conducted extensive research in order to achieve this object, and discovered that a roughened surface of low, uniform roughness could be formed by performing low roughening of the surface of the ultra-thin copper layer and forming fine roughening particles on the ultra-thin copper layer. The present inventors then discovered that this carrier-attached copper foil was especially effective in the formation of fine pitching.

The present invention is a product of these discoveries. One aspect of the present invention is carrier-attached copper foil including a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, the ultra-thin copper layer being roughened, and the Rz of the surface of the ultra-thin copper layer being 1.6 um or less when measured using anon-contact roughness meter.

Another aspect of the present invention is a carrier-attached copper foil including a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, the ultra-thin copper layer being roughened, and the Ra of the surface of the ultra-thin copper layer being 0.3 um or less when measured using a non-contact roughness meter.

Yet another aspect of the present invention is a carrier-attached copper foil including a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, the ultra-thin copper layer

40-90°C (Current Conditions)

Current Density: 1-50 A/dm’

Plating Time: 1-20 seconds - Chromate Treatment

K,Cr,07 (Na,Cr,05 or CrO3): 2-10 g/L

NaOH or KOH: 10-50 g/L

ZnOH or ZnSO4 7TH,0: 0.05-10 g/L pH: 7-13

Bath Temperature: 20-80°C

Current Density: 0.05-5 A/dm?

Time: 5-30 seconds - Silane Coupling Treatment

From 0.1 vol% to 0.3 vol% of 3-glycidoxypropyl trimethoxysilane aqueous solution was spray-applied, and heat-dried from 0.1 to 10 seconds in air from 100 to 200°C. < Example 2 >

After forming an ultra-thin copper layer on a copper foil carrier under the same conditions as those in Example 1, the first roughening treatment, the second roughening treatment, the anticorrosive treatment, the chromate treatment, and the silane coupling treatment described below were performed in this order. The thickness of the ultra-thin copper foil was 3 pm. - Roughening Treatment 1

Liquid Composition: Copper 10-20 g/L, Sulfuric Acid 50-100 g/L

Liquid Temperature: 25-50°C

Current Density: 1-58 A/dm?

Coulombs: 4-81As/dm’ - Roughening Treatment 2

Liquid Composition: Copper 10-20 g/L, Nickel 5-15 g/L, Cobalt 5-15 g/L pH: 2-3

Liquid Temperature: 30-50°C

Current Density: 24-50 A/dm’

Coulombs: 34-48 As/dm’ + Anticorrosive Treatment

Liquid Composition: Nickel 5-20 g/L, Cobalt 1-8 g/L pH: 2-3

Liquid Temperature: 40-60°C

Current Density: 5-20 A/dm*

Coulombs: 10-20 As/dm’ - Chromate Treatment

Liquid Composition: Potassium Dichromate 1-10 g/L, Zinc 0-5 g/L pH: 3-4

Liquid Temperature: 50-60°C

Current Density: 0-2 A/dm’ (electroless chromate treatment can be also performed due to immersion chromate treatment)

Coulombs: 0-2As/dm? (electroless chromate treatment can be also performed due to immersion chromate treatment) - Silane Coupling Treatment

Application of a diaminosilane aqueous solution (diaminosilane concentration: 0.1-0.5 wt%) < Example 3 >

After forming an ultra-thin copper layer on a copper foil carrier under the same conditions as those in Example 1, the first roughening treatment, the second roughening treatment, the anticorrosive treatment, the chromate treatment, and the silane coupling treatment described below were performed in this order. The thickness of the ultra-thin copper foil was 3 yum. - Roughening Treatment 1 (Liquid Composition 1)

a vo '

Cu: 10-30 g/L

H,SO4: 10-150 g/L

As: 0-200 mg/L (Electroplating Conditions 1)

Temperature: 30-70°C

Current Density: 25-110 A/dm’

Roughening Coulombs: 50-500 As/dm’

Plating Time: 0.5-20 seconds - Roughening Treatment 2 (Liquid Composition 2)

Cu: 20-80 g/L

H,S04: 50-200 g/L (Electroplating Conditions 2)

Temperature: 30-70°C

Current Density: 5-50 A/dm’

Roughening Coulombs: 50-300 As/dm®

Plating Time: 1-60 seconds - Anticorrosive Treatment (Liquid Composition )

NaOH: 40-200 g/L

NaCN: 70-250 g/L

CuCN: 50-200 g/L

Zn(CN),: 2-100 g/L

As;0;5: 0.01-1 g/L (Liquid Temperature) 40-90°C (Current Conditions)

Current Density: 1-50 A/dm?

Plating Time: 1-20 seconds - Chromate Treatment

K>Cr;,07 (Na;Cr07 or CrOs): 2-10 g/L

NaOH or KOH: 10-50 g/L fo bo ,

ZnOH or ZnSO4 7TH,0: 0.05-10 g/L pH: 7-13

Bath Temperature: 20-80°C

Current Density: 0.05-5 A/dm”

Time: 5-30 seconds + Silane Coupling Treatment

From 0.1 vol% to 0.3 vol% of 3-glycidoxypropyl trimethoxysilane aqueous solution was spray-applied, and heat-dried from 0.1 to 10 seconds in air from 100 to 200°C. < Example 4 >

After forming a Ni layer and a Cr layer on a copper foil carrier under the same conditions as those in Example 1, a 3 um-thick ultra-thin copper layer was electroplated on the Cr layer on the roll-to-roll continuous plating line to complete the carrier-attached copper foil. In this example, carrier-attached copper foils were also manufactured with ultra-thin copper layers of 2, 5, and 10 um, and these were evaluated in the same manner as the example having an ultra-thin copper layer of 3 pm. The results were the same regardless of the thickness. + Ultra-Thin Copper Layer

Copper Concentration: 30-120 g/L

H,SO4 Concentration: 20-120 g/L

Bis (3-Sulfopropyl) Disulfide Concentration: 10-100 ppm

Tertiary Amine Compound: 10-100 ppm

Chlorine: 10-100 ppm

Electrolyte Temperature: 20-80°C

Current Density: 10-100 A/dm?

. }

The following compound was used as the tertiary amine compound. [Formula 11]

P R

1

CHy=0-CH,=CH-CH,-N ?

CH-0-CH,-CH-CH,~ NR

OH Re

CHy=0-CH,=CH=-CH,=N{_ 1

OH

(In this chemical formula, R; and R; represent any group selected from among a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group. In this example, R; and

R; are both be a methyl group.)

This compound can be obtained by mixing together specific amounts of

Denacol Ex-314 from Nagase Chemtex Co., Ltd. and dimethyl amine, and reacting the mixture for three hours at 60°C.

After forming the ultra-thin copper layer on the copper foil carrier, the first roughening treatment, the second roughening treatment, the anticorrosive treatment, the chromate treatment, and the silane coupling treatment described below were performed in this order. - Roughening Treatment 1

Liquid Composition: Copper 10-20 g/L, Sulfuric Acid 50-100 g/L

Liquid Temperature: 25-50°C

Current Density: 1-58 A/dm’

Coulombs: 4-81As/dm* - Roughening Treatment 2

Liquid Composition: Copper 10-20 g/L, Nickel 5-15 g/L, Cobalt 5-15 g/L pH: 2-3

Liquid Temperature: 30-50°C

Current Density: 24-50 A/dm?

* i '

Coulombs: 34-48 As/dm’ - Anticorrosive Treatment

Liquid Composition: Nickel 5-20 g/L, Cobalt 1-8 g/L pH: 2-3

Liquid Temperature: 40-60°C

Current Density: 5-20 A/dm*

Coulombs: 10-20 As/dm* + Chromate Treatment

Liquid Composition: Potassium Dichromate 1-10 g/L, Zinc 0-5 g/L pH: 3-4

Liquid Temperature: 50-60°C

Current Density: 0-2 A/dm” (electroless chromate treatment can be also performed due to immersion chromate treatment)

Coulombs: 0-2As/dm’ (electroless chromate treatment can be also performed due to immersion chromate treatment) - Silane Coupling Treatment

Application of a diaminosilane aqueous solution (diaminosilane concentration: 0.1-0.5 wt%) < Example 5 >

After forming a Ni layer and a Cr layer on a copper foil carrier under the same conditions as those in Example 1, a 3 um-thick ultra-thin copper layer was electroplated on the Cr layer on the roll-to-roll continuous plating line to complete the carrier-attached copper foil. In this example, carrier-attached copper foils were also manufactured with ultra-thin copper layers of 2, 5, and 10 pm, and these were evaluated in the same manner as the example having an ultra-thin copper layer of 3 pm. The results were the same regardless of the thickness. - Ultra-Thin Copper Layer

Copper Concentration: 30-120 g/L

H,S0, Concentration: 20-120 g/L

Bis (3-Sulfopropyl) Disulfide Concentration: 10-100 ppm

Tertiary Amine Compound: 10-100 ppm

Chlorine: 10-100 ppm

Electrolyte Temperature: 20-80°C

Current Density: 10-100 A/dm?

The following compound was used as the tertiary amine compound. [Formula 12]

OH

AR 1

CHy=0-CH,=CH-CH,=N

CH-0-CH,~CH-CH,~ NR

N\R

OH XR

CHy=0-CH,~CH=-CH,-N{_

OH

(In this chemical formula, R; and R; represent any group selected from among a hydroxyalkyl group, an ether group, an aryl group, an aromatic-substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group. In this example, R; and

R, were both be a methyl group.)

This compound can be obtained by mixing together specific amounts of

Denacol Ex-314 from Nagase Chemtex Co., Ltd. and dimethyl amine, and reacting the mixture for three hours at 60°C.

After forming the ultra-thin copper layer on the copper foil carrier, the first roughening treatment, the second roughening treatment, the anticorrosive treatment, the chromate treatment, and the silane coupling treatment described below were performed in this order. - Roughening Treatment 1 (Liquid Composition 1)

Cu: 10-30 g/L

H,S04: 10-150 g/L

W:0.1-50 mg/L

Sodium Dodecyl Sulfate:0.1-50 mg/L

As: 0.1-200 mg/L (Electroplating Conditions 1)

Temperature: 30-70°C

Current Density: 25-110 A/dm?

Roughening Coulombs: 50-500 As/dm’

Plating Time: 0.5-20 seconds - Roughening Treatment 2 (Liquid Composition 2)

Cu: 20-80 g/L

H,S04: 50-200 g/L (Electroplating Conditions 2)

Temperature: 30-70°C

Current Density: 5-50 A/dm*

Roughening Coulombs: 50-300 As/dm’

Plating Time: 1-60 seconds - Anticorrosive Treatment (Liquid Composition )

NaOH: 40-200 g/L

NaCN: 70-250 g/L

CuCN: 50-200 g/L

Zn(CN),: 2-100 g/L

As;05: 0.01-1 g/L (Liquid Temperature) 40-90°C (Current Conditions)

Current Density: 1-50 A/dm’

Plating Time: 1-20 seconds - Chromate Treatment

K;Cr,07 (Na,Cr,0; or CrO;): 2-10 g/L

NaOH or KOH: 10-50 g/L

ZnOH or ZnSO4 7H,0: 0.05-10 g/L pH: 7-13

< RB ,

Bath Temperature: 20-80°C

Current Density: 0.05-5 A/dm?

Time: 5-30 seconds + Silane Coupling Treatment

From 0.1 vol% to 0.3 vol% of 3-glycidoxypropyl trimethoxysilane aqueous solution was spray-applied, and heat-dried from 0.1 to 10 seconds in air from 100 to 200°C. < Comparative Example 1 >

After forming a Ni layer and a Cr layer on a copper foil carrier under the same conditions as those in Example 1, a 3 pm-thick ultra-thin copper layer was electroplated on the Cr layer on the roll-to-roll continuous plating line to complete the carrier-attached copper foil. + Ultra-Thin Copper Layer

Copper Concentration: 30-120 g/L

H,SO, Concentration: 20-120 g/L

Electrolyte Temperature: 20-80°C

Current Density: 5-9 A/dm? Roughening Treatment 1 (Liquid Composition 1)

Cu: 10-30 g/L

H,SO4: 10-150 g/L

As: 0-200 mg/L (Electroplating Conditions 1)

Temperature: 30-70°C

Current Density: 25-110 A/dm?

Roughening Coulombs: 50-500 As/dm’

Plating Time: 0.5-20 seconds - Roughening Treatment 2 (Liquid Composition 2)

Cu: 20-80 g/L

H,SO04: 50-200 g/L (Electroplating Conditions 2)

Temperature: 30-70°C

Current Density: 5-50 A/dm”

Roughening Coulombs: 50-300 As/dm®

Plating Time: 1-60 seconds + Anticorrosive Treatment (Liquid Composition)

NaOH: 40-200 g/L

NaCN: 70-250 g/L

CuCN: 50-200 g/L

Zn(CN),: 2-100 g/L

As03: 0.01-1 g/L (Liquid Temperature) 40-90°C (Current Conditions)

Current Density: 1-50 A/dm?

Plating Time: 1-20 seconds + Chromate Treatment

K,Cr,07 (Na,Cr,O7 or CrOs): 2-10 g/L

NaOH or KOH: 10-50 g/L

ZnOH or ZnSO4 7H,0: 0.05-10 g/L pH: 7-13

Bath Temperature: 20-80°C

Current Density: 0.05-5 A/dm”

Time: 5-30 seconds - Silane Coupling Treatment

From 0.1 vol% to 0.3 vol% of 3-glycidoxypropyl trimethoxysilane aqueous solution was spray-applied, and heat-dried from 0.1 to 10 seconds in air from 100 to 200°C.

\ 3 v being roughened, and the Rt of the surface of the ultra-thin copper layer being 2.3 pm or less when measured using a non-contact roughness meter.

In one embodiment of the carrier-attached copper foil according to the present invention, the Rz of the surface of the ultra-thin copper layer is 1.4 um or less when measured using a non-contact roughness meter.

In another embodiment of the carrier-attached copper foil according to the present invention, the Ra of the surface of the ultra-thin copper layer is 0.25 pm or less when measured using a non-contact roughness meter.

In yet another embodiment of the carrier-attached copper foil according to the present invention, the Rt of the surface of the ultra-thin copper layer is 1.8 um or less when measured using a non-contact roughness meter.

In yet another embodiment of the carrier-attached copper foil according to the present invention, the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3.

In yet another embodiment of the carrier-attached copper foil according to the present invention, the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3.

Yet another aspect of the present invention is a carrier-attached copper foil including a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, the ultra-thin copper layer being roughened, and the surface area ratio of the surface of the ultra-thin copper layer being from 1.05 to 1.5.

In yet another embodiment of the carrier-attached copper foil according to the present invention, the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5.

., ’ \ < Comparative Example 2 >

After forming a Ni layer and a Cr layer on a copper foil carrier under the same conditions as those in Example 1, a 3 pm-thick ultra-thin copper layer was electroplated on the Cr layer on the roll-to-roll continuous plating line to complete the carrier-attached copper foil. + Ultra-Thin Copper Layer

Copper Concentration: 30-120 g/L

H,S0O, Concentration: 20-120 g/L.

Electrolyte Temperature: 20-80°C

Current Density: 10-100 A/dm? * Roughening Treatment 1 (Liquid Composition 1)

Cu: 10-30 g/L

H,SO4: 10-150 g/L

W: 0-50 mg/L

Sodium Dodecyl Sulfate:0-50 mg/L

As: 0-200 mg/L (Electroplating Conditions 1)

Temperature: 30-70°C

Current Density: 25-110 A/dm?

Roughening Coulombs: 50-500 As/dm’

Plating Time: 40 seconds * Roughening Treatment 2 (Liquid Composition 2)

Cu: 20-80 g/L

H,S04: 50-200 g/L (Electroplating Conditions 2)

Temperature: 30-70°C

Current Density: 5-50 A/dm?

Roughening Coulombs: 50-300 As/dm’

Plating Time: 80 seconds

< . , - Anticorrosive Treatment (Liquid Composition)

NaOH: 40-200 g/L

NaCN: 70-250 g/L

CuCN: 50-200 g/L

Zn(CN),: 2-100 g/L

As;03: 0.01-1 g/L (Liquid Temperature) 40-90°C (Current Conditions)

Current Density: 1-50 A/dm?

Plating Time: 1-20 seconds + Chromate Treatment

K>Cr,07 (Na;Cr,07 or CrOs): 2-10 g/L

NaOH or KOH: 10-50 g/L

ZnOH or ZnSO4 7TH,0: 0.05-10 g/L pH: 7-13

Bath Temperature: 20-80°C

Current Density: 0.05-5 A/dm?’

Time: 5-30 seconds + Silane Coupling Treatment

From 0.1 vol% to 0.3 vol% of 3-glycidoxypropyl trimethoxysilane aqueous solution was spray-applied, and heat-dried from 0.1 to 10 seconds in air from 100 to 200°C. 2. Evaluation of Carrier-Attached Copper Foil Properties

The properties of the carrier-attached copper foils obtained in the manner described above were evaluated using the following methods. The results are shown in Table 1. (Surface Roughness)

The surface roughness of the ultra-thin copper layer (Ra, Rt, Rz, Ssk, Sku) was measured using a non-contact type roughness measuring instrument (LEXT OLS4000

& ¢ from Olympus). The Ra and Rz values were measured in accordance with JIS B 0601- 1994, the Rt value was measured in accordance with JIS B 0601-2001, and the Ssk and Sku values were measured in accordance with the ISO 25178 draft standards under the following conditions. < Measurement Conditions >

Cutoff: None

Reference Length: 257.9 um

Reference Area: 6,6524 pm’

Ambient Temperature: 23-25°C

For comparison purposes, the surface roughness (Ra, Rt, Rz) of the ultra-thin copper layer was measured using a contact-type roughness measuring instrument (a

Surfcorder SE-3C contact roughness meter from the Kosaka Institute, Inc.). The Ra and Rz values were measured in accordance with JIS B 0601-1994, and the Rt value was measured in accordance with JIS B 0601-2001 under the following conditions. < Measurement Conditions >

Cutoff: 0.25mm

Reference Length: 0.8mm

Ambient Temperature: 23-25°C (Surface Area Ratio)

The surface area ratio was measured under the following conditions using a non-contact type roughness measuring instrument (LEXT OLS4000 from Olympus).

The surface area ratio is obtained by measuring the area and the actual area, and then using the quotient of the actual area by the area as the surface area ratio.

Here, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area. < Measurement Conditions >

Cutoff: None

Reference Length: 257.9 um

Reference Area: 66,524 um’

Ambient Temperature: 23-25°C (Volume of Roughened Surface)

The volume of the roughened surface was measured under the following conditions using a non-contact type roughness measuring instrument (laser microscope, LEXT OLS4000 from Olympus). The volume of the roughened surface is measured in the following way. (1) The height of the laser microscope is adjusted to focus on the surface of the sample. (2) The brightness is adjusted so that the overall illumination is at approximately 80% of the saturation point. (3) The laser microscope is brought closer to the sample, and the point at which the screen illumination is completely extinguished is set as zero. (4) The laser microscope is moved away from the sample, and the point at which the screen illumination is completely extinguished is set as the upper limit height. (5) The volume of the roughened surface is measured from the zero height to the upper limit height. < Measurement Conditions >

Cutoff: None

Reference Length: 257.9 ym

Reference Area: 66,524 pm?

Ambient Temperature: 23-25°C (Migration)

Each carrier-attached copper foil was bonded to a bismuth-based resin, and the carrier foil was peeled off. The exposed ultra-thin copper layer was then soft-etched to a thickness of 1.5 um. After washing and drying the surface, DF (RY-3625 from

Hitachi Chemical Co., Ltd.) was laminated on top of the ultra-thin copper layer. After exposing the laminate at 15 mJ/cm?, liquid injection oscillation was performed for one minute at 38°C using a developer (sodium carbonate) to form resist patterns at the pitches shown in Table 1. Next, after 15 um-thick of plating using copper sulfate plating (CUBRITE 21 from Ebara Udylite Co., Ltd.), the DF was delaminated using a stripping solution (sodium hydroxide). Afterwards, the ultra-thin copper layer was etched off using a sulfuric acid-hydrogen peroxide etchant to form wiring at the

“0 : , pitches shown in Table 1. The pitches shown in the table correspond to the line and space total values. It was also determined whether there had been any deterioration in the insulation between wires under the following conditions using a migration measuring device (MIG-9000 from IMV). < Measurement Conditions >

Threshold Value: 60% Below Initial Resistance

Measurement Time: 1,000 h

Voltage: 60 V

Temperature: 85°C

Relative Humidity: 85% RH [Table 1-1] mee Jefe

BT ol fos [aso [oor [om [oss [ux [si

C. Ex. | 0.30 2.80 2.10 0.62 3.90 3.46 0.396 | 2.683

OP

C. Ex. | 0.21 1.83 1.23 0.33 2.49 2.09 0.567 | 3.555

EE

[Table 1-2] en em Pree

¥ ’

In yet another embodiment of the carrier-attached copper foil according to the present invention, the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area is 300,000 pm’ or greater.

Yet another aspect of the present invention is a copper-clad laminate manufactured using one of these carrier-attached copper foils according to the present invention.

Yet another aspect of the present invention is a printed wiring board manufactured using one of these carrier-attached copper foils according to the present invention.

Yet another aspect of the present invention is a printed wiring board manufactured using one of these carrier-attached copper foils.

Yet another aspect of the present invention is a method for manufacturing a printed wiring board, the method including the steps of: preparing a carrier-attached copper foil according to the present invention and an insulating substrate; laminating the carrier-attached copper foil and the insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier-attached copper foil and insulating substrate have been laminated to form a copper-clad laminate; and forming a circuit using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

Effect of the Invention

The present invention is able to provide carrier-attached copper foil suitable for fine pitching. More specifically, it is able to provide carrier-attached copper foil on which wiring can be formed which is finer than L/S = 20 pum/20 pm, which is considered to be the limit for the formation of wiring using MSAP, such as fine wiring inwhich L/S =15 um/15 ym.

Brief Description of the Drawings

FIG. 1 is an SEM photograph of the M surface of the ultra-thin copper layer in

Example 1 and Example 2.

, » y

FIG. 2 (A) through FIG. 2 (C) are schematic views of a printed wiring board cross- section showing the steps in one example of the manufacturing method for a printed wiring board using carrier-attached copper foil according to the present invention up until the step in which the circuit plating has been performed and the resist has been removed.

FIG. 3 (D) through FIG. 3 (F) are schematic views of a printed wiring board cross-section showing the steps in one example of the manufacturing method for a printed wiring board using carrier-attached copper foil according to the present invention from the step of formation of the resin and the second carrier-attached copper film layer to the step in which a laser is used to open a hole.

FIG. 4 (G) through FIG. 4 (I) are schematic views of a printed wiring board cross-section showing the steps in one example of the manufacturing method for a printed wiring board using carrier-attached copper foil according to the present invention from the via fill step to the step in which the first carrier has been peeled off.

FIG. 5 (J) through FIG. 5 (K) are schematic views of a printed wiring board cross-section showing the steps in one example of the manufacturing method for a printed wiring board using carrier-attached copper foil according to the present invention from the flush etching step to the step in which the bump and copper pillar have been formed.

Embodiment of the Invention <1. Carrier >

Copper foil can be used as the carrier in the present invention. The carrier is typically provided in the form of rolled copper foil or electrolytic copper foil. Usually, electrolytic copper foil is manufactured by electrolytic deposition of copper on a titanium or stainless steel drum from a copper sulfate plating bath, and rolled copper foil is manufactured by repeatedly heating and working copper foil using a mill roll.

The materials used in the copper foil may be pure copper known as tough-pitch copper and oxygen-free copper, copper alloys such as Sn-containing copper, Ag- containing copper, copper alloys to which Cr, Zr or Mg, etc. has been added, or

Corson copper alloys to which Ni and Si, etc. have been added. In the present specification, “copper foil” may also refer to a copper alloy foil.

; b v

There are no particular restrictions on the thickness of the carrier used in the present invention. The thickness may be adjusted according to the intended use of the carrier, and can be, for example, 12 um or more. However, thicker copper foil increases manufacturing costs, so a thickness of 70 um or less is preferred. Therefore, the thickness of the carrier is typically from 12 to 70 um, and more typically from 18 to 35 um. <2. Release Layer >

A release layer is provided on top of the carrier. The release layer can be any release layer commonly applied to carrier-attached copper foil. For example, the release layer preferably includes at least one type of material selected from among Cr,

Ni, Co, Fe, Mo, Ti, W, P, Cu and Al, or an alloy thereof, a hydrate thereof, an oxide thereof, or an organic compound. More than one release layer may be used.

In the present embodiment of the invention, the release layer, from the carrier side, is composed of a single-metal layer of an element selected from among Cr, Ni,

Co, Fe, Mo, Ti, W, P, Cu and Al, or an alloy layer including one or more elements selected from among Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu and Al, and a hydrate or oxide layer of one or more elements selected from among Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu and Al laminated on top.

The release layer is preferably composed of two layers, a Ni layer and a Cr layer. In this laminate, the Ni layer forms the interface with the copper foil carrier, and the Cr layer forms the interface with the ultra-thin copper layer.

The release layer can be obtained using a wet plating method such as electroplating, non-electrolytic plating or immersion plating, or a dry plating method such as sputtering, CVD or PVD. Electroplating is preferred from a cost standpoint. <3. Ultra-Thin Copper Layer >

The ultra-thin copper layer is provided on top of the release layer. The ultra- thin copper layer can be formed by performing electroplating in an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfamate, and copper cyanide. A copper sulfate bath is preferred because it is commonly used for electrolytic copper foil and it can form copper foil with a high current density. There are no particular i, * v restrictions on the thickness of the ultra-thin copper layer. It is usually thinner than the carrier, for example, 12 um or less. It is typically from 0.5 to 12 pm, and more typically from 2 to 5 um. <4. Roughening Treatment and Other Surface Processing >

A roughening layer is provided on the surface of the ultra-thin copper layer through a roughening treatment in order to improve adhesion to the insulating substrate, etc. The roughening can be performed by forming roughening particles using copper or a copper alloy. The roughening layer is preferably composed of fine particles from the standpoint of fine pitching. As for the electroplating conditions used to form roughened particles, finer particles tend to be formed when the current density is higher, the concentration of copper in the plating bath is lower, or the coulomb is higher.

The roughening layer may be composed of electrodeposited grains of a single element selected from among copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, and an alloy containing any one or more thereof.

After the roughening has been completed, secondary particles or tertiary particles and/or an anticorrosive layer and/or a heat-resistant layer may be formed with a single element of nickel, cobalt, copper or zinc, or an alloy thereof, and a surface treatment such as chromate treatment or silane coupling treatment may also be performed. In other words, at least one layer selected from among an anticorrosive layer, a heat-resistant layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughening layer.

For example, a heat-resistant layer and/or anticorrosive layer may be provided on the roughening layer, a chromate layer may be provided on the heat-resistant layer and/or anticorrosive layer, and a silane coupling layer may be provided on the chromate treatment layer. There are no particular restrictions on the order in which the heat-resistant layer, anticorrosive layer, the chromate treatment layer, and the silane coupling treatment layer are formed. These layers may be formed on top of the roughening layer in any order.

Claims (112)

Claims | ©

1. A carrier-attached copper foil comprising a copper foil carrier, a release layer on laminated on the copper foil carrier, and an ultra-thin copper layer laminated - on the release layer, the ultra-thin copper layer being roughened, and the Rz of 7 the surface of the ultra-thin copper layer being 1.6 pm or less when measured using a non-contact roughness meter and the Sku of the surface of the ultra- - thin copper layer is from 2.8 to 3.3. BE ; og

2. A carrier-attached copper foil comprising a copper foil carrier, a release layer ~ laminated on the copper foil carrier, and an ultra-thin copper layer Jaminated ® on the release layer, wherein the ultra-thin copper layer is roughenetl, and the ~ Rz of the surface of the ultra-thin copper layer is 1.6 pum or less when . measured using a non-contact roughness meter, and the Ssk of the surface of the ultra-thin copper layer is from -0.058 to 0.3.

3. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the Rz of the surface of the ultra-thin copper layer is 1.35 yum or less when measured using a non-contact roughness meter, and the volume of the surface of the ultra-thin copper layer per 66,524 unit area as measured by a laser microscope is 350,000 um? or greater.

4. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer being roughened, the Ra of the surface of the ultra-thin copper layer is 0.3 pum or less when measured using a non-contact roughness meter and the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3.

5. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the Ra of the surface of the ultra-thin copper layer is 0.3 um or less when measured using a non-contact roughness meter, and the Ssk of the surface of the ultra-

i ‘ s ’ thin copper layer is from -0.058 to 0.3. =

6. A carrier-attached copper foil comprising a copper foil carrier, a release layer - laminated on the copper foil carrier, and an ultra-thin copper layer laminated - on the release layer, wherein the ultra-thin copper layer is roughened, the Rt of - the surface of the ultra-thin copper layer is 2.3 um or less when measured ~ using a non-contact roughness meter, and the Sku of the surface of the ultra- = thin copper layer is from 2.8 to 3.3. =

7. A carrier-attached copper foil comprising a copper foil carrier, a release layer o laminated on the copper foil carrier, and an ultra-thin copper layer laminated = on the release layer, wherein the ultra-thin copper layer is roughened, the Rt of = the surface of the ultra-thin copper layer is 2.3 um or less when measured using a non-contact roughness meter, and the Ssk of the surface of the ultra- thin copper layer is from -0.058 to 0.3.

8. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the Rz of the surface of the ultra-thin copper layer is 1.3 pm or less when measured using a non-contact roughness meter.

9. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the Rz of the surface of the ultra-thin copper layer is 1.10 pm or less when measured using a non-contact roughness meter.

10. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the Ra of the surface of the ultra-thin copper layer is 0.25 pum or less when measured using a non-contact roughness meter.

11. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Ra of the surface of the ultra-thin copper layer is 0.20 ym or less when measured using a non-contact roughness meter.

12. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the Ra of the surface of the ultra-thin copper layer is 0.16 pm or less when measured using a non-contact roughness meter.

J q ‘ ’

13. The carrier-attached copper foil according to any one of claims 1 through 7, . wherein the Rt of the surface of the ultra-thin copper layer is 1.8 ym or less when measured using a non-contact roughness meter. -

14. The carrier-attached copper foil according to anyone of claims 1 through 7, - wherein the Rt of the surface of the ultra-thin copper layer is 1.5 um or less ~ when measured using a non-contact roughness meter. so

15. The carrier-attached copper foil according to any one of claims 1 through 7, = wherein the Rt of the surface of the ultra-thin copper layer is 1.35 um or less - when measured using a non-contact roughness meter. =

16. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3.

17. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3.

18. The carrier-attached copper foil according to anyone of claims 1 through 7, wherein the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area.

19. The carrier-attached copper foil according to any one of claims 1 through 2, 4 through 7, wherein the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area as measured by a laser microscope is 300,000 pm’ or greater.

20. The carrier-attached copper foil according to any on of claims 1 through 7, wherein the volume of the surface of the ultra-thin copper layer per 66,524 pm” unit area as measured by a laser microscope is 350,000 pm’ or greater.

t “ 4 ’

21. The carrier-attached copper foil according to any one of claims 1 through 2 = on and 4 through 7, wherein the Rz of the surface of the ultra-thin copper layer is “

1.5 um or less when measured using a non-contact roughness meter. 51

22. The carrier-attached copper foil according to any one of claims 1 through 7, oe wherein the Rz of the surface of the ultra-thin copper layer is 1.35 gm or less o when measured using a non-contact roughness meter. @

23. The carrier-attached copper foil according to any one of claims 1 through 7, = wherein the Ra of the surface of the ultra-thin copper layer is 0.24 um or less = when measured using a non-contact roughness meter. o

24. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Ra of the surface of the ultra-thin copper layer is 0.23 pm or less when measured using a non-contact roughness meter.

25. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Rt of the surface of the ultra-thin copper layer is 1.2 um or less when measured using a non-contact roughness meter.

26. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.2.

27. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3.

28. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3.

29. The carrier-attached copper foil according to any one of claims 1 through 7, wherein the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the

6d : surface area within the measurement reference area. Re LE

30. The carrier-attached copper foil according to any one of claims 1 through 7, g wherein the surface area ratio of the surface of the ultra-thin copper layer is » from 1.1 to 1.3. (Here, the surface area ratio is the actual area/area when the = area and actual area have been measured using a laser microscope. The area indicates the measurement reference area, and the actual area indicates the = surface area within the measurement reference area.)

31. The carrier-attached copper foil according to any one of claims 1, 4 and 6, = wherein the carrier-attached copper foil satisfies one or more of the following o provisions: - - the Rz of the surface of the ultra-thin copper layer is 1.6 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.10 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is from 0.01um to

0.56 ym when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.3 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.25 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.24 pum or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.23 ym or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 pum or less

, , when measured using a non-contact roughness meter, oT - the Ra of the surface of the ultra-thin copper layer is from 0.005 gm to o

0.09 um when measured using a non-contact roughness meter, on - the Ra of the surface of the ultra-thin copper layer is from 0.02 pum to »

0.09 pum when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 2.3 pum or less = when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 1.8 um or less when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 1.5 pm or less = when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.35 pm or less = when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.2 pum or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3, - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1to 1.3, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area,

- the volume of the surface of the ultra-thin copper layer per 66,524 ym2 unit area as measured by a laser microscope is 300,000 um3 or greater, o - the volume of the surface of the ultra-thin copper layer per 66,524 um2 on unit area as measured by a laser microscope is 350,000 pm’ or greater. oo =

32. The carrier-attached copper foil according to any one of claims 2, 5 and 7, = wherein the carrier-attached copper foil satisfies one or more of the following = provisions: ’ - the Rz of the surface of the ultra-thin copper layer is 1.6 ym or less = when measured using a non-contact roughness meter, = - the Rz of the surface of the ultra-thin copper layer is 1.5 um or less o when measured using a non-contact roughness meter, = - the Rz of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.10 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is from 0.01um to

0.56 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.3 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.25 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.24 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.23 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 ym or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 ym to

0.09 ym when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 um to

; : ,

0.09 um when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 2.3 um or less - when measured using a non-contact roughness meter, ” - the Rt of the surface of the ultra-thin copper layer is 1.8 um or less - when measured using a non-contact roughness meter, - - the Rt of the surface of the ultra-thin copper layer is 1.5 pm or less when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 1.35 pm or less o when measured using a non-contact roughness meter, - - the Rt of the surface of the ultra-thin copper layer is 1.2 ym or less - when measured using a non-contact roughness meter, ol - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 = pm when measured using a non-contact roughness meter, - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.05to 1.5, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area - the volume of the surface of the ultra-thin copper layer per 66,524 um2 unit area as measured by a laser microscope is 300,000 um3 or greater, - the volume of the surface of the ultra-thin copper layer per 66,524 pm? unit area as measured by a laser microscope is 350,000 pm’ or greater.

33. The carrier-attached copper foil according to claim 3, wherein the carrier- attached copper foil satisfies one or more of the following provisions: - the Rz of the surface of the ultra-thin copper layer is 1.3 um or less

° ¥ ’ when measured ing a non-contact roughness meter, x - the Rz of the surface of the ultra-thin copper layer is 1.10 pm or less ~ when measured using a non-contact roughness meter, on - the Rz of the surface of the ultra-thin copper layer is from 0.01um to ~

0.56 um when measured using a non-contact roughness meter, co - the Ra of the surface of the ultra-thin copper layer is 0.3 um or less - when measured using a non-contact roughness meter, © - the Ra of the surface of the ultra-thin copper layer is 0.25 yum or less ~~ when measured using a non-contact roughness meter, = - the Ra of the surface of the ultra-thin copper layer is 0.24 pm or less = when measured using a non-contact roughness meter, o - the Ra of the surface of the ultra-thin copper layer is 0.23 pum or less ~ when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 ym or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 pm to

0.09 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 pum to

0.09 um when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.8 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.5 pgm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.35 ym or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.2 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3,

, ! ' - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, ry - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to - 03, - - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, » - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, ol - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5, = - the surface area ratio of the surface of the ultra-thin copper layer is = from 1.09 to 1.4, oO - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area.)

34. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the surface of the ultra-thin copper layer satisfies at least one of the following three conditions that Rz is 1.6 um or less, Ra is 0.3 pum or less, and Rt is 2.3 pm or less when measured using a non-contact roughness meter, the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, the Ssk of the surface of the ultra-thin copper layer is from -0.058 to 0.3, and the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5.

35. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the surface of the ultra-thin copper layer satisfies at least one of the following three conditions that Rz is 1.6 um or less, Ra is 0.25 um or less, and Rt is 1.8 pum or less when measured using a non-contact roughness meter, the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, and the surface

: , . area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4. -

36. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated - on the release layer, wherein the ultra-thin copper layer is roughened, the ~ surface of the ultra-thin copper layer satisfies at least one of the following ~ three conditions that Rz is 1.6 um or less, Ra is 0.25 um or less, and Rtis 1.8 ~~ = pm or less when measured using a non-contact roughness meter, the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, the Ssk of the ~ surface of the ultra-thin copper layer is from -0.058 to 0.3, and the surface ® area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4. »

37. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the surface of the ultra-thin copper layer satisfies at least one of the following three conditions that Rz is 1.6 um or less, Ra is 0.25 pm or less, and Rt is 1.8 pm or less when measured using a non-contact roughness meter, the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, the Ssk of the surface of the ultra-thin copper layer is from -0.058 to 0.3, and the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3.

38. The carrier-attached copper foil according to any one of claims 1 through 7 and 33 through 37, wherein at least one type of layer selected from among a heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer is formed on the roughened ultra-thin copper layer.

39. The carrier-attached copper foil according to claim 31, wherein at least one type of layer selected from among a heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer is formed on the roughened ultra-thin copper layer.

40. The carrier-attached copper foil according to claim 32, wherein at least one type of layer selected from among a heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer is formed on the roughened ultra-thin copper layer. © [y]

41. The carrier-attached copper foil according to any one of claims 1 through 7 wn» and 33 through 37, wherein a resin layer is provided on the roughened ultra- n thin copper layer. oo

42. The carrier-attached copper foil according to claim 31, wherein a resin layeris = provided on the roughened ultra-thin copper layer. Lr

43. The carrier-attached copper foil according to claim 32, wherein a resin layer is = provided on the roughened ultra-thin copper layer. -

44. The carrier-attached copper foil according to claim 41, wherein the resin layer comprises a dielectric.

45. The carrier-attached copper foil according to claim 38, wherein a resin layer 1s provided on at least one type of layer selected from among the heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer.

46. The carrier-attached copper foil according to claim 39, wherein a resin layer is provided on at least one type of layer selected from among the heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer.

47. The carrier-attached copper foil according to claim 46, wherein the resin layer comprises a dielectric.

48. A copper-clad laminate manufactured using the carrier-attached copper foil according to any one of claims 1 through 7 and 33 through 37.

49. A printed wiring board manufactured using the carrier-attached copper foil according to any one of claims 1 through 7 and 33 through 37.

50. A printed circuit board manufactured using the carrier-attached copper foil

; . according to any one of claims 1 through 7 and 33 through 37. -

51. An electronic devices comprising the printed wiring board according to claim

29. =

52. A method for manufacturing a printed wiring board , the method comprising B the steps of: = preparing a carrier-attached copper foil according to any one of claims - 1 through 7 and 33 through 37 and an insulating substrate; ~ laminating the carrier-attached copper foil and the insulating substrate; ® peeling off the carrier of the carrier-attached copper foil after the vo carrier-attached copper foil and insulating substrate have been laminated to } form a copper-clad laminate; and forming a circuit using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

53. A method for manufacturing a printed wiring board comprising the steps of: forming a circuit on the surface of the ultra-thin copper layer side of a carrier-attached copper foil according to any one of claims 1 through 7 and 33 through 37; forming a resin layer on the surface of the ultra-thin copper layer side of the carrier-attached copper foil so as to embed the circuit; forming a circuit on the resin layer; peeling off the carrier after the circuit has been formed on the resin layer; and removing the ultra-thin copper layer after the carrier has been peeled off to expose the circuit formed on the surface of the ultra-thin copper layer and embedded in the resin layer.

54. The method for manufacturing a printed wiring board according to claim 53, wherein the step of forming the circuit on the resin layer includes the steps of affixing another carrier-attached copper foil on the resin layer from the ultra- thin copper layer side, and forming the circuit using the carrier-attached copper foil affixed to the resin layer.

, .

55. The method for manufacturing a printed wiring board according to claim 54, ee wherein the other carrier-attached copper foil affixed to the resin layer is a - carrier-attached copper foil according to any one of claims 1 through 7 and 33 through 37. wo ol

56. The method for manufacturing a printed wiring board according to claim 53, - wherein the step of forming the circuit on the resin layer is performed using i. the semi-additive method, subtractive method, partly additive method, or modified semi-additive method. - =

57. The method for manufacturing a printed wiring board according to claim 53 oO further comprising the step of forming a substrate on the carrier surface of the vr carrier-attached copper foil before peeling off the carrier.

58. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to

1.5, and the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area as measured by a laser microscope being 300,000 pm’ or greater wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area.

59. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to

1.5, and the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area.

60. A carrier-attached copper foil comprising a copper foil carrier, a release layer a laminated on the copper foil carrier, and an ultra-thin copper layer laminated ~ on the release layer, wherein the ultra-thin copper layer is roughened, the - surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to =

1.5, and the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, = wherein the surface area ratio is the actual area/area when the area and actual ~ area have been measured using a laser microscope. The area indicates the - measurement reference area, and the actual area indicates the surface area within the measurement reference area. 2 =

61. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3.

62. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the volume of the surface of the ultra-thin copper layer per 66,524 pm? unit area as measured by a laser microscope is 350,000 pm’ or greater.

63. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3.

64. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3.

65. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.2.

66. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3.

67. The carrier-attached copper foil according to any one of claims 58 through 60, wherein the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3.

68. The carrier-attached copper foil according to any one of claims 58 through 60, = wherein the surface area ratio of the surface of the ultra-thin copper layer is ~ from 1.09 to 1.4. on

69. The carrier-attached copper foil according to any one of claims 58 through 60, ol wherein the surface area ratio of the surface of the ultra-thin copper layer is = from 1.05 to 1.5. .

70. The carrier-attached copper foil according to claim 58, wherein the carrier- attached copper foil satisfies one or more of the following provisions: = - the Rz of the surface of the ultra-thin copper layer is 1.6 pum or less Ol when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.35 pm or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 ym or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.10 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is from 0.01um to

0.56 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.3 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.25 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.24 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.23 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 ym or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 pum or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 pum to

. , .

0.09 pm when measured using a non-contact roughness meter, w= - the Ra of the surface of the ultra-thin copper layer is from 0.02 pm to -

0.09 um when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 um or less o> when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 1.8 ym or less when measured using a non-contact roughness meter, = - the Rt of the surface of the ultra-thin copper layer is 1.5 pm or less when measured using a non-contact roughness meter, - - the Rt of the surface of the ultra-thin copper layer is 1.35 um or less = when measured using a non-contact roughness meter, oO - the Rt of the surface of the ultra-thin copper layer is 1.2 pm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3, - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1t0 1.3, wherein, the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area. - the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area as measured by a laser microscope is 350,000 pm’ or greater.

, .

71. The carrier-attached copper foil according to claim 59, wherein the carrier- attached copper foil satisfies one or more of the following provisions: o - the Rz of the surface of the ultra-thin copper layer is 1.6 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 pm or less - when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.35 um or less ~ when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 ym or less when measured using a non-contact roughness meter, = - the Rz of the surface of the ultra-thin copper layer is 1.10 um or less Oo when measured using a non-contact roughness meter, = - the Rz of the surface of the ultra-thin copper layer is from 0.01pm to

0.56 ym when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.3 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.25 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.24 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.23 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 ym to

0.09 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 ym to

0.09 um when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.8 pm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.5 pgm or less

. , . when measured using a non-contact roughness meter, Pe - the Rt of the surface of the ultra-thin copper layer is 1.35 um or less - when measured using a non-contact roughness meter, o - the Rt of the surface of the ultra-thin copper layer is 1.2 um or less i» when measured using a non-contact roughness meter, ol - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 - pm when measured using a non-contact roughness meter, - - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, on - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, = - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, ol - the surface area ratio of the surface of the ultra-thin copper layer is ~~ ’ from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, wherein, the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area. - the volume of the surface of the ultra-thin copper layer per 66,524 um? unit area as measured by a laser microscope is 300,000 um3 or greater, - the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area as measured by a laser microscope is 350,000 pm’ or greater.

72. The carrier-attached copper foil according to claim 60, wherein the carrier- attached copper foil satisfies one or more of the following provisions: - the Rz of the surface of the ultra-thin copper layer is 1.6 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 ym or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.10 pm or less when measured using a non-contact roughness meter, | wi - the Rz of the surface of the ultra-thin copper layer is from 0.01um to zo

0.56 pm when measured using a non-contact roughness meter, on - the Ra of the surface of the ultra-thin copper layer is 0.3 um or less - when measured using a non-contact roughness meter, ol - the Ra of the surface of the ultra-thin copper layer is 0.25 um or less = when measured using a non-contact roughness meter, - - the Ra of the surface of the ultra-thin copper layer is 0.24 um or less on when measured using a non-contact roughness meter, . - the Ra of the surface of the ultra-thin copper layer is 0.23 um or less = when measured using a non-contact roughness meter, Ol - the Ra of the surface of the ultra-thin copper layer is 0.20 pm or less - when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 um to

0.09 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 um to

0.09 um when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 pm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.8 pum or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.5 pm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.35 gm or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.2 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3, te! - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is io from 1.09 to 1.4, = - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, = wherein the surface area ratio is the actual area/area when the area and actual area » have been measured using a laser microscope, the area indicates the measurement - reference area, and the actual area indicates the surface area within the measurement = reference area. 0 - the volume of the surface of the ultra-thin copper layer per 66,524 yum2 - unit area as measured by a laser microscope is 300,000 um3 or greater. - the volume of the surface of the ultra-thin copper layer per 66,524 pm’ unit area as measured by a laser microscope is 350,000 pm?’ or greater.

73. The carrier-attached copper foil according to any one of claims 58 through 60 and 70 through 72 wherein at least one type of layer selected from among a heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer is formed on the roughened ultra-thin copper layer.

74. The carrier-attached copper foil according to any one of claims 58 through 60 and 70 through 72, wherein a resin layer is provided on the roughened ultra- thin copper layer.

75. The carrier-attached copper foil according to claim 74, wherein the resin layer comprises a dielectric.

76. The carrier-attached copper foil according to claim 73, wherein a resin layer is provided on at least one type of layer selected from among the heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer.

77. The carrier-attached copper foil according to claim 76, wherein the resin layer comprises a dielectric.

Lr

78. A copper-clad laminate manufactured using the carrier-attached copper foil according to any one of claims 58 through 60 and 70 through 72. bo

79. A printed wiring board manufactured using the carrier-attached copper foil - according to any one of claims 58 through 60 and 70 through 72. ~

80. A printed circuit board manufactured using the carrier-attached copper foil ol according to any one of claims 58 through 60 and 70 through 72. ~ &

81. An electronic devices comprising the printed wiring board according to claim w i” Ja

82. A method for manufacturing a printed wiring board comprising the steps of: preparing a carrier-attached copper foil according to any one of claims 58 through 60 and 70 through 72 and an insulating substrate; laminating the carrier-attached copper foil and the insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier-attached copper foil and insulating substrate have been laminated to form a copper-clad laminate; and forming a circuit using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

83. A method for manufacturing a printed wiring board comprising the steps of: forming a circuit on the surface of the ultra-thin copper layer side of a carrier-attached copper foil according to any one of claims 58 through 60 and 70 through 72; forming a resin layer on the surface of the ultra-thin copper layer side of the carrier-attached copper foil so as to embed the circuit; forming a circuit on the resin layer; peeling off the carrier after the circuit has been formed on the resin layer; and removing the ultra-thin copper layer after the carrier has been peeled off to expose the circuit formed on the surface of the ultra-thin copper layer and embedded in the resin layer.

=

84. The method for manufacturing a printed wiring board according to claim 83, wherein the step of forming the circuit on the resin layer includes the steps of oy affixing another carrier-attached copper foil on the resin layer from the ultra- . thin copper layer side, and forming the circuit using the carrier-attached copper foil affixed to the resin layer. -

85. The method for manufacturing a printed wiring board according to claim 84, i. wherein the other carrier-attached copper foil affixed to the resin layer is a = carrier-attached copper foil according to any one of claims 58 through 60 and = 70 through 72. o

86. The method for manufacturing a printed wiring board according to claim 83, wherein the step of forming the circuit on the resin layer is performed using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

87. The method for manufacturing a printed wiring board according to claim 83 further comprising the step of forming a substrate on the carrier surface of the carrier-attached copper foil before peeling off the carrier.

88. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, and the Rz of the surface of the ultra-thin copper layer is from 0.01 to 0.56 ym when measured using a non-contact roughness meter.

89. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer is roughened, and the Ra of the surface of the ultra-thin copper layer is from 0.005 to 0.09 um when measured using a non-contact roughness meter.

90. A carrier-attached copper foil comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultra-thin copper layer laminated on the release layer, wherein the ultra-thin copper layer being roughened, and @ the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 um N when measured using a non-contact roughness meter. y

91. The carrier-attached copper foil according to any one of claims 88 through 90, ~ wherein the Rz of the surface of the ultra-thin copper layer is from 0.1 to 0.56 ” pm when measured using a non-contact roughness meter. =

92. The carrier-attached copper foil according to any one of claims 88 through 90, 7 wherein the Ra of the surface of the ultra-thin copper layer is from 0.02 to 0.09 - pm when measured using a non-contact roughness meter. o

93. The carrier-attached copper foil according to any one of claims 88 through 90, wherein the Rt of the surface of the ultra-thin copper layer is from 0.1 to 0.84 pm when measured using a non-contact roughness meter.

94. The carrier-attached copper foil according to any one of claims 88 through 90, wherein the surface area ratio of the surface of the ultra-thin copper layer is from 1.05t0 1.5, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area.

95. The carrier-attached copper foil according to claim 88, wherein the carrier- attached copper foil satisfies one or more of the following provisions: - the Ra of the surface of the ultra-thin copper layer is 0.3 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.25 pm or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.24 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.23 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 um or less when measured using a non-contact roughness meter, oy - the Ra of the surface of the ultra-thin copper layer is 0.16 um or less zo when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 pm to

0.09 um when measured using a non-contact roughness meter, - - the Ra of the surface of the ultra-thin copper layer is from 0.02 ym to >

0.09 um when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.8 um or less = when measured using a non-contact roughness meter, ol - the Rt of the surface of the ultra-thin copper layer is 1.5 ym or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.2 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to 03, - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.05 to 1.5, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1to 1.3,

wherein the surface area ratio is the actual area/area when the area and actual area a have been measured using a laser microscope, the area indicates the measurement - reference area, and the actual area indicates the surface area within the measurement reference area. o - the volume of the surface of the ultra-thin copper layer per 66,524 um?* - unit area as measured by a laser microscope is 300,000 um’ or greater. - - the volume of the surface of the ultra-thin copper layer per 66,524 pum’ ® unit area as measured by a laser microscope is 350,000 um’ or greater. Lr

96. The carrier-attached copper foil according to claim 89, wherein the carrier- 5 attached copper foil satisfies one or more of the following provisions: ol - the Rz of the surface of the ultra-thin copper layer is 1.6 ym or less = when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.10 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is from 0.01um to

0.56 um when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 ym to

0.09 pm when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 2.3 pum or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.8 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.5 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.35 um or less when measured using a non-contact roughness meter, - the Rt of the surface of the ultra-thin copper layer is 1.2 ym or less when measured using a non-contact roughness meter,

- the Rt of the surface of the ultra-thin copper layer is from 0.01 to 0.84 on pm when measured using a non-contact roughness meter, - - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, “1 - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, ~ - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to -

0.3, > - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, 1 - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, i» - the surface area ratio of the surface of the ultra-thin copper layer is + from 1.05 to 1.5, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, wherein the surface area ratio is the actual area/area when the area and actual area have been measured using a laser microscope, the area indicates the measurement reference area, and the actual area indicates the surface area within the measurement reference area. - the volume of the surface of the ultra-thin copper layer per 66,524 yum2 unit area as measured by a laser microscope is 300,000 um3 or greater. - the volume of the surface of the ultra-thin copper layer per 66,524 pm? unit area as measured by a laser microscope is 350,000 pm’ or greater.

97. The carrier-attached copper foil according to claim 90, wherein the carrier- attached copper foil satisfies one or more of the following provisions: - the Rz of the surface of the ultra-thin copper layer is 1.6 um or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.5 pm or less when measured using a non-contact roughness meter, - - the Rz of the surface of the ultra-thin copper layer is 1.35 pum or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is 1.3 pm or less when measured using a non-contact roughness meter, = - the Rz of the surface of the ultra-thin copper layer is 1.10 pm or less when measured using a non-contact roughness meter, - the Rz of the surface of the ultra-thin copper layer is from 0.01um to »

0.56 um when measured using a non-contact roughness meter, o - the Ra of the surface of the ultra-thin copper layer is 0.3 um or less when measured using a non-contact roughness meter, = - the Ra of the surface of the ultra-thin copper layer is 0.25 um or less when measured using a non-contact roughness meter, - - the Ra of the surface of the ultra-thin copper layer is 0.24 um or less = when measured using a non-contact roughness meter, Pa - the Ra of the surface of the ultra-thin copper layer is 0.23 um or less = when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.20 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is 0.16 um or less when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.005 um to

0.09 pm when measured using a non-contact roughness meter, - the Ra of the surface of the ultra-thin copper layer is from 0.02 um to

0.09 pm when measured using a non-contact roughness meter, - the Ssk of the surface of the ultra-thin copper layer is from -0.3 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.2 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.1 to 0.3, - the Ssk of the surface of the ultra-thin copper layer is from -0.058 to

0.3, - the Sku of the surface of the ultra-thin copper layer is from 2.7 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.8 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 2.9 to 3.3, - the Sku of the surface of the ultra-thin copper layer is from 3.0 to 3.3, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.05to 1.5, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.09 to 1.4, - the surface area ratio of the surface of the ultra-thin copper layer is from 1.1 to 1.3, = wherein the surface area ratio is the actual area/area when the area and actual area - have been measured using a laser microscope, - the area indicates the measurement reference area, and =» the actual area indicates the surface area within the measurement reference area.) oe - the volume of the surface of the ultra-thin copper layer per 66,524 um?2 - unit area as measured by a laser microscope is 300,000 um3 or greater. = - the volume of the surface of the ultra-thin copper layer per 66,524 pm? . unit area as measured by a laser microscope is 350,000 ym’ or greater. - -

98. The carrier-attached copper foil according to any one of claims 88 through 90 and 95 through 97, wherein at least one type of layer selected from among a ~ heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer is formed on the roughened ultra-thin copper layer.

99. The carrier-attached copper foil according to any one of claims 88 through 90 and 95 through 97, wherein a resin layer is provided on the roughened ultra- thin copper layer.

100. The carrier-attached copper foil according to claim 99, wherein the resin layer comprises a dielectric.

101. The carrier-attached copper foil according to claim 98, wherein a resin layer is provided on at least one type of layer selected from among the heat-resistant layer, anticorrosive layer, chromate treatment layer, and silane coupling treatment layer.

102. The carrier-attached copper foil according to claim 101, wherein the resin layer comprises a dielectric.

103. A copper-clad laminate manufactured using the carrier-attached copper foil according to any one of claims 88 through 90, 95 through 97 and 100 through

102.

104. A printed wiring board manufactured using the carrier-attached copper foil

‘ Jb according to any one of claims 88 through 90, 95 through 97 and 100 through -

102. oe

105. A printed circuit board manufactured using the carrier-attached copper foil = according to any one of claims 88 through 90, 95 through 97 and 100 through

102. i.

106. An electronic devices comprising the printed wiring board according to claim ~~

104. _ :

107. A method for manufacturing a printed wiring board, the method comprising the steps of: - preparing a carrier-attached copper foil according to any one of claims 88 through 90, 95 through 97 and 100 through 102 and an insulating substrate; laminating the carrier-attached copper foil and the insulating substrate; peeling off the carrier of the carrier-attached copper foil after the carrier-attached copper foil and insulating substrate have been laminated to form a copper-clad laminate; and forming a circuit using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

108. A method for manufacturing a printed wiring board, the method comprising the steps of: forming a circuit on the surface of the ultra-thin copper layer side of a carrier-attached copper foil according to any one of claims 88 through 90, 95 through 97 and 100 through 102; forming a resin layer on the surface of the ultra-thin copper layer side of the carrier-attached copper foil so as to embed the circuit; forming a circuit on the resin layer; peeling off the carrier after the circuit has been formed on the resin layer; and removing the ultra-thin copper layer after the carrier has been peeled off to expose the circuit formed on the surface of the ultra-thin copper layer and embedded in the resin layer.

»

109. The method for manufacturing a printed wiring board according to claim 108, » LA wherein the step of forming the circuit on the resin layer includes the steps of affixing another carrier-attached copper foil on the resin layer from the ultra- = thin copper layer side, and forming the circuit using the carrier-attached copper foil affixed to the resin layer. foe

110. The method for manufacturing a printed wiring board according to claim 109, on wherein the other carrier-attached copper foil affixed to the resin layer isa carrier-attached copper foil according to any one of claims 88 through 90, 95 = through 97 and 100 through 102. =

111. The method for manufacturing a printed wiring board according to claim 108, wherein the step of forming the circuit on the resin layer is performed using the semi-additive method, subtractive method, partly additive method, or modified semi-additive method.

112. The method for manufacturing a printed wiring board according to claim 108 further comprising the step of forming a substrate on the carrier surface of the carrier-attached copper foil before peeling off the carrier.