KR102050646B1 - Copper foil provided with carrier - Google Patents

Abstract

The copper foil with a carrier suitable for fine pitch formation is provided. The copper foil with a carrier which has a copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling layer, an ultrathin copper layer is roughened, and Rz of the ultrathin copper layer surface is a non-contact roughness meter. Copper foil with a carrier measured and 1.6 micrometers or less.

Description

Copper foil with suitcase {COPPER FOIL PROVIDED WITH CARRIER}

The present invention relates to a copper foil with a carrier. More specifically, this invention relates to the copper foil with a carrier used as a material of a printed wiring board.

A printed wiring board is generally manufactured by adhering an insulated substrate to copper foil, making it a copper clad laminated board, and forming a conductor pattern on the copper foil surface by etching. In recent years, with the increase in the demand for miniaturization and high performance of electronic devices, high-density mounting of high-frequency components and high frequency of signals have been advanced, and the printed circuit board has been required to have finer conductor patterns (fine pitch) and higher frequency.

In response to fine pitching, copper foils having a thickness of 9 μm or less, and even 5 μm or less in recent years have been required. However, such ultra-thin copper foils have low mechanical strength and are cracked or wrinkled during manufacture of printed wiring boards. Since it is easy to carry out, the copper foil with a carrier which electrodeposited the ultra-thin copper layer through the peeling layer using the metal foil with a thickness as a carrier has emerged. After bonding the surface of an ultra-thin copper layer to an insulated substrate, and carrying out thermocompression bonding, the carrier is peeled off through a peeling layer. After forming a circuit pattern with a resist on the exposed ultra-thin copper layer, a microcircuit is formed by the method (MSAP: Modified-Semi-Additive-Process) which etchant removes an ultra-thin copper layer with the sulfuric acid-hydrogen peroxide type | system | group etchant.

Here, about the surface of the ultra-thin copper layer of the copper foil with a carrier used as the adhesive surface with resin, the thing with sufficient peeling strength of an ultrathin copper layer and a resin base material, and the peeling strength are high temperature heating, a wet process, soldering, chemicals It is desired to be sufficiently maintained even after the treatment or the like. As a method of increasing the peeling strength between an ultra-thin copper layer and a resin base material, generally, the method of attaching a large amount of roughening particle | grains on the ultra-thin copper layer which enlarged the surface profile (unevenness | corrugation, roughness) is typical. .

However, when the ultra-thin copper layer with such a large profile (concave-convex, roughness) is used for the semiconductor package substrate which needs to form especially a fine circuit pattern among printed wiring boards, an unnecessary copper particle remains at the time of circuit etching, and a circuit pattern Problems such as poor insulation between them occur.

For this reason, in WO2004 / 005588 (Patent Document 1), as a copper foil with a carrier for fine circuit applications including a semiconductor package substrate, it has been attempted to use a copper foil with a carrier which has not been subjected to a roughening treatment on the surface of an ultrathin copper layer. . The adhesiveness (peel strength) of the ultrathin copper layer and the resin which has not been subjected to such a roughening treatment tends to be lowered compared to a general copper foil for a printed wiring board under the influence of its low profile (unevenness, roughness, roughness). Therefore, further improvement is calculated | required about the copper foil with a carrier.

So, in Unexamined-Japanese-Patent No. 2007-007937 (patent document 2) and Unexamined-Japanese-Patent No. 2010-006071 (patent document 3), the surface which contacts (adheses) with the polyimide resin substrate of the ultra-thin copper foil with a carrier. Forming Ni layer or / and Ni alloy layer, forming chromate layer, forming Cr layer or / and Cr alloy layer, forming Ni layer and chromate layer, Ni layer and Cr layer Forming is described. By providing these surface treatment layers, the desired adhesive strength is obtained, without adjusting the adhesion strength of a polyimide-type resin substrate and the ultra-thin copper foil with a carrier, without reducing roughening process (fineness). Moreover, it also describes surface-treating with a silane coupling agent, or performing antirust process.

WO2004 / 005588 Japanese Unexamined Patent Publication No. 2007-007937 Japanese Unexamined Patent Publication No. 2010-006071

In the development of the copper foil with a carrier, the emphasis has been placed on securing the peel strength of the ultra-thin copper layer and the resin substrate until now. For this reason, the fine pitch has not been sufficiently studied yet, and there is still room for improvement. Then, this invention makes it a subject to provide the copper foil with a carrier suitable for fine pitch formation. Specifically, the object of the present invention is to provide a copper foil with a carrier capable of forming a finer wiring than L / S = 20 μm / 20 μm, which is considered to be a limit that can be formed by conventional MSAP.

In order to achieve the above object, the present inventors have intensively studied, and as a result, the surface of the ultrathin copper layer is lowered, and by forming fine roughened particles in the ultrathin copper layer, a uniform and low roughness roughened surface is formed. Found out it was possible to do. And it discovered that the said copper foil with a carrier was very effective for fine pitch formation.

This invention was completed based on the said knowledge, In one side, it is ultra-thin copper as a copper foil with a copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling layer. The layer is roughened, and Rz on the surface of the ultrathin copper layer is a copper foil with a carrier of 1.6 µm or less measured by a noncontact roughness meter.

This invention is another one side WHEREIN: The copper foil with a carrier provided with the copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling layer, The ultra-thin copper layer is roughly processed, and is ultra-thin Ra of the copper layer surface is copper foil with a carrier which is 0.3 micrometers or less measured by the non-contact roughness meter.

This invention is another one side. WHEREIN: As a copper foil with a carrier provided with the copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling layer, an ultra-thin copper layer is roughening-processed, Rt of the ultra-thin copper layer surface is copper foil with a carrier which is 2.3 micrometers or less measured by the non-contact roughness meter.

In one Embodiment of the copper foil with a carrier which concerns on this invention, Rz of the ultra-thin copper layer surface is 1.4 micrometers or less measured by the non-contact roughness meter.

In another embodiment of the copper foil with a carrier according to the present invention, Ra on the surface of the ultrathin copper layer is measured by a non-contact roughness meter and is 0.25 µm or less.

In another embodiment of the copper foil with a carrier according to the present invention, Rt on the surface of the ultrathin copper layer is 1.8 µm or less as measured by a non-contact roughness meter.

In another embodiment of the copper foil with a carrier according to the present invention, the ultrathin copper layer surface has an Ssk of −0.3 to 0.3.

In another one Embodiment of the copper foil with a carrier which concerns on this invention, Sku is 2.7-3.3 on the ultra-thin copper layer surface.

In another embodiment of the copper foil with a carrier according to the present invention, there is provided an ultrathin copper layer as a copper foil with a carrier, a peeling layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the peeling layer. Silver roughening process is carried out and the surface area ratio of the ultra-thin copper layer surface is 1.05-1.5.

In another embodiment of the copper foil with a carrier according to the present invention, the surface area ratio of the ultrathin copper layer surface is 1.05 to 1.5.

In another one Embodiment of the copper foil with a carrier which concerns on this invention, the volume per area 66524 micrometer <^2> of the ultra-thin copper layer surface is 300000 micrometer <^3> or more.

This invention is another one side. WHEREIN: It is the copper clad laminated board manufactured using the copper foil with a carrier which concerns on this invention.

This invention is another one side. WHEREIN: It is the printed wiring board manufactured using the copper foil with a carrier which concerns on this invention.

This invention is another one side. WHEREIN: It is the printed circuit board manufactured using the copper foil with a carrier.

In another aspect of the present invention,

The process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, a copper clad laminated board is formed through the process of peeling the carrier of the said copper foil with a carrier,

Then, it is a manufacturing method of the printed wiring board containing the process of forming a circuit by any method of the semiadditive method, the subtractive method, the partly additive method, or the modified semiadditive method.

The copper foil with a carrier which concerns on this invention is suitable for fine pitch formation, For example, wiring finer than L / S = 20 micrometer / 20 micrometer which was considered the limit which can be formed by MSAP process, for example, L / S It is possible to form a fine wiring of = 15 µm / 15 µm.

1 is an SEM photograph of the ultrathin copper layer M surface in Example 1 and Example 2. FIG.
2: C is a schematic diagram of the wiring board cross section in the process to circuit plating and resist removal concerning the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.
3: F is a schematic diagram of the wiring board cross section in the process from resin and copper foil laminated with a 2nd layer carrier to laser hole formation which concerns on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. .
FIG. 4: GI is a schematic diagram of the wiring board cross section in the process from via fill formation to 1st layer carrier peeling which concerns on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.
J-K of FIG. 5 is a schematic diagram of the wiring board cross section in the process from flash etching to bump copper filler formation which concerns on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention.

<1. Carrier

Copper foil is used as a carrier which can be used for this invention. The carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, an electrolytic copper foil is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating the plastic working by a rolling roll and heat processing. As the material of the copper foil, in addition to high-purity copper such as tough pitch copper or oxygen-free copper, for example, a copper alloy containing Sn-containing copper, Ag-containing copper, Cr, Zr, or Mg, or a Coulson-based copper containing Ni and Si, etc. Copper alloys such as copper alloys may also be used. In addition, when using the term "copper foil" independently in this specification, copper alloy foil shall also be included.

Although there is no restriction | limiting in particular also about the thickness of the carrier which can be used for this invention, What is necessary is just to adjust suitably to suitable thickness in fulfilling a role as a carrier, for example, it can be 12 micrometers or more. However, when it is too thick, since production cost will become high, it is generally preferable to set it as 70 micrometers or less. Therefore, the thickness of a carrier is typically 12-70 micrometers, More typically, it is 18-35 micrometers.

<2. Release Layer>

The release layer is formed on the carrier. As a peeling layer, it can be set as the arbitrary peeling layer known to a person skilled in the art in copper foil with a carrier. For example, the release layer may be any one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, their alloys, their hydrates, their oxides, or organics. It is preferable to form in the layer it contains. The release layer may be composed of a plurality of layers.

In one embodiment of this invention, a peeling layer is a single metal layer which consists of any 1 type of elements from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al from the carrier side, or An alloy layer composed of one or more elements selected from the group of elements Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Cr, Ni, Co, Fe, Mo, Ti, It consists of the layer which consists of the hydrate or oxide of 1 or more types of elements chosen from the element group of W, P, Cu, and Al.

It is preferable that a peeling layer consists of two layers, Ni and Cr. In this case, the Ni layer is laminated so as to be in contact with the interface with the copper foil carrier and the Cr layer is in contact with the interface with the ultrathin copper layer, respectively.

The release layer can be obtained, for example, by wet plating such as electroplating, electroless plating and immersion plating, or by dry plating such as sputtering, CVD and PDV. Electroplating is preferable from the viewpoint of cost.

<3. Ultrathin Copper Layer>

An ultrathin copper layer is formed on the release layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrolate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil, and copper sulfate bath can be formed at high current density. This is preferred. Although the thickness of an ultra-thin copper layer does not have a restriction | limiting in particular, Usually, it is thinner than a carrier and is 12 micrometers or less, for example. Typically, it is 0.5-12 micrometers, More typically, it is 2-5 micrometers.

<4. Surface treatment such as roughening process>

On the surface of an ultra-thin copper layer, a roughening process layer is formed by performing a roughening process, for example, for making adhesiveness with an insulating substrate favorable. A roughening process can be performed by forming roughening particle | grains with copper or a copper alloy, for example. It is preferable that a roughening process layer is comprised from fine particle from a viewpoint of fine pitch formation. Regarding the electroplating conditions when forming the roughened particles, when the current density is high, the copper concentration in the plating liquid is low, or the amount of coulomb is increased, the particles tend to be miniaturized.

The roughened layer may be composed of an electrodeposited grain made of an alloy containing any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc or any one or more kinds. have.

After the roughening treatment, secondary particles, tertiary particles, and / or rustproof layers and / or heat-resistant layers are formed of a single or alloy of nickel, cobalt, copper, zinc, or the like, and further chromated on the surface thereof, You may perform surface treatment, such as a silane coupling process. That is, you may form at least 1 type of layer chosen from the group which consists of a rustproof layer, a heat resistant layer, a chromate treated layer, and a silane coupling process layer on the surface of a roughening process layer.

For example, a heat resistant layer and / or a rustproof layer may be provided on the roughening process layer, and a chromate treated layer may be provided on the heat resistant layer and / or rustproof layer, and a silane coupling treatment layer may be provided on the chromate treated layer. It may be provided. In addition, the order which forms the said heat-resistant layer, a rustproof layer, a chromate treatment layer, and a silane coupling process layer is not mutually limited, You may form these layers in any order on a roughening process layer.

The surface of the ultra-thin copper layer (also referred to as "harmonized surface") after various surface treatments, such as roughening treatment, has a fine pitch formation of Rz (10 point average roughness) of 1.6 µm or less when measured by a non-contact roughness meter. It is very advantageous from the point of view. Rz is preferably 1.5 µm or less, more preferably 1.4 µm or less, even more preferably 1.35 µm or less, even more preferably 1.3 µm or less, even more preferably 1.2 µm or less, and still more. Preferably it is 1.0 micrometer or less, More preferably, it is 0.8 micrometer or less, More preferably, it is 0.6 micrometer or less. However, when Rz becomes too small, since adhesive force with resin falls, it is preferable that it is 0.01 micrometer or more, It is more preferable that it is 0.1 micrometer or more, It is still more preferable that it is 0.2 micrometer or more.

The surface of the ultrathin copper layer (also referred to as the "harmonized surface") after various surface treatments such as roughening treatment, has a Ra (arithmetic mean roughness) of 0.30 µm or less when measured with a non-contact roughness meter. Very advantageous in Ra is preferably 0.27 μm or less, more preferably 0.26 μm or less, even more preferably 0.25 μm or less, even more preferably 0.24 μm or less, even more preferably 0.23 μm or less, even more preferably 0.20 μm or less. It is still more preferably 0.18 µm or less, still more preferably 0.16 µm or less, still more preferably 0.15 µm or less, even more preferably 0.13 µm or less. However, when Ra becomes too small, since adhesive force with resin falls, it is preferable that it is 0.005 micrometers or more, It is more preferable that it is 0.009 micrometers or more, 0.01 micrometers or more, 0.02 micrometers or more, It is more preferable that it is 0.05 micrometers or more, 0.10 It is more preferable that it is micrometer or more.

The surface of the ultrathin copper layer (also referred to as a "harmonized surface") after performing various surface treatments such as roughening treatment, is very advantageous from the viewpoint of fine pitch formation to make Rt 2.3 m or less when measured by a non-contact roughness meter. Rt is preferably 2.2 µm or less, preferably 2.1 µm or less, preferably 2.07 µm or less, more preferably 2.0 µm or less, more preferably 1.9 µm or less, even more preferably 1.8 µm or less, further More preferably, it is 1.5 micrometers or less, More preferably, it is 1.2 micrometers or less, More preferably, it is 1.0 micrometer or less. However, when Rt becomes too small, since adhesive force with resin falls, it is preferable that it is 0.01 micrometer or more, It is more preferable that it is 0.1 micrometer or more, It is more preferable that it is 0.3 micrometer or more, It is more preferable that it is 0.5 micrometer or more.

Moreover, it is preferable from the viewpoint of fine pitch formation that the surface of the ultra-thin copper layer after performing various surface treatments, such as a roughening process, is set to -0.3-0.3 by Ssk (skewness) when it measures with a non-contact roughness meter. Preferably the minimum of Ssk is -0.2 or more, More preferably, it is -0.1 or more, More preferably, it is -0.070 or more, More preferably, it is -0.065 or more, More preferably, it is -0.060 or more, More preferably Preferably it is -0.058 or more, More preferably, it is 0 or more. The upper limit of Ssk is preferably 0.2 or less.

Moreover, it is preferable from the viewpoint of fine pitch formation that the surface of the ultra-thin copper layer after performing various surface treatments, such as a roughening process, shall be 2.7-3.3 when it measures with a non-contact roughness meter. Preferably the minimum of Sku is 2.8 or more, More preferably, it is 2.9 or more, More preferably, it is 3.0 or more. The upper limit of Sku is preferably 3.2 or less.

In the present invention, the roughness parameters of Rz and Ra on the surface of the ultrathin copper layer are based on JIS B0601-1994, the roughness parameters of Rt are based on JIS B0601-2001, and the ISO25178 draft for the roughness parameters of Ssk and Sku. Measure with a non-contact illuminometer according to

In the case where an insulating substrate such as a resin is adhered to the surface of an ultrathin copper layer such as a printed wiring board or a copper clad laminate, the surface roughness (Ra, Rt, Rz) can be measured.

For fine pitch formation, it is also important to control the volume of the roughened surface in order to reduce the etching amount of the roughened particle layer. The volume here refers to the value measured with a laser microscope, and becomes an index which evaluates the volume of the roughened particle which exists in a roughening process surface. When the volume of a roughening process surface is large, there exists a tendency for the adhesive force of an ultra-thin copper layer and resin to become high. And when the adhesive force of an ultra-thin copper layer and resin becomes high, there exists a tendency for migration resistance to improve. Specifically, the volume is measured by a laser microscope, preferably 300000 μm ³ or more, and more preferably 350000 μm ³ or more per 66524 μm ² of the roughened surface. However, when the volume is too large, the etching amount increases and a fine pitch cannot be formed, so the volume is preferably 500000 µm ³ or less, and more preferably 450000 µm ³ or less.

In addition, for fine pitch formation, it is also important to control the surface area ratio of the roughening process surface in order to ensure adhesiveness with resin by fine roughening particle | grains. The surface area ratio here is a value measured with a laser microscope and is a value of actual area / area when the area and the real area were measured. An area refers to a measurement reference area, and an actual area refers to the surface area in a measurement reference area. If the surface area ratio is too large, the adhesive strength increases, but the etching amount increases, and a fine pitch cannot be formed, while if the surface area ratio is too small, the adhesive strength cannot be secured. Therefore, the surface area ratio is preferably 1.05 to 1.5, preferably 1.07 to 1.47. , It is preferable that it is 1.09-1.4, and it is more preferable that it is 1.1-1.3.

<5. Resin Layer

In the copper foil with a carrier which concerns on this invention, you may further provide a resin layer on the surface of the ultra-thin copper layer after giving various surface treatments, such as a roughening process. For example, you may provide a resin layer on a roughening process layer, a heat resistant layer, a rustproof layer, a chromate treatment layer, or a silane coupling process layer. The resin layer may be an insulated resin layer.

The resin layer may be an adhesive resin, that is, an adhesive, or an insulating resin layer in a semi-cured state (B stage state) for adhesion. The semi-cured state (B stage state) does not have a tackiness even when the surface is touched by a finger, and the insulating resin layer can be superimposed and stored, and includes a state in which a curing reaction occurs when subjected to heat treatment.

Moreover, the said resin layer may contain thermosetting resin, and a thermoplastic resin may be sufficient as it. Moreover, the said resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. The resin layer is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application Laid-Open No. 11-140281. , Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 376375, Japanese Patent Application Publication No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Publication No. 2002-179772, Japanese Patent Application Publication Japanese Unexamined Patent Publication No. 2002-359444, Japanese Unexamined Patent Publication No. 2003-304068, Japanese Patent No. 3992225, Japanese Unexamined Patent Publication No. 2003-249739, Japanese Patent No. 4136509, Japanese Unexamined Patent Publication No. 2004-82687 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent Publication No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent Publication No. 4570070, Japanese Patent Application Laid-Open No. 2005-53218, Japanese Patent Publication No. 3949676 , Japanese Patent Publication No. 4178415, International Publication WO2004 / 005588, Japanese Unexamined Patent Publication No. 2006-257153, Japanese Unexamined Patent Publication No. 2007-326923, Japanese Unexamined Patent Publication No. 2008-111169, Japanese Patent No. 5014930, International Publication No. WO2006 / 028207, Japanese Patent Publication No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent Publication No. 5046927, Japanese Patent Application Publication No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Laid-Open Patent Publication 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, Japanese Laid-Open Patent Publication 2013-19056 You may form using the material (resin, resin hardening | curing agent, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, a polymer, a prepreg, a framework | skeletal material, etc.) and / or the formation method of a resin layer, and the formation apparatus which are described in the heading. .

Moreover, the kind of the said resin layer is not specifically limited, For example, an epoxy resin, a polyimide resin, a polyfunctional cyanate ester compound, a maleimide compound, a polymaleimide compound, a maleimide-type resin, aromatic maleim Mid resin, polyvinyl acetal resin, urethane resin, polyethersulfone (also called polyethersulfone, polyethersulfone), polyethersulfone (also called polyethersulfone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide Resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting poly Phenylene oxide resin, cyanate ester resin, carboxylic acid Anhydrides, anhydrides of polyhydric carboxylic acids, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-bis (4-cyanatophenyl) propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2- Bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin, isoprene, hydrogenated poly Resin containing 1 or more types chosen from the group of butadiene, polyvinyl butyral, phenoxy, high molecular weight epoxy, aromatic polyamide, fluorine resin, bisphenol, a block copolymerization polyimide resin, and a cyano ester resin is mentioned as a preferable thing. .

Moreover, if the said epoxy resin has two or more epoxy groups in a molecule | numerator, and can be used for an electrical / electronic material use, it can use without a problem especially. Moreover, the epoxy resin which the said epoxy resin epoxidized using the compound which has 2 or more glycidyl group in a molecule | numerator is preferable. In addition, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated (cancelled) epoxy Resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanate Glycidyl amine compounds, such as anurate and N, N- diglycidyl aniline, glycidyl ester compounds, such as tetrahydrophthalic acid diglycidyl ester, phosphorus containing epoxy resin, biphenyl type epoxy resin, and biphenyl furnace 1 type selected from the group of a volac type epoxy resin, a tris hydroxyphenylmethane type epoxy resin, and a tetraphenyl ethane type epoxy resin It may may be used by mixing two or more kinds, or to use a halogenated material chena hydrogenation of the epoxy resin.

As said phosphorus containing epoxy resin, the epoxy resin containing well-known phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in a molecule thereof. desirable.

The epoxy resin obtained as a derivative from this 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10. Naphthoquinone or hydroquinone was reacted with -oxide to form a compound represented by the following Chemical Formula 1 (HCA-NQ) or Chemical Formula 2 (HCA-HQ), and then an epoxy resin was reacted with a portion of the OH group to contain phosphorus. It was made with epoxy resin.

[Formula 1]

[Formula 2]

It is preferable that the phosphorus containing epoxy resin which is the said E component obtained using the above-mentioned compound as a raw material mixes 1 type or 2 types of the compound which has a structural formula shown in any of the following formula (3)-(5). This is because the stability of the resin quality in the semi-cured state is excellent and at the same time the flame retardant effect is high.

[Formula 3]

[Formula 4]

[Formula 5]

As the brominated (cancelled) epoxy resin, a known brominated (canceled) epoxy resin can be used. For example, the said brominated (cancelled) epoxy resin is a brominated epoxy resin provided with the structural formula shown in Formula 6 obtained as a derivative from tetrabromobisphenol A which has two or more epoxy groups in a molecule | numerator, and is shown by following formula (7) It is preferable to use 1 type or 2 types of brominated epoxy resins which have a structural formula.

[Formula 6]

[Formula 7]

As said maleimide resin, aromatic maleimide resin, a maleimide compound, or a polymaleimide compound, well-known maleimide resin, aromatic maleimide resin, a maleimide compound, or a polymaleimide compound can be used. For example, as maleimide resin, aromatic maleimide resin, maleimide compound, or polymaleimide compound, 4,4'- diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4 , 4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonbismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy ) Benzene and the compound and the polymer which polymerized the said compound or another compound, etc. can be used. The maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in a molecule, or may be a polymerization adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in a molecule, and a polyamine or an aromatic polyamine. do.

As said polyamine or aromatic polyamine, a well-known polyamine or aromatic polyamine can be used. For example, as a polyamine or an aromatic polyamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine , 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylether, 4,4'-diamino-3-methyldiphenylether , 4,4'-diaminodiphenylsulphide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulphone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diamino Diphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2- Bis (3-methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3-dimethyl-4-aminophenyl ) Phenyl ethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, and a polymer obtained by polymerizing the compound with the compound or the like can be used. Moreover, 1 type, or 2 or more types of well-known polyamine and / or aromatic polyamine or the above-mentioned polyamine or aromatic polyamine can be used.

A well-known phenoxy resin can be used as said phenoxy resin. Moreover, what is synthesize | combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin. As an epoxy resin, a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.

As said bisphenol, well-known bisphenol can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'- dihydroxy biphenyl, HCA (9,10-Dihydro-9- Bisphenol etc. which are obtained as an adduct of quinones, such as Oxa-10-Phosphaphenanthrene-10-Oxide), hydroquinone and a naphthoquinone, can be used.

As a linear polymer which has the said crosslinkable functional group, the linear polymer which has a well-known crosslinkable functional group can be used. For example, it is preferable that the linear polymer which has the said crosslinkable functional group is equipped with the functional group which contributes to hardening reaction of epoxy resins, such as a hydroxyl group and a carboxyl group. And it is preferable that the linear polymer which has this crosslinkable functional group is soluble in the organic solvent whose boiling point is 50 degreeC-200 degreeC temperature. Specific examples of the linear polymer having a functional group include polyvinyl acetal resin, phenoxy resin, polyether sulfone resin, polyamideimide resin and the like.

The said resin layer may also contain a crosslinking agent. As a crosslinking agent, a well-known crosslinking agent can be used. As a crosslinking agent, urethane type resin can be used, for example.

The rubbery resin may be a known rubbery resin. For example, the rubbery resin is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, Acrylic rubber (acrylic acid ester copolymer), polybutadiene rubber, isoprene rubber and the like. Moreover, when securing the heat resistance of the resin layer to form, it is also useful to select and use the synthetic rubber provided with heat resistance, such as a nitrile rubber, a chloroprene rubber, a silicone rubber, and a urethane rubber. About these rubbery resins, in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin, it is preferable to provide various functional groups at both ends. In particular, it is useful to use CTBN (carboxyl terminal butadienenitrile). Moreover, in an acrylonitrile butadiene rubber, if it is a carboxyl modified body, it can take a crosslinked structure with an epoxy resin, and can improve the flexibility of the resin layer after hardening. As a carboxyl modified body, a carboxyl terminal nitrile butadiene rubber (CTBN), a carboxyl terminal butadiene rubber (CTB), and a carboxy modified nitrile butadiene rubber (C-NBR) can be used.

As said polyamideimide resin, a well-known polyimide amide resin can be used. Moreover, as said polyimide amide resin, trimellitic anhydride, benzophenone tetracarboxylic anhydride, and bitolylene diisocyanate are N-methyl- 2-pyrrolidone or / and N, N- dimethylacetamide, for example. N-methyl-2-pyrrolidone or / and N, N-dimethylacetamide and the like obtained by heating in a solvent such as resin, trimellitic anhydride, diphenylmethane diisocyanate and carboxyl terminal acrylonitrile-butadiene rubber What is obtained by heating in the solvent of can be used.

As the rubber-modified polyamideimide resin, a known rubber-modified polyamideimide resin can be used. Rubber modified polyamideimide resin is obtained by making polyamideimide resin and rubbery resin react. The reaction of the polyamideimide resin with the rubbery resin is carried out for the purpose of improving the flexibility of the polyamideimide resin itself. That is, a polyamideimide resin and rubbery resin are made to react, and a part of acid components (cyclohexane dicarboxylic acid etc.) of a polyamideimide resin are substituted by a rubber component. As the polyamideimide resin, a known polyamideimide resin can be used. Moreover, well-known rubbery resin or the above-mentioned rubbery resin can be used for rubbery resin. When the rubber-modified polyamideimide resin is polymerized, solvents used for dissolving the polyamideimide resin and the rubbery resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and nitro. It is preferable to use 1 type, or 2 or more types of methane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, (gamma) -butyrolactone, etc. used.

As the phosphazene-based resin, a known phosphazene-based resin can be used. The phosphazene-based resin is a resin containing phosphazene having a double bond containing phosphorus and nitrogen as constituent elements. The phosphazene-based resin can significantly improve the flame retardant performance by synergistic effects of nitrogen and phosphorus in the molecule. In addition, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, the resin is stably present in the resin and an effect of preventing migration from occurring is obtained.

As said fluororesin, a well-known fluororesin can be used. Moreover, as a fluororesin, PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene hexafluoropropylene, for example) Copolymer (4.6 fluoride)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (bifluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallyl sulfone Or a fluororesin comprising at least one thermoplastic resin and a fluororesin selected from aromatic polysulfides and aromatic polyethers.

Moreover, the said resin layer may also contain the resin hardening | curing agent. As a resin hardener, a well-known resin hardener can be used. For example, as a resin hardening | curing agent, amines, such as dicyandiamide, imidazole, aromatic amine, phenols, such as bisphenol A and brominated bisphenol A, novolaks, such as a phenol novolak resin and cresol novolak resin, phthalic anhydride, etc. Acid anhydride, biphenyl type phenol resin, phenol aralkyl type phenol resin, etc. can be used. Moreover, the said resin layer may also contain 1 type (s) or 2 or more types of the above-mentioned resin hardening | curing agent. These curing agents are particularly effective for epoxy resins.

The specific example of the said biphenyl type phenol resin is shown in General formula (8).

[Formula 8]

Moreover, the specific example of the said phenol aralkyl type phenol resin is shown in General formula (9).

[Formula 9]

As imidazole, a well-known thing can be used, For example, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4- methylimidazole, 2-phenyl-4- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. can be mentioned, These can be used individually or in mixture.

Moreover, it is preferable to use the imidazole provided with the structural formula shown by following formula (10) especially. By using the imidazole of the structural formula shown in this formula (10), the hygroscopicity of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. It is because imidazole performs a catalytic action at the time of hardening of an epoxy resin, and contributes as a reaction initiator which causes the self-polymerization reaction of an epoxy resin in the initial stage of a hardening reaction.

[Formula 10]

As the resin curing agent of the amines, known amines can be used. Moreover, as the resin curing agent of the said amines, the above-mentioned polyamine and aromatic polyamine can be used, for example, Moreover, aromatic polyamine, polyamide, and the amine adduct obtained by superposing | polymerizing or condensing these with an epoxy resin or polyhydric carboxylic acid, You may use 1 type, or 2 or more types chosen from the group of. Moreover, as a resin hardening | curing agent of the said amines, 4,4'- diamino diphenylene sulfone, 3,3'- diamino diphenylene sulfone, 4, 4- diamino diphenyrel, 2, 2-bis [ It is preferable to use any one or more of 4- (4-aminophenoxy) phenyl] propane or bis [4- (4-aminophenoxy) phenyl] sulfone.

The said resin layer may also contain a hardening accelerator. As a hardening accelerator, a well-known hardening accelerator can be used. For example, tertiary amine, imidazole, urea-type hardening accelerator, etc. can be used as a hardening accelerator.

The said resin layer may also contain a reaction catalyst. As a reaction catalyst, a well-known reaction catalyst can be used. For example, finely divided silica, antimony trioxide, or the like can be used as the reaction catalyst.

It is preferable that the anhydride of the said polyhydric carboxylic acid is a component which contributes as a hardening | curing agent of an epoxy resin. Moreover, the anhydride of the said polyhydric carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, a pyromellitic dianhydride, tetrahydroxy phthalic anhydride, hexahydroxy phthalic anhydride, methyl hexahydroxy phthalic anhydride, nadine acid, It is preferable that it is methylnadic acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than the epoxy resin and the alcoholic hydroxyl group polymerizable.

The polyvinyl acetal resin may have a functional group polymerizable with an epoxy resin or maleimide compound other than an acid group and a hydroxyl group. Moreover, the polyvinyl acetal resin may introduce | transduce a carboxyl group, an amino group, or an unsaturated double bond in the molecule | numerator.

As said aromatic polyamide resin polymer, what is obtained by making an aromatic polyamide resin and rubbery resin react is mentioned. Here, an aromatic polyamide resin is synthesize | combined by polycondensation of aromatic diamine and dicarboxylic acid. 4,4'- diamino diphenylmethane, 3,3'- diamino diphenyl sulfone, m-xylenediamine, 3,3'- oxydianiline, etc. are used for aromatic diamine at this time. And phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, etc. are used for dicarboxylic acid.

As the rubbery resin to be reacted with the aromatic polyamide resin, a known rubbery resin or the above-mentioned rubbery resin can be used.

This aromatic polyamide resin polymer is used for the purpose of not being damaged by under etching by etching liquid, when etching the copper foil after processing with the copper clad laminated board.

In addition, the said resin layer sequentially turns a cured resin layer (a "cured resin layer shall mean a hardened resin layer) and a semi-hardened resin layer in order from the copper foil side (namely, the ultra-thin copper layer side of the copper foil with a carrier). The formed resin layer may be sufficient. The cured resin layer may be composed of a polyimide resin having a thermal expansion coefficient of 0 ppm / ° C to 25 ppm / ° C, a polyamideimide resin, or a resin component of any of these composite resins.

Moreover, you may form the semi-hardened resin layer whose thermal expansion coefficient after hardening is 0 ppm / degreeC-50 ppm / degreeC on the said cured resin layer. Moreover, the thermal expansion coefficient of the whole resin layer after hardening of the said cured resin layer and the said semi-hardened resin layer may be 40 ppm / degrees C or less. 300 degreeC or more of glass transition temperature may be sufficient as the said cured resin layer. The semi-cured resin layer may be formed by using a maleimide resin or an aromatic maleimide resin. It is preferable that the resin composition for forming the said semi-hardened resin layer contains maleimide resin, an epoxy resin, and the linear polymer which has a crosslinkable functional group. The epoxy resin can use a well-known epoxy resin or the epoxy resin described in this specification. Moreover, as a linear polymer which has a maleimide resin, an aromatic maleimide resin, and a crosslinkable functional group, a well-known maleimide resin, aromatic maleimide resin, the linear polymer which has a crosslinkable functional group, or the above-mentioned maleimide type resin, aromatic maleim The linear resin which has a mid resin and a crosslinkable functional group can be used.

Moreover, when providing the copper foil with a carrier which has a resin layer suitable for the use for manufacture of a three-dimensionally molded printed wiring board, it is preferable that the said cured resin layer is a high polymer polymer layer which has hardened flexibility. It is preferable that the said high molecular polymer layer consists of resin which has a glass transition temperature of 150 degreeC or more so that a solder mounting process can be endured. It is preferable that the said high molecular polymer layer consists of any 1 type, or 2 or more types of mixed resin of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin. . Moreover, it is preferable that the thickness of the said high molecular polymer layer is 3 micrometers-10 micrometers.

Moreover, it is preferable that the said high molecular polymer layer contains any 1 type, or 2 or more types of an epoxy resin, a maleimide-type resin, a phenol resin, and a urethane resin. Moreover, it is preferable that the said semi-hardened resin layer is comprised from the epoxy resin composition whose thickness is 10 micrometers-50 micrometers.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component-E component.

A component: The epoxy resin which is an epoxy equivalent of 200 or less and consists of 1 type (s) or 2 or more types chosen from the group of a liquid bisphenol-A epoxy resin, bisphenol F-type epoxy resin, and a bisphenol AD-type epoxy resin at room temperature.

B component: High heat resistant epoxy resin.

C component: Phosphorus containing flame-retardant resin which is any 1 type of phosphorus containing epoxy resin and phosphazene resin, or resin which mixed these.

D component: Rubber modified polyamideimide resin modified | denatured by the liquid rubber component which has a boiling point in the solvent in the range of 50 degreeC-200 degreeC.

E component: Resin hardener.

B component is "high heat resistant epoxy resin" with high so-called glass transition point Tg. It is preferable that "high heat resistant epoxy resin" here is polyfunctional epoxy resins, such as a novolak-type epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, and a naphthalene type epoxy resin.

As a phosphorus containing epoxy resin of C component, the above-mentioned phosphorus containing epoxy resin can be used. Moreover, the phosphazene-type resin mentioned above can be used as C component phosphazene-type resin.

As the rubber-modified polyamideimide resin of the D component, the rubber-modified polyamideimide resin described above can be used. As the resin curing agent of the E component, the above-mentioned resin curing agent can be used.

A solvent is added to the resin composition shown above and used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. Resin when the said resin varnish adds a solvent to the resin composition mentioned above, it is prepared in the range whose resin solid content is 30 wt%-70 wt%, and measured based on MIL-P-13949G in MIL specification. Formation of the semi-hardened resin film in which a flow is 5 to 35% of range is possible. A well-known solvent or the solvent mentioned above can be used for a solvent.

The said resin layer is a resin layer which has a 1st thermosetting resin layer and the 2nd thermosetting resin layer located in the surface of the said 1st thermosetting resin layer in order from a copper foil side, and a 1st thermosetting resin layer is a wiring board It is formed with the resin component which does not melt | dissolve in the chemical | medical agent at the time of the desmear process in a manufacturing process, The 2nd thermosetting resin layer uses resin which melt | dissolves and wash | cleans and removes the chemical | medical agent at the time of desmear process in a wiring board manufacturing process. And may be formed. The said 1st thermosetting resin layer may be formed using the resin component which mixed any 1 type or 2 or more types of polyimide resin, polyether sulfone, and polyphenylene oxide. The second thermosetting resin layer may be formed by using an epoxy resin component. When thickness t1 (micrometer) of a said 1st thermosetting resin layer makes rough surface roughness of copper foil with a carrier Rz (micrometer), and when thickness of the 2nd thermosetting resin layer is t2 (micrometer), t1 is Rz It is preferable that it is thickness which satisfy | fills the conditions of <t1 <t2.

The resin layer may be a prepreg in which the skeleton is impregnated with a resin. It is preferable that resin impregnated to the said skeleton material is a thermosetting resin. The prepreg may be a known prepreg or a prepreg used for manufacturing a printed wiring board.

The framework may include aramid fibers or glass fibers or wholly aromatic polyester fibers. It is preferable that the said framework material is a nonwoven fabric or a woven fabric of aramid fiber or glass fiber, or a wholly aromatic polyester fiber. Moreover, it is preferable that the said total aromatic polyester fiber is a wholly aromatic polyester fiber whose melting | fusing point is 300 degreeC or more. The said all aromatic polyester fiber whose melting point is 300 degreeC or more is a fiber manufactured using resin called what is called a liquid crystal polymer, The said liquid crystal polymer is a polymer of 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid. It is a main ingredient. Since this all aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has the outstanding performance as a component of an electrical insulation layer, and can use it like a glass fiber and an aramid fiber.

Moreover, in order to improve the wettability with resin of the surface, the fiber which comprises the said nonwoven fabric and a woven fabric is preferable to process a silane coupling agent. The silane coupling agent at this time can use silane coupling agents, such as a well-known amino type and epoxy type, or the above-mentioned silane coupling agent according to a use purpose.

The prepreg may be a non-woven fabric using aramid fibers or glass fibers having a nominal thickness of 70 μm or less, or a prepreg impregnated with a thermosetting resin in a skeleton made of glass cross having a nominal thickness of 30 μm or less.

(When the resin layer contains a dielectric (dielectric filler))

The resin layer may contain a dielectric (dielectric filler).

In the case where the dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, the capacitance of the capacitor circuit can be increased for use in forming a capacitor layer. This dielectric material (dielectric filler) includes a dielectric powder of a composite oxide having a pebrose structure such as BaTiO 3, SrTiO 3, Pb (Zr-Ti) O 3 (common name PZT), PbLaTiO 3 · PbLaZrO (common name PLZT), and SrBi2Ta2O9 (common name SBT). Use

The dielectric (dielectric filler) may be powdery. In the case where the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) need to be in the range of 0.01 µm to 3.0 µm, preferably 0.02 µm to 2.0 µm, in particle size. The particle diameter used here is used because the granules form a certain secondary agglomerated state, and thus the precision is inferior in the indirect measurement of estimating the average particle diameter from measured values such as laser diffraction scattering particle size distribution measurement method or BET method. It refers to an average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. In this specification, the particle diameter at this time is represented by DIA. In addition, the image analysis of the powder of the dielectric (dielectric filler) observed using the scanning electron microscope (SEM) in this specification uses the Asahi Engineering Co., Ltd. IP-1000PC, and is a roundness threshold. Circular particle analysis was performed with the value 10 and the overlap degree 20, and the average particle diameter DIA was calculated | required.

By the above-mentioned embodiment, the carrier which has a resin layer containing the dielectric material for improving the adhesiveness of the inner-layer circuit surface of the said inner-layer core material, and the resin layer containing a dielectric material, and forming a capacitor circuit layer with low dielectric tangent. Attached copper foil can be provided.

Resin and / or resin composition and / or compound contained in the above-mentioned resin layer are, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol , Ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylform It melt | dissolves in solvents, such as an amide, and makes it resin resin (resin varnish), and rolls it on the said ultra-thin copper layer, or the said heat-resistant layer, a rustproof layer, or the said chromate treatment layer, or the said silane coupling agent layer, for example. Coating is carried out by a coater method or the like, followed by heating and drying as necessary to remove the solvent to obtain a B stage state. For drying, for example, a hot air drying furnace may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the said resin layer is melt | dissolved using a solvent, The resin solid content is 3 wt%-70 wt%, Preferably it is 3 wt%-60 wt%, Preferably it is 10 wt%-40 wt%, More preferably, It is good also as a resin liquid of 25 wt%-40 wt%. In addition, dissolution using a mixed solvent of methyl ethyl ketone and cyclopentanone is most preferable at this stage from an environmental point of view. Moreover, it is preferable to use the solvent whose boiling point is a range of 50 degreeC-200 degreeC for a solvent.

Moreover, it is preferable that the said resin layer is a semi-hardened resin film whose resin flow at the time of measuring based on MIL-P-13949G in MIL specification exists in 5 to 35% of range.

In this specification, with resin resin, based on MIL-P-13949G in MIL specification, four samples of 10 cm in width and width are sampled from the copper foil with resin which made resin thickness 55 micrometers, and these four samples Is bonded based on the press temperature of 171 ° C., the press pressure of 14 kgf / cm 2, and the press time of 10 minutes in an overlapped state (laminate), and the value calculated based on Equation 1 from the result of measuring the resin outflow weight at that time. to be.

The copper foil with a carrier (copper foil with a carrier with a resin) with the said resin layer superimposes the resin layer, and heat-presses the whole, thermosets the resin layer, and then peels a carrier and makes an ultra-thin copper layer It is used in the aspect which expresses (the natural thing is surface of the intermediate | middle layer side of the ultra-thin copper layer), and forms a predetermined wiring pattern there.

When the copper foil with a carrier with this resin is used, the number of sheets of prepreg material at the time of manufacture of a multilayer printed wiring board can be reduced. Moreover, the thickness of a resin layer can be made into the thickness which can ensure interlayer insulation, or a copper clad laminated board can be manufactured, without using a prepreg material at all. At this time, the surface of the substrate can be undercoated with an insulating resin to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is reduced, and the lamination process is simplified, which is economically advantageous, and the thickness of the multilayer printed wiring board manufactured by the thickness of the prepreg material is There is an advantage that it can be made thin and an ultra-thin multilayer printed wiring board having a thickness of one layer of 100 µm or less can be produced.

It is preferable that the thickness of this resin layer is 0.1-120 micrometers.

When the thickness of the resin layer becomes thinner than 0.1 µm, the adhesive force decreases, and when the copper foil with a carrier with this resin is laminated on a substrate having an inner layer material without interposing a prepreg material, the interlayer insulation between the circuits of the inner layer material It may be difficult to secure. On the other hand, when the thickness of a resin layer is thicker than 120 micrometers, it becomes difficult to form the resin layer of the target thickness in one application | coating process, and it may become disadvantageous economically because extra material cost and process number are needed.

Moreover, when the copper foil with a carrier which has a resin layer is used for manufacturing an ultra-thin multilayer printed wiring board, the thickness of the said resin layer is 0.1 micrometer-5 micrometers, More preferably, 0.5 micrometer-5 micrometers, More preferably, It is preferable to set it as 1 micrometer-5 micrometers in order to make thickness of a multilayer printed wiring board small.

Moreover, when a resin layer contains a dielectric material, it is preferable that the thickness of a resin layer is 0.1-50 micrometers, It is preferable that it is 0.5 micrometer-25 micrometers, It is more preferable that it is 1.0 micrometer-15 micrometers.

The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 µm to 120 µm, preferably 5 µm to 120 µm, preferably 10 µm to 120 µm, and 10 µm. It is more preferable that it is-60 micrometers. And it is preferable that the thickness of cured resin layer is 2 micrometers-30 micrometers, It is preferable that it is 3 micrometers-30 micrometers, It is more preferable that it is 5-20 micrometers. Moreover, it is preferable that the thickness of a semi-hardened resin layer is 3 micrometers-55 micrometers, It is preferable that it is 7 micrometers-55 micrometers, It is more preferable that it is 15-115 micrometers. When the total resin layer thickness exceeds 120 µm, it may be difficult to manufacture a thin multilayer printed wiring board, and when it is less than 5 µm, it becomes easy to form a thin multilayer printed wiring board, but between circuits of the inner layer This is because the resin layer, which is an insulating layer of, may become too thin and a tendency to destabilize the insulation between circuits of the inner layer may occur. Moreover, when the cured resin layer thickness is less than 2 micrometers, the surface roughness of a copper foil roughening surface may arise. On the contrary, when the thickness of cured resin layer exceeds 20 micrometers, the effect by the hardened resin layer may not improve especially, and the total insulation layer thickness will become thick.

Moreover, when setting the thickness of the said resin layer to 0.1 micrometer-5 micrometers, in order to improve the adhesiveness of a resin layer and copper foil with a carrier, a heat-resistant layer and / or an rustproof layer, and / or a chromate treatment layer on an ultra-thin copper layer, and After forming a silane coupling process layer, it is preferable to form a resin layer on the said heat-resistant layer, a rustproof layer, a chromate treatment layer, or a silane coupling process layer.

In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary ten points.

Moreover, as another product form of the copper foil with a carrier with this resin, a resin layer is on the said ultra-thin copper layer, or on the said heat-resistant layer, a rustproof layer, or the said chromate treatment layer, or the said silane coupling process layer. It is also possible to coat | cover with and to make it semi-hardened, and then peeling a carrier and manufacturing it in the form of the copper foil with resin which carrier does not exist.

<6. Copper foil with suitcase ＞

Thus, the copper foil with a carrier provided with the copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, the ultra-thin copper layer laminated | stacked on the peeling layer, and a voluntary resin layer is manufactured. Although the usage method of the copper foil with a carrier itself is well-known to those skilled in the art, For example, the surface of an ultra-thin copper layer is made into a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth, a paper composite base material epoxy resin, and a glass cloth. An ultra-thin copper layer bonded to an insulating substrate such as a glass nonwoven composite base epoxy resin and a glass cloth base epoxy resin, a polyester film, a polyimide film, and bonded to a copper-clad laminate by peeling a carrier after thermal compression, is used. It can be etched with a conductor pattern to be used and finally a printed wiring board can be manufactured. Moreover, a printed circuit board is completed by mounting electronic components in a printed wiring board. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

In one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention, the process of preparing the copper foil with a carrier and an insulated substrate concerning this invention, the process of laminating the said copper foil with a carrier, and an insulated substrate, the said copper foil with a carrier, and an insulated substrate After lamination | stacking so that an ultra-thin copper layer side may face an insulated substrate, a copper clad laminated board is formed through the process of peeling the carrier of the said copper foil with a carrier, and the semiadditive process, the modified semiadditive process, and a partly The process of forming a circuit by any of an additive method and a subtractive method is included. It is also possible for the insulating substrate to have an inner layer circuit inserted therein.

In the present invention, the semi-additive method refers to a method of forming a conductive pattern using electroplating and etching after forming a pattern on a thin electroless plating on an insulating substrate or a copper foil seed layer.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Removing all of the ultra-thin copper layers exposed by peeling the carrier by a method such as etching or plasma using a corrosion solution such as an acid,

A step of forming through-holes and / or blind vias in the insulating substrate exposed by removing the ultrathin copper layer by etching and, if present, in the resin layer;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on a region comprising said resin and said through hole or / and blind via,

Forming a plating resist on the electroless plating layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Removing all of the ultra-thin copper layers exposed by peeling the carrier by a method such as etching or plasma using a corrosion solution such as an acid,

Forming an electroless plating layer on the surface of the insulating substrate exposed or the resin layer, if present, by removing the ultrathin copper layer by etching;

Forming a plating resist on the electroless plating layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In the present invention, the modified semi-additive method is to remove a resist after laminating a metal foil on an insulating layer, protecting the non-circuit forming portion by a plating resist, and forming the copper thickness of the circuit forming portion by electroplating. And the method of forming a circuit on an insulating layer by removing metal foils other than the said circuit formation part by (flash) etching is pointed out.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the Modified semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier;

After forming the plating resist, forming a circuit by electroplating,

Removing the plating resist,

Removing the ultrathin copper layer exposed by removing the plating resist by flash etching;

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the modified semiadditive process, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Peeling the carrier to form a plating resist on the exposed ultrathin copper layer,

Exposing to the plating resist and then removing the plating resist in the region where the circuit is formed;

Forming an electroplating layer in a region where the circuit from which the plating resist is removed is formed;

Removing the plating resist,

Removing the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like,

It includes.

In the present invention, the partly additive method is provided with a catalyst nucleus on a substrate formed by forming a conductor layer and a substrate formed through holes for through holes and via holes, if necessary, to form a conductor circuit, After forming a soldering resist or plating resist as needed, the method of manufacturing a printed wiring board is performed by forming thickness by electroless-plating process on the said conductor circuit, a through hole, a via hole, etc.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using a partly additive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Applying a catalyst nucleus to a region comprising said through hole or / and blind via,

Forming an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier;

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

Removing the ultrathin copper layer and the catalyst nucleus by etching or plasma using a corrosion solution such as an acid to form a solder resist or a plating resist on the exposed surface of the insulating substrate,

Forming an electroless plating layer in a region where the solder resist or the plating resist is not formed,

It includes.

In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of copper foil on a copper clad laminate by etching or the like to form a conductor pattern.

Therefore, in one Embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the subtractive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming an electroplating layer on the surface of the electroless plating layer,

Forming an etching resist on the surface of the electroplating layer and / or the ultrathin copper layer,

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer, the electroless plating layer, and the electroplating layer by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

It includes.

In another embodiment of the manufacturing method of the printed wiring board which concerns on this invention using the subtractive method, the process of preparing the copper foil with a carrier which concerns on this invention, and an insulated substrate,

Laminating the copper foil with a carrier and an insulating substrate;

After laminating | stacking the said copper foil with a carrier and an insulated substrate, the process of peeling the carrier of the said copper foil with a carrier,

Forming a through hole or / and a blind via in the ultrathin copper layer and the insulating substrate exposed by peeling the carrier;

Performing a desmear treatment on the region including the through hole and / or the blind via,

Forming an electroless plating layer on the region including the through hole and / or the blind via,

Forming a mask on the surface of the electroless plating layer,

Forming an electroplating layer on the surface of the electroless plating layer on which no mask is formed;

Forming an etching resist on the surface of the electroplating layer and / or the ultrathin copper layer,

Exposing the etching resist and forming a circuit pattern;

Removing the ultrathin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosion solution such as an acid to form a circuit,

Removing the etching resist,

It includes.

The step of forming the through hole or / and the blind via and the subsequent desmear step need not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, although the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer was formed here is demonstrated to an example, it is not limited to this, The same print is also performed using the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer is not formed. The manufacturing method of a wiring board can be implemented.

First, as shown to FIG. 2-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed in the surface is prepared.

Next, as shown to FIG. 2-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and development are performed, and a resist is etched to a predetermined shape.

Next, as shown to FIG. 2-C, after forming metal plating for circuits, circuit plating of a predetermined shape is formed by removing a resist.

Next, as shown to FIG. 3-D, embedding resin is formed on the ultra-thin copper layer so that circuit plating may be covered (so that circuit plating may be buried), a resin layer is laminated | stacked, and copper foil with another carrier (2nd layer) is then continued. Is bonded from the ultrathin copper layer side.

Next, as shown to FIG. 3-E, a carrier is peeled off from the copper foil with a carrier of a 2nd layer.

Next, as shown to FIG. 3-F, a laser hole is formed in the predetermined position of a resin layer, and circuit plating is exposed and a blind via is formed.

Next, as shown to FIG. 4-G, copper is embedded in a blind via and a via fill is formed.

Next, as shown to FIG. 4-H, circuit plating is formed on a via fill like FIG. 2-B and FIG. 2-C.

Next, as shown to FIG. 4-I, a carrier is peeled off from the copper foil with a carrier of a 1st layer.

Next, as shown to FIG. 5-J, the ultra-thin copper layer of both surfaces is removed by flash etching, and the surface of the circuit plating in a resin layer is exposed.

Next, as shown to FIG. 5-K, bump is formed on the circuit plating in a resin layer, and a copper filler is formed on the said solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is manufactured.

The said other copper foil with a carrier (2nd layer) may use the copper foil with a carrier of this invention, you may use the conventional copper foil with a carrier, and may use a normal copper foil. Moreover, you may form a circuit 1 layer or multiple layers further on the 2nd layer circuit shown to FIG. 4-H, and those circuit formation may be semiadditive method, subtractive method, partly additive method, or modified. You may implement by any method of the semiadditive process.

Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate or the resin layer, the copper foil with a carrier used for 1st layer is supported, and since a wrinkle becomes hard to enter, there exists an advantage that productivity improves. Moreover, as long as there is an effect which supports the copper foil with a carrier used for the said 1st layer, all the board | substrates can be used for the said board | substrate. For example, as said board | substrate, the carrier, prepreg, resin layer, a well-known carrier, prepreg, resin layer, a metal plate, metal foil, the plate of an inorganic compound, the foil of an inorganic compound, the plate of an organic compound, the organic compound which are described in this specification Park can be used.

Although there is no restriction | limiting in particular about the timing which forms a board | substrate on a carrier side surface, It is necessary to form before peeling a carrier. It is preferable to form before a process of forming a resin layer in the said ultra-thin copper layer side surface of the said copper foil with a carrier especially, and to form before a process of forming a circuit in the said ultra-thin copper layer side surface of the copper foil with a carrier.

It is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the ultra-thin copper layer surface may satisfy the following (1). In this invention, when the color difference of the surface of an ultra-thin copper layer or various surface treatments, such as a roughening process, is given, the color difference of the surface treatment layer surface is shown. That is, it is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, or a rustproof layer, or a chromate treatment layer, or a silane coupling layer may satisfy the following (1). .

(1) Color difference (DELTA) E * ab based on JISZ8730 of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, or a rustproof layer, or a chromate treated layer, or a silane coupling process layer is 45 or more.

Here, color difference (DELTA) L, (D) a, (DELTA) b is a comprehensive index measured with a color difference meter, respectively, and adds black / white / red / green / yellow / blue, and shows it using the L * a * b colorimeter based on JIS Z8730, ΔL: black and white, Δa: red green, Δb: yellow. Moreover, (DELTA) E * ab is represented by a following formula using these color differences.

The color difference mentioned above can be adjusted by making the current density at the time of ultra-thin copper layer formation high, making copper concentration low in a plating liquid, and making high the line flow velocity of a plating liquid.

Moreover, the color difference mentioned above can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer, and forming a roughening process layer. In the case of forming the roughened layer, the current density is higher than the conventional one (for example, 40 to 60 A) by using an electric field solution containing at least one element selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / dm 2) and can be adjusted by shortening the treatment time (for example, 0.1 to 1.3 seconds). When the roughening layer is not formed on the surface of the ultrathin copper layer, an ultrathin copper layer or a heat resistant layer or an rustproof layer or a chromate treated layer or a silane coupler is used by using a plating bath having a concentration of Ni 2 times or more of other elements. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, and Ni-Zn alloy plating) is treated on the surface of the ring treatment layer at a lower current density (0.1 to 1.3 A / dm 2) than before. It can achieve by setting time (20 second-40 second) and processing.

When the color difference ΔE * ab based on JISZ8730 on the ultrathin copper layer surface is 45 or more, for example, when forming a circuit on the ultrathin copper layer surface of the copper foil with a carrier, the contrast between the ultrathin copper layer and the circuit becomes clear, and as a result, The visibility is good, and the circuit can be aligned with good accuracy. Color difference (DELTA) E * ab based on JISZ8730 on the surface of an ultra-thin copper layer becomes like this. Preferably it is 50 or more, More preferably, it is 55 or more, More preferably, it is 60 or more.

When the color difference of the surface of an ultra-thin copper layer or a roughening process layer, a heat resistant layer, or a rustproof layer, or a chromate treatment layer, or a silane coupling layer is controlled as mentioned above, contrast with circuit plating becomes clear and visibility is favorable. Therefore, in the manufacturing process as shown in FIG. 2-C of the printed wiring board mentioned above, for example, it becomes possible to form circuit plating in a predetermined position with favorable precision. Moreover, according to the manufacturing method of the printed wiring board mentioned above, since the circuit plating is a structure embedded in the resin layer, when the ultra-thin copper layer is removed by flash etching as shown to FIG. 5-J, for example. In this way, the circuit plating is protected by the resin layer, and the shape thereof is maintained, thereby facilitating formation of a fine circuit. Moreover, since circuit plating is protected by a resin layer, migration resistance improves and the conduction of the wiring of a circuit is suppressed favorably. For this reason, formation of a fine circuit becomes easy. Moreover, when the ultra-thin copper layer is removed by flash etching as shown to FIG. 5-J and FIG. 5-K, since the exposed surface of circuit plating becomes the shape recessed from the resin layer, bumps are formed on the said circuit plating, Moreover, a copper filler becomes easy to form on it, respectively, and manufacturing efficiency improves.

In addition, well-known resin and prepreg can be used for embedding resin (resin). For example, prepreg which is glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film and ABF made by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg described in this specification can be used for the said embedded resin (resin).

Example

Hereinafter, although an Example of this invention demonstrates this invention still in detail, this invention is not limited at all by these Examples.

1. Manufacture of Copper Foil with Carrier

<Example 1>

As the copper foil carrier, a long electrolytic copper foil (JTC manufactured by JX Nikko-Niseki Metal Co., Ltd.) having a thickness of 35 µm was prepared. About the shiny surface of this copper foil, Ni layer of 4000 microgram / dm <2> adhesion amount was formed by electroplating with the roll-to-roll type continuous plating line on condition of the following.

Ni layer

Nickel sulfate: 250 to 300 g / l

Nickel chloride: 35 to 45 g / l

Nickel acetate: 10 to 20 g / l

Trisodium citrate: 15 to 30 g / l

Brightener: Saccharin, butynediol

Sodium dodecyl sulfate: 30 to 100 ppm

pH ： 4 to 6

Bath temperature: 50-70 degrees Celsius

Current density: 3 to 15 A / dm 2

After water washing and pickling, a Cr layer having an adhesion amount of 11 µg / dm 2 was deposited on the Ni layer by an electrolytic chromate treatment on a roll-to-roll type continuous plating line 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 degrees Celsius

Current density: 0.1 to 2.6 A / dm 2

Coulomb amount: 0.5-30 As / dm 2

Subsequently, on the continuous rolling line of a roll-to-roll type | mold, it formed by electroplating the ultra-thin copper layer of thickness 3micrometer on the Cr layer on condition of the following, and manufactured copper foil with a carrier. In addition, in the present Example, it manufactured also about the copper foil with a carrier which made the thickness of an ultra-thin copper layer 2, 5, and 10 micrometers, and evaluated similarly to the Example whose thickness of an ultra-thin copper layer is 3 micrometers. The results were the same regardless of the thickness.

Ultrathin copper layer

Copper concentration: 30-120 g / l

H ₂ SO ₄ concentration: 20-120 g / l

Electrolyte temperature: 20-80 degreeC

Current density: 10 to 100 A / dm 2

Next, the following roughening process 1, roughening process 2, rust prevention process, chromate treatment, and silane coupling process were performed to the ultra-thin copper layer surface in this order.

Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

W ： 0-50 mg / l

Sodium dodecyl sulfate: 0-50 mg / l

As: 0-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 degrees Celsius

Current density: 25 to 110 A / dm 2

Harmonic coulomb amount: 50-500 As / dm 2

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

Temperature: 30-70 degrees Celsius

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50-300 As / dm 2

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH ： 40 to 200 g / l

NaCN ： 70-250 g / ℓ

CuCN ： 50 to 200 g / ℓ

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Liquid temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 to 20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l

NaOH or KOH ： 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20-80 degrees Celsius

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

<Example 2>

After the ultrathin copper layer was formed on the copper foil carrier on the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust-preventing treatment, chromate treatment, and silane coupling treatment were performed in this order. In addition, the thickness of ultra-thin copper foil was 3 micrometers.

Harmonization processing 1

Liquid composition: Copper 10-20 g / l, sulfuric acid 50-100 g / l

Liquid temperature: 25-50 degrees Celsius

Current density: 1 to 58 A / dm 2

Amount of coulomb ： 4 to 81 As / dm 2

Harmony 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 degrees Celsius

Current density: 24 to 50 A / dm 2

Coulomb amount: 34-48 As / dm 2

Antirust treatment

Liquid composition: Nickel 5-20 g / L, cobalt 1-8 g / L

pH: 2-3

Liquid temperature: 40-60 degrees Celsius

Current density: 5 to 20 A / dm 2

Coulomb amount: 10-20 As / dm 2

Chromate treatment

Liquid composition: Potassium dichromate 1-10 g / l, zinc 0-5 g / l

pH: 3-4

Liquid temperature: 50-60 degrees Celsius

Current density: 0 to 2 A / dm 2 (Can also be done electrolessly for immersion chromate treatment)

Coulomb amount: 0 to 2 As / dm 2 (Can be carried out in electroless for immersion chromate treatment)

Silane coupling treatment

Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1-0.5 wt%)

<Example 3>

After the ultrathin copper layer was formed on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, rust preventing treatment, chromate treatment, and silane coupling treatment were carried out on the ultrathin copper layer surface. It carried out in order. In addition, the thickness of ultra-thin copper foil was 3 micrometers.

Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

As: 0-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 degrees Celsius

Current density: 25 to 110 A / dm 2

Harmonic coulomb amount: 50-500 As / dm 2

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

* Temperature: 30-70 degreeC

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50-300 As / dm 2

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH ： 40 to 200 g / l

NaCN ： 70-250 g / ℓ

CuCN ： 50 to 200 g / ℓ

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Liquid temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 to 20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l

NaOH or KOH ： 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20-80 degrees Celsius

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

<Example 4>

After forming a Ni layer and a Cr layer on the copper foil carrier on the conditions similar to Example 1, on a roll-to-roll type continuous plating line, it electroplated the ultra-thin copper layer of thickness 3micrometer on the Cr layer on condition of the following. It formed by forming and manufactured the copper foil with a carrier. In addition, in the present Example, it manufactured also about the copper foil with a carrier which made the thickness of an ultra-thin copper layer 2, 5, and 10 micrometers, and evaluated similarly to the Example whose thickness of an ultra-thin copper layer is 3 micrometers. The results were nearly identical regardless of the thickness.

Ultrathin copper layer

Copper concentration: 30-120 g / l

H ₂ SO ₄ concentration: 20-120 g / l

Bis (3 sulfopropyl) disulfide concentration: 10-100 ppm

Tertiary amine compound: 10-100 ppm

Chlorine: 10 to 100 ppm

Electrolyte temperature: 20-80 degreeC

Current density: 10 to 100 A / dm 2

In addition, the following compounds were used as the above-mentioned tertiary amine compound.

[Formula 11]

(In the above formula, R ₁ and R ₂ are selected from the group consisting of hydroxyalkyl group, ether group, aryl group, aromatic substituted alkyl group, unsaturated hydrocarbon group, alkyl group. Here, R ₁ and R ₂ together are a methyl group. )

The said compound can be obtained by mixing predetermined amount of Deconal Ex-314 by Nagase Chemtex Co., Ltd., and dimethylamine, for example, and performing reaction for 3 hours at 60 degreeC.

After the ultrathin copper layer was formed on the copper foil carrier, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order.

Harmonization processing 1

Liquid composition: Copper 10-20 g / l, sulfuric acid 50-100 g / l

Liquid temperature: 25-50 degrees Celsius

Current density: 1 to 58 A / dm 2

Amount of coulomb ： 4 to 81 As / dm 2

Harmony 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 degrees Celsius

Current density: 24 to 50 A / dm 2

Coulomb amount: 34-48 As / dm 2

Antirust treatment

Liquid composition: Nickel 5-20 g / L, cobalt 1-8 g / L

pH: 2-3

Liquid temperature: 40-60 degrees Celsius

Current density: 5 to 20 A / dm 2

Coulomb amount: 10-20 As / dm 2

Chromate treatment

Liquid composition: Potassium dichromate 1-10 g / l, zinc 0-5 g / l

pH: 3-4

Liquid temperature: 50-60 degrees Celsius

Current density: 0 to 2 A / dm 2 (Can also be done electrolessly for immersion chromate treatment)

Coulomb amount: 0 to 2 As / dm 2 (Can be carried out in electroless for immersion chromate treatment)

Silane coupling treatment

Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1-0.5 wt%)

<Example 5>

After forming a Ni layer and a Cr layer on the copper foil carrier on the conditions similar to Example 1, on a roll-to-roll type continuous plating line, it electroplated the ultra-thin copper layer of thickness 3micrometer on the Cr layer on condition of the following. It formed by forming and manufactured the copper foil with a carrier. In addition, in the present Example, it manufactured also about the copper foil with a carrier which made the thickness of an ultra-thin copper layer 2, 5, and 10 micrometers, and evaluated similarly to the Example whose thickness of an ultra-thin copper layer is 3 micrometers. The results were nearly identical regardless of the thickness.

Ultrathin copper layer

Copper concentration: 30-120 g / l

H ₂ SO ₄ concentration: 20-120 g / l

Bis (3 sulfopropyl) disulfide concentration: 10-100 ppm

Tertiary amine compound: 10-100 ppm

Chlorine: 10 to 100 ppm

Electrolyte temperature: 20-80 degreeC

Current density: 10 to 100 A / dm 2

In addition, the following compounds were used as the above-mentioned tertiary amine compound.

[Formula 12]

(In the above formula, R ₁ and R ₂ are selected from the group consisting of hydroxyalkyl group, ether group, aryl group, aromatic substituted alkyl group, unsaturated hydrocarbon group, alkyl group. Here, R ₁ and R ₂ together are a methyl group. )

The said compound can be obtained, for example by mixing predetermined amount of Deconal Ex-314 by Nagase Chemtex Co., Ltd., and dimethylamine, and performing reaction for 3 hours at 60 degreeC.)

After the ultrathin copper layer was formed on the copper foil carrier, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order.

Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

W: 0.1-50 mg / l

Sodium dodecyl sulfate: 0.1-50 mg / l

As ： 0.1-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 degrees Celsius

Current density: 25 to 110 A / dm 2

Harmonic coulomb amount: 50-500 As / dm 2

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

* Temperature: 30-70 degreeC

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50-300 As / dm 2

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH ： 40 to 200 g / l

NaCN ： 70-250 g / ℓ

CuCN ： 50 to 200 g / ℓ

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Liquid temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 to 20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l

NaOH or KOH ： 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20-80 degrees Celsius

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

<Comparative Example 1>

After forming a Ni layer and a Cr layer on the copper foil carrier on the conditions similar to Example 1, on a roll-to-roll type continuous plating line, it electroplated the ultra-thin copper layer of thickness 3micrometer on the Cr layer on condition of the following. It formed by forming and manufactured the copper foil with a carrier.

Ultrathin copper layer

Copper concentration: 30-120 g / l

H ₂ SO ₄ concentration: 20-120 g / l

Electrolyte temperature: 20-80 degreeC

Current density: 5 to 9 A / dm 2

Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

As: 0-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 degrees Celsius

Current density: 25 to 110 A / dm 2

Harmonic coulomb amount: 50-500 As / dm 2

Plating time: 0.5-20 seconds

Harmony treatment 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

* Temperature: 30-70 degreeC

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50-300 As / dm 2

Plating time: 1 to 60 seconds

Antirust treatment

(Liquid composition)

NaOH ： 40 to 200 g / l

NaCN ： 70-250 g / ℓ

CuCN ： 50 to 200 g / ℓ

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Liquid temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 to 20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l

NaOH or KOH ： 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20-80 degrees Celsius

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

<Comparative Example 2>

After forming a Ni layer and a Cr layer on the copper foil carrier on the conditions similar to Example 1, on a roll-to-roll type continuous plating line, it electroplated the ultra-thin copper layer of thickness 3micrometer on the Cr layer on condition of the following. It formed by forming and manufactured the copper foil with a carrier.

Ultrathin copper layer

Copper concentration: 30-120 g / l

H ₂ SO ₄ concentration: 20-120 g / l

Electrolyte temperature: 20-80 degreeC

Current density: 10 to 100 A / dm 2

Harmonization processing 1

(Liquid composition 1)

Cu: 10 to 30 g / l

H ₂ SO ₄ : 10 to 150 g / l

W ： 0-50 mg / l

Sodium dodecyl sulfate: 0-50 mg / l

As: 0-200 mg / l

(Electroplating condition 1)

Temperature: 30-70 degrees Celsius

Current density: 25 to 110 A / dm 2

Harmonic coulomb amount: 50-500 As / dm 2

Plating time ： 40 seconds

Harmony treatment 2

(Liquid composition 2)

Cu: 20 to 80 g / l

H ₂ SO ₄ : 50 to 200 g / l

(Electroplating condition 2)

* Temperature: 30-70 degreeC

Current density: 5 to 50 A / dm 2

Harmonic coulomb amount: 50-300 As / dm 2

Plating time ： 80 seconds

Antirust treatment

(Liquid composition)

NaOH ： 40 to 200 g / l

NaCN ： 70-250 g / ℓ

CuCN ： 50 to 200 g / ℓ

Zn (CN) ₂ : 2-100 g / l

As ₂ O ₃ : 0.01-1 g / l

(Liquid temperature)

40-90 degreeC

(Current condition)

Current density: 1 to 50 A / dm 2

Plating time: 1 to 20 seconds

Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / l

NaOH or KOH ： 10-50 g / l

ZnOH or ZnSO ₄ 7H ₂ O: 0.05 to 10 g / l

pH: 7-13

Bath temperature: 20-80 degrees Celsius

Current density: 0.05 to 5 A / dm 2

Time: 5-30 seconds

Silane coupling treatment

After spray-coating 0.1 vol%-0.3 vol% of 3-glycidoxy propyl trimethoxysilane aqueous solution, it dries and heats for 0.1 to 10 second in 100-200 degreeC air.

2. Evaluation of characteristics of copper foil with carrier

About the copper foil with a carrier obtained by making it above, the characteristic evaluation was performed with the following method. The results are shown in Table 1.

(Surface roughness)

The surface roughness (Ra, Rt, Rz, Ssk, Sku) of the ultrathin copper layer was measured using a non-contact roughness measuring instrument (LEXT OLS 4000 manufactured by Olympus) according to JIS B0601-1994 for Ra and Rz, and JIS B0601 for Rt. Based on -2001, Ssk and Sku were measured on the following measurement conditions based on ISO25178 draft.

<Measurement conditions>

Cutoff: None

Reference length: 257.9 μm

Reference area: 6624μm ²

Measurement environment temperature: 23-25 degrees Celsius

In addition, for comparison, the following measurement conditions were carried out in accordance with JIS B0601-1994 (Ra, Rz) and JIS B0601-2001 (Rt) using a contact roughness measuring instrument (contact illuminometer Surfcorder SE-3C manufactured by Kosaka Research Co., Ltd.). Also, the surface roughness (Ra, Rt, Rz) of the ultrathin copper layer was measured.

<Measurement conditions>

Cutoff: 0.25mm

Reference length: 0.8mm

Measurement environment temperature: 23-25 degrees Celsius

(Surface area ratio)

It measured on the following measurement conditions using the non-contact roughness measuring instrument (LEXT OLS 4000 by Olympus). The surface area ratio measured an area and an actual area, and made the value of an actual area / area the surface area ratio. Here, an area refers to a measurement reference area, and an actual area refers to the surface area in a measurement reference area.

<Measurement conditions>

Cutoff: None

Reference length: 257.9 μm

Reference area: 6624μm ²

Measurement environment temperature: 23-25 degrees Celsius

(Volume of harmonic processing side)

It measured on the following measurement conditions using the non-contact roughness measuring instrument (laser microscope, LEXT OLS 4000 by Olympus). In addition, the volume of a roughening process surface is measured as follows.

(1) The laser microscope is set at a height that is focused on the surface of the sample.

(2) Brightness is adjusted and adjusted so that the total illuminance may be about 80% of the saturation point.

(3) Place the laser microscope close to the sample and zero the point where the screen illuminance is completely lost.

(4) Keep the laser microscope away from the sample and set the point where the screen illuminance is completely lost to the upper limit.

(5) The volume of the roughening process surface from height zero to an upper limit is measured.

<Measurement conditions>

Cutoff: None

Reference length: 257.9 μm

Reference area: 6624μm ²

Measurement environment temperature: 23-25 degrees Celsius

(Migration)

Each copper foil with a carrier was bonded to bismuth-based resin, and then the carrier foil was peeled off. The thickness of the exposed ultrathin copper layer was 1.5 micrometers by soft etching. Then, after washing and drying, DF (Hitachi Chemical Co., Ltd. make, brand name RY-3625) was laminated | stacked on the ultra-thin copper layer. It exposed on the conditions of 15 mJ / cm <2>, liquid-sprayed fluctuation | variation for 1 minute at 38 degreeC using the developing solution (sodium carbonate), and formed the resist pattern in the various pitches of Table 1. Subsequently, 15 micrometers plating UP was carried out using copper sulfate plating (CUBRITE21 by Ebara Eudylite), and DF was peeled off with the peeling liquid (sodium hydroxide). Thereafter, the ultrathin copper layer was etched away with an sulfuric acid-hydrogen peroxide-based etchant to form wirings of various pitches shown in Table 1.

The pitch described in the table corresponds to the total value of the lines and the spaces.

About the obtained wiring, the presence or absence of insulation deterioration between wiring patterns was evaluated on the following measurement conditions using the migration measuring device (IMV-made MIG-9000).

<Measurement conditions>

Threshold: Initial resistance 60% down

Measurement time: 1000h

Voltage: 60 V

Temperature: 85 degrees Celsius

Relative humidity: 85% RH

Table 1-1

TABLE 1-2

Claims (1)

The copper foil with a carrier which has a copper foil carrier, the peeling layer laminated | stacked on the copper foil carrier, and the ultra-thin copper layer laminated | stacked on the peeling layer WHEREIN: An ultrathin copper layer is roughened and Rz of the ultra-thin copper layer surface Is 1.6 µm or less as measured by a non-contact roughness meter, Ra on the surface of the ultrathin copper layer is 0.25 µm or less as measured by a non-contact roughness meter, and Rt of the ultrathin copper layer surface is 1.8 µm or less as measured by a non-contact roughness meter and Copper foil with a carrier whose Ssk is -0.3-0.3 and Sku of the ultra-thin copper layer surface is 2.8-3.3.

Images