KR20170086691A - Carrier-attached metal foil - Google Patents

Abstract

It is possible to provide a metal foil with a carrier which is not inadvertently peeled off between the metal foil and the plate-like carrier, and which is intentionally peeled off. A metal foil with a carrier comprising a resinous plate-like carrier and a metal foil peelably adhered to at least one surface of the carrier, wherein the peel strength of the metal foil and the plate-like carrier is not less than 10 gf / Cm or less.

Description

CARRIER-ATTACHED METAL FOIL}

The present invention relates to a metal foil with a carrier. More particularly, the present invention relates to a metal foil with a carrier used in the production of a single-sided, two-layer or more multi-layer laminated board used in a printed wiring board, or a very thin coreless board.

A representative example of a multilayer laminate is a printed circuit board. Generally, the printed wiring board is made of a dielectric material called " prepreg " obtained by impregnating a base material such as a synthetic resin plate, a glass plate, a glass nonwoven fabric, or paper with a synthetic resin as a basic constituent material. A sheet such as a copper or copper alloy foil having electrical conductivity is bonded to the side opposed to the prepreg. The thus assembled laminate is generally called a CCL (Copper Clad Laminate) material. The surface of the copper foil in contact with the prepreg is usually subjected to a roughening treatment for preventing oxidation after the roughening treatment for enhancing the bonding strength. Instead of copper or copper alloy foil, foil of aluminum, nickel, zinc or the like may be used. Their thickness is about 5 to 200 mu m. This commonly used CCL (Copper Clad Laminate) material is shown in Fig.

Patent Document 1 proposes a metal foil with a carrier made of a synthetic resin-made plate-like carrier and a metal foil which is mechanically peelably brought into close contact with at least one surface of the carrier, and the carrier- And the like. The peel strength between the plate-like carrier and the metal foil is preferably from 1 gf / cm to 1 kgf / cm. According to such a carrier-coated metal foil, since the copper foil is supported over the entire surface by the synthetic resin, the occurrence of wrinkles in the copper foil during the lamination can be prevented. Since the metal foil with a carrier and the synthetic resin are in close contact with each other without any gaps, when the metal foil surface is plated or etched, it can be put into the plating or etching chemical liquid. Since the coefficient of linear expansion of the synthetic resin is at the same level as that of the copper foil as the constituent material of the substrate and the post-polymerization prepreg, the positional deviation of the circuit does not occur, so that generation of defective products is reduced, Effect.

Japanese Patent Application Laid-Open No. 2009-272589

The copper foil with a carrier described in Patent Document 1 is an epoch-making invention that contributes greatly to the manufacturing process of the printed circuit board by simplifying the manufacturing process and the yield, thereby reducing the manufacturing cost. However, There is no mention of the configuration considering the subsequent peeling, and there is room for improvement.

For example, in applications such as a shielding material formed by performing mesh processing and the like, which are used without being subjected to an excessive heating process, the metal foil and the synthetic resin adhered to each other are removed inadvertently And it is important that the metal can be intentionally peeled off at the interface between the metal foil and the synthetic resin when the peeling operation is performed. That is, when the peel strength of both of them is excessively increased in order to avoid inadvertent peeling, the resin part is broken at this time when peeling the metal foil and the synthetic resin, and the resin powder may remain on the surface of the metal foil, It is not.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a metal foil with a carrier capable of deliberate peeling at the interface between a metal foil and a plate-like carrier, while exploring conditions useful for peeling the plate-shaped carrier and the metal foil.

As a result of intensive studies on the above problems, the present inventors have found that, by setting the peeling strength between the metal foil and the plate-like carrier within a certain range, it is possible to prevent deliberate peeling between the metal foil and the plate- And have come to accomplish the present invention.

That is, the present invention is as follows.

(1) A carrier-coated metal foil comprising a resin-made plate-like carrier and a metal foil peelably adhered to at least one surface of the carrier, characterized in that the peel strength of the metal foil and the plate-like carrier is from 10 gf / cm to 200 gf / Or less.

(2) The metal foil with a carrier according to (1), wherein the resinous plate-like carrier contains a thermosetting resin.

(3) The resin-made plate-like carrier is a prepreg. The carrier-coated metal foil according to (1) or (2)

(4) The metal foil with a carrier according to (2) or (3)

Wherein the resinous plate-like carrier has a glass transition temperature Tg of 120 to 320 占 폚.

(5) The metal foil with a carrier according to any one of (1) to (4)

And a ten-point average roughness (Rz jis) of the side surface of the metal foil in contact with the carrier is 3.5 m or less.

(6) The metal foil with a carrier according to any one of (1) to (5)

Wherein the peel strength of the metal foil and the plate-like carrier after heating at 220 ° C for at least 3 hours, 6 hours, or 9 hours is 10 gf / cm or more and 200 gf / cm or less.

(7) The plate-like carrier and the metal foil constituting the metal foil with a carrier satisfy the following formula:

[Chemical Formula 1]

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ And R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom)

The metal foil with a carrier according to any one of (1) to (6), which is obtained by kneading a silane compound represented by the formula (1), a hydrolysis product thereof and a hydrolysis product thereof in a single or a plurality of combinations.

(8) A multilayer metal clad laminate comprising a resin laminated on at least one metal foil side of the carrier-coated metal foil according to any one of (1) to (7) ≪ / RTI >

(9) A method for producing a resin-coated metal foil according to any one of (1) to (7), which comprises laminating a resin on at least one metal foil side of a carrier foil, A method for producing a multilayer metal clad laminate comprising the steps of: laminating a carrier-coated metal foil or a metal foil described above one or more times repeatedly.

(10) The method for producing a multilayer metal clad laminate according to (8) or (9), further comprising a step of peeling and separating the plate-like carrier of the carrier-bonded metal foil and the metal foil.

(11) The method for producing a multilayer metal clad laminate according to (10), which comprises a step of removing a part or the whole of a metal foil separated and removed by etching.

(12) A multilayer metal clad laminate obtained by the production method according to any one of (8) to (11).

(13) A method for manufacturing a build-up board comprising the step of forming at least one build-up wiring layer on at least one metal foil side of the carrier-coated metal foil according to any one of (1) to (7).

(14) The method for manufacturing a build-up substrate according to (13), wherein the build-up wiring layer is formed using at least one of a subtractive method or a full additive method or a semi-additive method.

(15) A resin-coated metal foil according to any one of (1) to (7), wherein the resin is laminated on at least one metal foil side, (7), wherein the carrier-bonded metal foil or the metal foil is repeatedly laminated one or more times.

(16) The method for manufacturing a build-up substrate according to (15), wherein the metal foil of the carrier metal foil, the plate-like carrier of the metal foil with the carrier, Further comprising a step of performing conduction plating on side surfaces and bottom surfaces of the hole.

(17) The method of manufacturing a build-up board according to (15) or (16), wherein the metal foil constituting the single-sided wiring board, the metal foil constituting the single- Wherein the step of forming a wiring on at least one of the metal foil is performed at least once.

(18) The method for producing a metal foil according to any one of (15) to (17), further comprising a step of laminating a resin plate side of the metal foil with a carrier according to any one of (1) to (7) The method of manufacturing a build-up substrate according to any one of claims 1 to 3.

(19) A step of laminating a metal foil of one of the metal foil with a carrier described in any one of (1) to (7), wherein a resin is laminated on the wired surface and a metal foil is closely attached to the resin, Up board according to any one of (15) to (17).

(20) The method for manufacturing a build-up substrate according to any one of (15) to (19), wherein at least one of the resin is a prepreg.

(21) The method of manufacturing a build-up board according to any one of (13) to (20), further comprising a step of separating and separating the plate-like carrier and the metal foil of the carrier- .

(22) The method of manufacturing a build-up wiring board according to (21), further comprising the step of removing part or all of the metal foil in close contact with the plate-shaped carrier by etching.

(23) A build-up wiring board obtained by the manufacturing method according to (21) or (22).

(24) A method for manufacturing a printed circuit board, comprising the step of manufacturing a build-up substrate by the manufacturing method according to any one of (13) to (20).

(25) A process for producing a printed circuit board, comprising the step of producing a build-up wiring board by the manufacturing method according to (21) or (22).

According to the present invention, it is possible to provide a metal foil with a carrier which can be deliberately peeled without inadvertent peeling between the metal foil and the plate-like carrier.

1 shows a configuration example of a CCL.
Fig. 2 shows a constitutional example of a metal foil with a carrier according to the present invention.
Fig. 3 shows an example of assembling a multilayer CCL using a copper foil with a carrier according to the present invention (in which a copper foil is bonded to both surfaces of a resin plate).

In one embodiment of the carrier-coated metal foil according to the present invention, a metal foil with a carrier made of a resin-made plate-like carrier and a metal foil adhered on one or both surfaces, preferably both surfaces of the carrier, Fig. 2 and Fig. 3 show one configuration example of the metal foil with a carrier according to the present invention. Particularly, in the first part of Fig. 3, a metal foil 11 with a carrier in which a metal foil 11a is in peelable contact with both surfaces of a resinous plate-like carrier 11c is shown. The plate-like carrier 11c and the metal foil 11a are bonded using a silane compound 11b to be described later.

Structurally, it is similar to the CCL shown in Fig. 1, but in the carrier-adhered metal foil of the present invention, the metal foil and the resin are finally separated, so that they can be easily peeled off. At this point, the structure and function are completely different because the CCL is not peeled off.

Although the metal foil with a carrier used in the present invention has to be peeled at one time, it has a problem that the adhesion is excessively high. However, the plate-like carrier and the metal foil have such adhesiveness as not to be peeled off in the chemical liquid treatment process, need. From this viewpoint, the peel strength between the metal foil and the plate-like carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, still more preferably 50 gf / cm or more, and more preferably 200 gf / More preferably 150 gf / cm or less, and even more preferably 80 gf / cm or less. When the peeling strength between the metal foil and the plate-like carrier is set within the above range, peeling is not caused at the time of conveyance or during processing, and peeling can be easily performed by a human hand, that is, mechanical peeling can be performed.

Further, in the manufacturing process of the multilayer printed wiring board, the heat treatment is often performed by a lamination press process or a desmear process. Therefore, the thermal history received by the carrier-adhered metal foil becomes more severe as the number of laminated layers increases. Therefore, in consideration of application to a multilayered printed circuit board, it is preferable that the peel strength between the metal foil and the plate-like carrier is in the range described above even after the necessary thermal history is obtained.

Therefore, in a more preferred embodiment of the present invention, it is preferable that the heating conditions in the manufacturing process of the multilayered printed circuit board, for example, at 220 deg. C for at least 3 hours, 6 hours, or 9 hours after heating The peel strength of the metal foil and the plate-like carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, further preferably 50 gf / cm or more, More preferably 80 gf / cm or less.

The peel strength after heating at 220 캜 is preferably in a range in which the peel strength satisfies the above-described range in both of 3 hours and 6 hours after, or 6 hours and 9 hours after, , And it is more preferable that all the peel strengths after 3 hours, 6 hours and 9 hours satisfy the above-mentioned range.

In the present invention, the peel strength is measured in accordance with the 90 degree peel strength measurement method specified in JIS C6481.

Hereinafter, concrete constituent requirements of each material for realizing such peel strength will be described.

The resin to be a plate-shaped carrier is not particularly limited, and a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a rosin and the like can be used, but a thermosetting resin is preferable. A prepreg may also be used. It is recommended that the prepress before bonding with the metal foil is in the state of the B stage. The coefficient of linear expansion of the prepreg (C stage) was 12 to 18 (占 10 ^-6 / 占 폚), 16.5 (占^10-6 / 占 폚) of copper foil as a constituent material of the substrate, or 17.3 ^-6 / DEG C), it is advantageous in that the positional deviation of the circuit due to the phenomenon (scaling change) in which the substrate size before and after the press is different from that at the time of designing does not occur. Further, as a synergistic effect of these advantages, it becomes possible to produce a multi-layer ultra-thin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

The plate-like carrier has a high glass transition temperature Tg in view of maintaining the peel strength after heating in the optimum range, and is, for example, a glass transition temperature Tg of 120 to 320 ° C, preferably 170 to 240 ° C . The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

It is also preferable that the thermal expansion coefficient of the resin is within +10% and -30% of the thermal expansion coefficient of the metal foil. This makes it possible to effectively prevent the positional deviation of the circuit due to the difference in thermal expansion between the metal foil and the resin, to reduce the generation of defective products, and to improve the yield.

The thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, if it is excessively large, it adversely affects the heat distribution in the hot press, while if it is too thin, Mu] m or more and 1000 mu m or less, more preferably 50 mu m or more and 900 mu m or less, and more preferably 100 mu m or more and 400 mu m or less.

As the metal foil, copper or a copper alloy foil is typical, but foils of aluminum, nickel, and zinc may be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil may be used. Although the metal foil is not limited, it is general to have a thickness of 1 占 퐉 or more, preferably 5 占 퐉 or more, and 400 占 퐉 or less, preferably 120 占 퐉 or less, when considering the use as a wiring of a printed circuit board. When a metal foil is pasted on both sides of the plate-like carrier, metal foils of the same thickness may be used, or metal foils of different thickness may be used.

The metal foil to be used may be subjected to various surface treatments. For example, a metal plating (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni alloy plating Chromate treatment (including the case where one or more alloying elements such as Zn, P, Ni, Mo, Zr and Ti are contained in the chromate treatment liquid) and surface roughness adjustment (Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Copper alloy plating, copper alloy plating, Cu-As alloy plating, Cu-As-W alloy plating, etc.). The roughening treatment not only affects the peeling strength between the metal foil and the plate-like carrier, but also the chromate treatment has a great influence. The chromate treatment is important from the viewpoints of rust resistance and discoloration resistance, but it tends to significantly increase the peel strength, so that it is also important as a means for adjusting the peel strength.

In the conventional CCL, it is desired that the resin and the copper foil have high peel strength. For example, when the matte surface (M side) of the electrolytic copper foil is used as the bonding surface with the resin, And improvement of the adhesive force by the physical anchor effect is being promoted. Also, in the resin side, various binders are added to increase the adhesive force with the metal foil. As described above, in the present invention, unlike the CCL, since the metal foil and the resin need to be finally peeled off, it is disadvantageous that the peel strength is excessively high.

Thus, in a preferred embodiment of the carrier-coated metal foil according to the present invention, in order to adjust the peel strength of the metal foil and the plate-like carrier to the preferable range described above, the surface roughness of the coplanar surface is measured according to JIS B 0601: 2001 Point average roughness (Rz jis) of the surface of one metal foil, and it is preferably 3.5 mu m or less and 3.0 mu m or less. However, it is preferable that the surface roughness is reduced to be as small as possible because it requires a lot of work and causes cost increase. Therefore, it is preferably 0.1 탆 or more, more preferably 0.3 탆 or more. When an electrolytic copper foil is used as the metal foil, any one of a glossy surface (shiny surface, S-surface) and a roughened surface (matte surface or M-surface) can be used if the surface roughness is adjusted. However, It is easy to adjust the surface roughness. On the other hand, the 10-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the carrier is preferably 0.4 μm or more and 10.0 μm or less.

In a preferred embodiment of the metal foil with a carrier according to the present invention, the surface treatment for improving the peel strength, such as roughening treatment, is not performed on the surface of the metal foil to be laminated with the resin. In a preferred embodiment of the metal foil with a carrier according to the present invention, no binder is added to the resin to increase the adhesive force with the metal foil.

The adjustment of the peel strength may be carried out by using a silane compound represented by the following formula, a hydrolysis-producing substance thereof, or a condensate of the hydrolysis-producing substance thereof (hereinafter, simply referred to as a silane compound) singly or in combination. When the sheet carrier and the metal foil are bonded to each other by using the silane compound, adhesiveness is appropriately lowered, and the peel strength can be easily adjusted to the above-mentioned range.

Expression:

(2)

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ And R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom)

The silane compound needs to have at least one alkoxy group. In the case where a substituent is constituted by a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, but not an alkoxy group, adhesion between the plate- There is a tendency to be excessively deteriorated. The silane compound is preferably a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or at least one hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom. If the hydrocarbon group is not present, the adhesion between the plate-like carrier and the surface of the metal foil tends to increase. In addition, the alkoxy group according to the present invention includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom.

In order to adjust the peel strength between the plate-like carrier and the metal foil to the above-mentioned range, it is preferable that the silane compound has three alkoxy groups and one hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) Do. In the above formula, both R ³ and R ⁴ are referred to as an alkoxy group.

Alkoxy groups include but are not limited to methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neopentoxy, n- Branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as a cyclohexyl group, an n-heptoxy group, and an n- .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group include, but are not limited to, methyl, ethyl, n- or isopropyl, n-, iso- or tert-butyl, n-, An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, .

Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as a phenyl group, a phenyl group substituted with an alkyl group (e.g., a tolyl group, a xylyl group), a 1- or 2-naphthyl group, have.

These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane: alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyl Trimethoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyl Phenyl triethoxysilane, alkyl substituted phenyltriethoxysilane (for example, p- (methyl) phenyltriethoxysilane), (3, 4-dimethylphenyltriethoxysilane), triethylsilane, triethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, 3,3-trifluoropropyl) trimethoxysilane, and tridecafluorooctyltriethoxysilane, methyltrichlorosilane , Dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, hydrolysis products of these, and condensation products of these hydrolysis products . Of these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane and decyltrimethoxysilane are preferable from the viewpoint of availability.

The carrier-adhered metal foil can be manufactured by bringing a plate-shaped carrier and a metal foil into hot-press contact. For example, the silane compound may be coated on the metal foil and / or the planar carrier, if necessary, followed by hot press lamination of a B-stage resin plate carrier on the metal foil.

The silane compound can be used in the form of an aqueous solution. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of alcohol is particularly effective when a silane compound having high hydrophobicity is used. The aqueous solution of the silane compound accelerates the hydrolysis of the alkoxy group by stirring, and the condensation of the hydrolysis product is promoted if the stirring time is long. Generally, the use of a silane compound which has undergone hydrolysis and condensation through a sufficient stirring time tends to lower the peeling strength between the metal foil and the plate-like carrier. Therefore, the peeling strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the silane compound in water can be, for example, 1 to 100 hours, although it is not particularly limited, and can be typically 1 to 30 hours. Naturally, there is a method of using without stirring.

The higher the concentration of the silane compound in the aqueous solution of the silane compound is, the lower the peel strength between the metal foil and the plate-like carrier tends to be lowered, and the peel strength can be adjusted by adjusting the concentration of the silane compound. The concentration of the silane compound in the aqueous solution may be 0.01 to 10.0% by volume, and typically 0.1 to 5.0% by volume, though it is not limited thereto.

The pH of the aqueous solution of the silane compound is not particularly limited and may be an acidic side or an alkaline side. For example, at a pH ranging from 3.0 to 10.0. From the viewpoint that no special pH adjustment is necessary, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

As the conditions of the hot press for producing the carrier-adhered metal foil, when a prepreg is used as the plate-shaped carrier, it is preferable to hot press at a pressure of 30 to 40 kg / cm 2 and a temperature higher than the glass transition temperature of the prepreg.

The surface of the metal foil or resin is measured by a device such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis) The silane compound is present on the surface of the metal foil or the resin.

In addition, from another point of view, the present invention provides the use of the above-described carrier metal foil.

First, a multilayer metal clad laminate including a resin laminated on at least one metal foil side of the above-described carrier-bonded metal foil, and then a resin or metal foil is laminated one or more times, for example, Is provided.

Secondly, a resin, a one-sided or double-sided metal clad laminate, or a metal foil with a carrier or a metal foil of the present invention is laminated one or more times, for example, 1 to 10 Layered metal clad laminate, which comprises repeatedly laminating a plurality of metal clad laminate layers.

In the above-described method for producing a multilayer metal clad laminate, it is possible to further include a step of separating and separating the plate-like carrier of the carrier-adhered metal foil from the metal foil.

Further, the method may further include a step of removing a part or the whole of the metal foil by etching after peeling and separating the plate-like carrier from the metal foil.

Fourthly, the resin is laminated on the metal foil side of the above-mentioned carrier-bonded metal foil, and then the resin, single-sided or double-sided wiring board, single-sided or double-sided metal clad laminate, For example, one to ten times by repeating the above steps.

Fifthly, there is provided a method of manufacturing a build-up substrate including a step of laminating at least one build-up wiring layer on the metal foil side of the above-mentioned carrier-bonded metal foil. At this time, the build-up wiring layer can be formed using at least one of a subtractive method, a pull additive method or a semi-additive method.

The subtractive method refers to a method of forming a conductor pattern by selectively removing an unnecessary portion of a metal foil on a metal clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like. The pull additive method is a method in which a conductor pattern is formed by electroless plating and / or electrolytic plating without using a metal foil for a conductor layer. The semi-additive method is a method in which, for example, A conductor pattern is formed by forming a conductor pattern by using a combination of copper metal deposition, electrolytic plating, etching, or both, and then removing an unnecessary seed layer by etching to obtain a conductor pattern.

In the method of manufacturing the build-up substrate, a single-sided or double-sided wiring board, a single-sided or double-sided metal clad laminate, a metal foil of a metal foil with a carrier, And a step of carrying out conduction plating on the substrate. The step of forming the wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal clad laminate, and the metal foil constituting the carrier- .

In the method of manufacturing a build-up substrate, a step of adhering a metal foil to one side of the wiring-formed surface and laminating the carrier side of the metal foil with a carrier according to the present invention may further be included. It is also possible to further include a step of laminating a metal foil with a carrier according to the present invention in which a resin is laminated on the wired surface and a metal foil is adhered to both surfaces of the resin.

The term " wired surface " refers to a portion formed on the surface that appears every time during the build-up process, and the build-up substrate includes the final product or the intermediate product.

In the above method of manufacturing a build-up substrate, a step of peeling and separating the plate-like carrier of the carrier-coated metal foil and the metal foil may be further included.

The method may further include a step of peeling and separating the plate-like carrier from the metal foil and then removing a part or the entire surface of the metal foil by etching.

Further, in the above-described method of manufacturing a multilayer metal clad laminate and the method of manufacturing a build-up substrate, the layers may be laminated by thermocompression bonding. The thermocompression bonding may be performed each time one layer of one layer is laminated, or may be laminated to some extent, or may be carried out collectively at the end.

Hereinafter, as a concrete example of the above-mentioned use, a method of producing a coreless build-up substrate using a copper foil 11 with a carrier in which a copper foil is adhered to both surfaces of a plate-like carrier 11c of a resin plate according to the present invention, . In this method, a necessary number of buildup layers 16 are stacked on both sides of the copper foil 11 with a carrier, and copper foils on both sides are peeled off from the copper foil 11 with a carrier (see Fig. 3).

For example, a resin as an insulating layer, a two-layer circuit board and a resin as an insulating layer are sequentially stacked on a metal foil side of the carrier-coated metal foil of the present invention, and the metal foil side is brought into contact with the resin plate, Up board can be manufactured by sequentially stacking the metal foil of the carrier-bonded metal foil of the present invention.

As another method, a resin as an insulating layer and a metal foil as a conductor layer are laminated in order on at least one metal foil side of a carrier-bonded metal foil in which a metal foil is adhered to both sides or one side of a resin-made plate-like carrier 11c . Next, a step of adjusting the thickness by half-etching the entire surface of the metal foil as required may be included. Next, a predetermined position of the laminated metal foil is subjected to laser processing to form a via hole passing through the metal foil and the resin, followed by a desmear treatment for removing the smear in the via hole, and then the entire surface of the via hole, Is subjected to electroless plating to form an interlayer connection, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance in a portion where the electroless plating on the metal foil or the electrolytic plating is unnecessary before each plating is carried out. If the adhesion between the electroless plating, the electrolytic plating, and the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically matched in advance. When a plating resist is used, the plating resist is removed after plating. Next, a metal foil, an electroless plating portion, and an unnecessary portion of the electroplated portion are removed by etching to form a circuit. Thus, a build-up substrate is obtained. A multilayer buildup substrate may be formed by repeating the steps from the lamination of the resin and copper foil to the circuit formation a plurality of times.

The resin-coated metal foil may be laminated on the outermost surface of the build-up substrate by contacting the resin-coated metal foil with the metal foil closely contacting the one side of the present invention. Alternatively, A metal foil of a carrier-adhered metal foil in contact with one another may be laminated.

Here, as the resin plate used for manufacturing the build-up substrate, a prepreg containing a thermosetting resin can be preferably used.

As another method, a resin as an insulating layer, for example, a prepreg or a photosensitive resin, for example, is coated on the exposed surface of a metal foil of a laminate obtained by bonding a metal foil, for example, a copper foil, . Thereafter, a via hole is formed at a predetermined position of the resin. When a prepreg, for example, is used as the resin, the via hole can be formed by laser processing. After the laser processing, a desmear treatment for removing the smear in the via holes may be performed. When a photosensitive resin is used as the resin, the resin in the via-hole forming portion can be removed by photolithography. Next, electroless plating is performed on the via hole bottom, the side surface, and the entire surface or part of the resin to form an interlayer connection, and electrolytic plating is further carried out if necessary. A plating resist may be formed in advance in a portion where the resin-based electroless plating or electrolytic plating is unnecessary before each plating is carried out. When the electroless plating, the electroplating, and the adhesion between the plating resist and the resin are insufficient, the surface of the resin may be chemically matched in advance. When a plating resist is used, the plating resist is removed after plating. Next, an unnecessary portion of the electroless plating portion or the electrolytic plating portion is removed by etching to form a circuit. Thus, a build-up substrate is obtained. The build up substrate may be a multilayer structure in which the steps from the lamination of the resin to the circuit formation are repeated a plurality of times.

The top surface of the build-up substrate may be laminated on the resin side of the laminate in which the metal foil is adhered to one side of the present invention or the resin side of the carrier-coated metal foil in which the metal foil is in close contact with one side, One of the metal foils of the laminate in which the metal foil is adhered to both surfaces of the present invention or one of the metal foils of the carrier metal foil in which the metal foil is adhered to both surfaces of the laminate may be laminated.

The core-less build-up substrate thus produced is subjected to a plating step and / or an etching step to form wirings on the surface thereof, and further to peel separation between the carrier resin and the copper foil, thereby completing a build-up wiring board. Wiring may be formed with respect to the peeling surface of the metal foil after peeling and separation, or the entire surface of the metal foil may be removed by etching to form a build-up wiring board. In addition, by mounting electronic parts on the build-up wiring board, the printed circuit board is completed. In addition, a printed circuit board can be obtained even if the electronic parts are directly mounted on the core-less build-up substrate before the resin is peeled off.

Example

EXAMPLES Hereinafter, examples and comparative examples of the present invention will be described, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

≪ Experimental Example 1 >

A nickel-zinc (Ni-Zn) alloy plating treatment and a chromate treatment (Cr-Zn) were performed on the shiny (S) surface of each electrolytic copper foil under the following conditions, Chromate) treatment was carried out so that the 10-point average roughness (measured in terms of Rz jis: according to JIS B 0601: 2001) of the coplanar surface (S-surface in this case) was 1.5 탆, (BT resin) was laminated with the S-side of the electrolytic copper foil and hot pressed at 190 캜 for 100 minutes to prepare a copper foil with a carrier.

(Nickel-zinc alloy plating)

Ni concentration of 17 g / l (added as NiSO ₄ )

Zn concentration 4 g / l (added as ZnSO ₄ )

pH 3.1

Solution temperature 40 ℃

Current density 0.1 to 10 A / dm 2

Plating time 0.1 to 10 seconds

(Chromate treatment)

Cr concentration 1.4 g / l (added as CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01 to 1.0 g / l (added as ZnSO ₄ )

Na ₂ SO ₄ concentration 10 g / l

pH 4.8

Solution temperature 55 ° C

Current density 0.1 to 10 A / dm 2

Plating time 0.1 to 10 seconds

For some of the electrolytic copper foils, an aqueous solution of the silane compound was applied to the S-plane using a spray coater, followed by drying the surface of the copper foil in air at 100 ° C, followed by bonding with the prepreg. Table 1 shows the types of the silane compound, the stirring time until the silane compound is dissolved in water, the concentration of the silane compound in the aqueous solution, the alcohol concentration in the aqueous solution, and the pH of the aqueous solution.

It is also assumed that thermal history is applied to some of the copper foils with a carrier on the carrier-adhered copper foil during additional heat treatment such as circuit formation, and the conditions described in Table 1 (here, 220 ° C for 3 hours) Heat treatment was performed.

The peel strength between the copper foil with a carrier obtained by hot pressing and the copper foil with a carrier after carrying out further heat treatment and the plate-like carrier (resin after heating) was measured. The results are shown in Table 1.

Further, in order to evaluate the peeling workability, the working time (hours / pieces) by the hands of a person per unit number was evaluated. The results are shown in Table 2.

≪ Experimental Examples 2 to 18 >

A copper foil with a carrier was produced in the same manner as in Experimental Example 1, using the copper foil, the resin (prepreg) and a part of the silane compound shown in Table 1. In some experimental examples, heat treatment was further performed under the conditions shown in Table 1. The same evaluation as in Experimental Example 1 was carried out for each. The results are shown in Tables 1 and 2.

Table 1 shows the type of the coplanar surface of the copper foil, the conditions of the surface treatment and the surface roughness Rz jis, the conditions of use of the silane compound, the type of the prepreg, and the lamination conditions of the copper foil and the prepreg.

Specific conditions of the epoxy silane (treatment) and the roughening treatment in the surface treatment conditions of the treated surface of the copper foil are as follows.

(Epoxy silane treatment)

Treatment solution: 0.9 volume% aqueous solution of 3-glycidoxypropyltrimethoxysilane

pH 5.0 to 9.0

Stirred for 12 hours at room temperature

Treatment method: Apply the treatment liquid using a spray coater, and dry the treated surface for 5 minutes in air at 100 ° C.

(Harmonization processing)

Cu concentration 20 g / l (added as CuSO ₄ )

H ₂ SO ₄ concentration 50 to 100 g / ℓ

As concentration 0.01 to 2.0 g / l (added as arvic acid)

* Liquid temperature 40 ℃

Current density 40 to 100 A / dm 2

Plating time 0.1 to 30 seconds

≪ Experimental Examples 19 to 20 &

Copper foil with a carrier was produced in the same manner as in Experimental Example 1, using the copper foil, the resin (prepreg) and a part of the silane compound shown in Table 3. And further subjected to heat treatment under the conditions shown in Table 3. The thus obtained copper foil with a carrier was evaluated in the same manner as in Experimental Example 1. The results are shown in Tables 3 and 4.

Furthermore, the S face was used as the coplanar face of the copper foil, and the surface thereof was subjected to a chromate treatment under the above-described conditions. Table 3 shows the surface roughness Rz jis of the copper foil, the type of the prepreg, conditions for using the silane compound for the surface treatment of the prepreg, and conditions for laminating the copper foil and the prepreg.

According to the table, it can be seen that even when the silane compound is treated on the surface of the copper foil and the surface of the prepreg, the same results are obtained in the peel strength of the laminate, the peel strength after heating, and the peeling workability .

(Build-up wiring board)

An FR-4 prepreg (manufactured by Nanya Plastic Company) and a copper foil (JTC 12 mm (product name), manufactured by Nikko Nisseki Kikinzoku K.K.) were superimposed in this order on both sides of the copper foil with the carrier thus produced , And 3 MPa under the heating conditions shown in the respective tables to prepare a four-layer copper clad laminate.

Next, a hole having a diameter of 100 mu m penetrating through the copper foil on the surface of the above-mentioned four-layer copper clad laminate and the insulating layer (cured prepreg) beneath it was drilled using a laser processor. Subsequently, copper plating was carried out by electroless copper plating on the copper foil on the copper foil-coated copper foil exposed on the bottom of the hole, on the side surface of the hole, on the copper foil on the surface of the four-layer copper clad laminate, An electrical connection was formed between the copper foil on the copper foil with a carrier and the copper foil on the surface of the four-layer copper clad laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. Thus, a four-layer buildup substrate was obtained.

Subsequently, in the four-layer build-up substrate, the plate-like carrier of the copper foil with the carrier and the copper foil were separated and separated to obtain two sets of two-layer build-up wiring boards.

Subsequently, the copper foil on the side of the plate carrier on the two sets of two-layer build-up wiring boards adhered was etched to form wiring, and two sets of two-layer build-up wiring boards were obtained.

In each of the examples, a plurality of four-layer build-up substrates were manufactured, and the degree of adhesion between the copper foil and the prepreg constituting the copper foil with a carrier in the build- In the build-up wiring board using the copper foil with a carrier produced under the condition that the peel strength and the peel strength after heating are evaluated as "S" and "G" in Table 3, the resin (plate- Was peeled off without destruction. However, as for the conditions evaluated as " G ", copper foil peeled off from the plate-like carrier without peeling at the time of build-up, as described in Tables 1 and 3.

With respect to the condition evaluated as "N", the resin was not broken or peeled off during the peeling operation of the copper foil on the copper foil with a carrier at the time of build-up, and the resin remained on the surface of the copper foil.

Regarding the condition evaluated as " - ", during the peeling operation of the copper foil on the copper foil with a carrier at the time of build-up, the resin was peeled without being broken, but the copper foil peeled off without peeling.

11 Carrier metal foil
11a metal foil
11b silane compound
11c plate carrier
16 buildup layer

Claims (27)

A carrier metal foil comprising a resin plate-like carrier and a metal foil peelably adhered to at least one surface of the carrier, wherein the peel strength of the metal foil and the plate-like carrier is not less than 10 gf / cm and not more than 200 gf /
The peel strength between the metal foil and the plate-like carrier after heating at 220 DEG C for at least 3 hours, 6 hours, or 9 hours is not less than 10 gf / cm and not more than 200 gf /
Wherein the surface of the metal foil on the side not in contact with the plate-like carrier has a 10-point average roughness (Rz jis) of 0.4 탆 or more and 10.0 탆 or less. The method according to claim 1,
A metal foil with a carrier, wherein the resinous sheet-like carrier contains a thermosetting resin. The method according to claim 1,
Wherein the resin-made plate-like carrier is a prepreg. 3. The method of claim 2,
Wherein the resinous plate-like carrier has a glass transition temperature Tg of 120 to 320 캜. The method according to claim 1,
And a 10-point average roughness (Rz jis) of the side surface of the metal foil in contact with the carrier is 3.5 m or less. The method according to claim 1,
The plate-like carrier and the metal foil constituting the carrier-adhered metal foil satisfy the following formula:
[Chemical Formula 1]

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ And R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom)
, A hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either alone or in combination. A multilayer metal clad laminate comprising a resin laminated on at least one metal foil side of the carrier-coated metal foil according to any one of claims 1 to 6, and then repeatedly laminating resin or metal foil one or more times Gt; A resin is laminated on at least one metal foil side of the first carrier-bonded metal foil, and then one or two or more of the resin, one-side or both-side metal-clad laminate, the second carrier-attached metal foil and the metal foil are repeated one or more times And then laminating,
Wherein the first carrier-bonded metal foil and the second carrier-bonded metal foil are the carrier-bonded metal foil according to any one of claims 1 to 6, respectively. 8. The method of claim 7,
Further comprising peeling and separating the plate-like carrier of the carrier-coated metal foil and the metal foil. 10. The method of claim 9,
And removing a part or the whole of the separated metal foil by etching. A multilayer metal clad laminate obtained by the production method according to claim 7. A method for manufacturing a build-up board, comprising the step of forming at least one build-up wiring layer on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 6. 13. The method of claim 12,
Wherein the build-up wiring layer is formed using at least one of a subtractive method, a full additive method, and a semi-additive method. A resin is laminated on at least one metal foil side of the first carrier-bonded metal foil, and then one or two or more of the resin, one-side or both-side metal-clad laminate, the second carrier-attached metal foil and the metal foil are repeated one or more times And then laminating,
Wherein the first carrier-adhered metal foil and the second carrier-adhered metal foil are the metal foil with a carrier according to any one of claims 1 to 6, respectively. 15. The method of claim 14,
The method further comprises a step of forming a hole in one side or both sides of the wiring substrate, one side or both sides of the metal clad laminate, the metal foil of the carrier-adhered metal foil, the plate-like carrier of the metal foil with the carrier, or the resin, , And a method of manufacturing a build-up substrate. 15. The method of claim 14,
Further comprising at least one step of forming a wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal clad laminate, and the metal foil constituting the carrier-bonded metal foil , And a method of manufacturing a build-up substrate. 15. The method of claim 14,
Further comprising a step of laminating a resin plate side of the carrier-bonded metal foil having a metal foil adhering to one side thereof in contact with the wiring-formed surface. 15. The method of claim 14,
A method for manufacturing a build-up board, comprising the steps of: laminating a resin on a wiring-formed surface, and laminating one of the metal foils of the metal foil with a carrier adhering the metal foil on both sides thereof. 15. The method of claim 14,
Wherein at least one of the resin is a prepreg. The method for manufacturing a build-up substrate according to claim 12, further comprising a step of peeling and separating the plate-like carrier and the metal foil of the carrier-adhered metal foil. 21. The method of claim 20,
Further comprising the step of removing a part or all of the metal foil adhered to the plate-shaped carrier by etching. A build-up wiring board obtained by the manufacturing method according to claim 20. A manufacturing method of a printed circuit board comprising a step of manufacturing a build-up substrate by the manufacturing method according to claim 12. A manufacturing method of a printed circuit board comprising a step of producing a build-up wiring board by the manufacturing method according to claim 20. A method for producing a resin plate-like carrier, comprising the steps of: preparing the carrier-coated metal foil according to any one of claims 1 to 6; and peeling the resin-made plate-like carrier from the carrier-coated metal foil. A method for manufacturing a build-up board, comprising the steps of: preparing the carrier-coated metal foil according to any one of claims 1 to 6; and peeling the metal foil from the carrier-coated metal foil. A metal foil for use in producing a carrier-bonded metal foil comprising a resin-made plate-like carrier and a metal foil peelably adhered to at least one surface of the carrier,
The peel strength of the metal foil and the plate-like carrier is not less than 10 gf / cm and not more than 200 gf / cm, and further, at 220 ° C for 3 hours, 6 hours, or 9 hours The peel strength of the metal foil and the plate-like carrier after at least one heating is not less than 10 gf / cm and not more than 200 gf /
Wherein the surface of the metal foil on the side not to be brought into close contact with the plate-like carrier has a 10-point average roughness (Rz jis) of 0.4 탆 or more and 10.0 탆 or less.

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