KR20190099096A - Carrier-attached metal foil - Google Patents

Abstract

Between a metal foil and a plate-shaped carrier, it becomes possible to provide the metal foil with a carrier which inadvertent peeling does not occur and intentional peeling is possible. MEANS TO SOLVE THE PROBLEM This invention is a metal foil with a carrier which consists of a resin plate-shaped carrier and the metal foil which contact | adhered mechanically to at least one surface of this carrier so that peeling was possible, and it is at least one of 3 hours, 6 hours, or 9 hours at 220 degreeC. The peeling strength of the metal foil after heating and a plate-shaped carrier is metal foil with a carrier of 10 gf / cm or more and 200 gf / cm or less.

Description

Metal foil with suitcase {CARRIER-ATTACHED METAL FOIL}

The present invention relates to a metal foil with a carrier. More specifically, it is related with the metal foil with a carrier used in manufacture of the single side | surface used for a printed wiring board, a multilayer laminated board of 2 or more layers, or an ultra-thin coreless board | substrate.

A representative example of a multilayer laminate is a printed circuit board. Generally, a printed circuit board uses the dielectric material called "prepreg" obtained by impregnating synthetic resin in base materials, such as a synthetic resin board, a glass plate, a glass nonwoven fabric, and paper, as a basic structural material. Moreover, the sheet | seats, such as copper or copper alloy foil which have electrical conductivity, are joined by the side which opposes a prepreg. The laminate thus assembled is commonly referred to as CCL (Copper Clad Laminate) material. It is common to make the surface which contact | connects the prepreg of copper foil a mat surface, in order to raise joint strength. Instead of copper or copper alloy foil, foil such as aluminum, nickel or zinc may be used. These thicknesses are about 5-200 micrometers. This commonly used CCL (Copper Clad Laminate) material is shown in FIG.

In patent document 1, the metal foil with a carrier which consists of a plate-shaped carrier made from synthetic resins and the metal foil which contact | adhered mechanically to at least one surface of the carrier so that peeling is proposed, and this metal foil with a carrier provides for assembly of a printed wiring board. It is described that it can. And the peeling strength of a plate-shaped carrier and metal foil showed that it is preferable that they are 1 gf / cm-1 kgf / cm. According to the said metal foil with a carrier, since copper foil is supported by synthetic resin over the whole surface, generation | occurrence | production of a wrinkle in a copper foil can be prevented during lamination. In addition, since the metal foil with the carrier is in close contact with the metal foil and the synthetic resin without a gap, when the metal foil surface is plated or etched, it can be added to the plating or etching chemical. In addition, since the coefficient of linear expansion of the synthetic resin is at the same level as that of the copper foil which is the constituent material of the substrate and the prepreg after polymerization, it does not cause the positional shift of the circuit, resulting in less defective products and improved yield. Has an effect.

Japanese Unexamined Patent Publication No. 2009-272589

The copper foil with a carrier described in Patent Literature 1 is a revolutionary invention that greatly contributes to the reduction of manufacturing cost by simplifying the manufacturing process of a printed circuit board and increasing the yield, but is a temporary adhesion between the plate-shaped carrier and the metal foil in a specific use of the metal foil with a carrier and There is no mention of the configuration in consideration of the subsequent peeling, and there is room for improvement.

For example, in applications used without undergoing too many steps of heat processing, for example, shield materials formed by performing mesh processing, metal foil and synthetic resin that are in close contact are inadvertently peeled off prior to the peeling operation. It is important to be able to intentionally peel at the interface between the metal foil and the synthetic resin when the peeling operation is not performed. That is, in order to avoid inadvertent peeling, if both peeling strengths are excessively high, when this peels a metal foil and a synthetic resin, the resin part may break and resin may remain on the surface of a metal foil, and this is preferable. It is not.

Then, this invention explores the conditions useful for peeling a plate-shaped carrier and metal foil so that peeling can be carried out, and makes it a subject to provide the metal foil with a carrier which can intentionally peel at the interface of a metal foil and a plate-shaped carrier.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching the said subject, when the peeling strength between a metal foil and a plate-shaped carrier is made into a fixed range, careless peeling does not arise between a metal foil and a plate-shaped carrier, and intentional peeling becomes possible. It was found out and completed this invention.

That is, this invention is as follows.

(1) Metal foil with a carrier which consists of a plate-shaped carrier made of resin and the metal foil which contact | adhered to at least one surface of this carrier so that peeling was possible, After heating at 220 degreeC for 3 hours, 6 hours, or at least one of 9 hours. Metal foil with a carrier whose peeling strength of a metal foil and a plate-shaped carrier is 10 gf / cm or more and 200 gf / cm or less.

(2) Metal foil with a carrier as described in (1) in which the resin plate-shaped carrier contains a thermosetting resin.

(3) Said resin plate-shaped carrier is metal foil with a carrier as described in (1) or (2) which is prepreg.

(4) The said metal plate carrier with a carrier as described in (2) or (3) which has a glass transition temperature Tg of 120-320 degreeC.

(5) Metal foil with a carrier in any one of (1)-(4) whose 10-point average roughness (Rz jis) of the side surface which contact | connects the said carrier of the said metal foil is 3.5 micrometers or less.

(6) The metal foil with a carrier as described in any one of (1)-(5) whose peeling strength of the said metal foil and the said plate-shaped carrier before the said heating is 10 gf / cm or more and 200 gf / cm or less.

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

[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 at least one hydrogen group is any of those hydrocarbon groups substituted with halogen atoms, R ³ And R ⁴ is 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 at least one hydrogen group in which at least one hydrogen atom is substituted with a halogen atom)

The metal foil with a carrier as described in any one of (1)-(6) formed by bonding together using the silane compound shown to this, the hydrolysis product, and the condensate of this hydrolysis product individually or in combination.

(8) A multilayer metal-clad laminate comprising laminating a resin to at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then laminating a resin or a metal foil one or more times. Method of preparation.

(9) Resin is laminated | stacked on the at least 1 metal foil side of the metal foil with a carrier in any one of (1)-(7), and then resin, single-sided or double-sided metal clad laminated board, or any of (1)-(7) The manufacturing method of the multilayer metal coating laminated board containing repeating laminating | stacking the metal foil with a carrier as described in one, or metal foil one or more times.

(10) The manufacturing method of the multilayer metal coating laminated board as described in (8) or (9) which further includes the process of peeling and separating the plate-shaped carrier and metal foil of the said metal foil with a carrier.

(11) The manufacturing method as described in (10) WHEREIN: The manufacturing method of the multilayer metal coating laminated board containing the process of removing part or all of the metal foil which peeled and isolate | separated by etching.

The multilayer metal coating laminated board obtained by the manufacturing method in any one of (12) (8)-(11).

The manufacturing method of the buildup board | substrate which includes the process of forming one or more layers of buildup wiring layers in the metal foil side with a carrier in any one of (13) (1)-(7).

The buildup wiring layer is a manufacturing method of the buildup board | substrate as described in (13) formed using at least one of a subtractive method, a full additive method, or a semiadditive method.

(15) Resin is laminated | stacked on at least one metal foil side of the metal foil with a carrier in any one of (1)-(7), and then resin, a single side | side or a double-sided wiring board, a single side | side or a double-sided metal clad laminated board, (1)- The manufacturing method of the buildup board | substrate which repeats laminating | stacking the metal foil with a carrier as described in any one of (7), or a metal foil repeatedly one or more times.

(16) In the manufacturing method of a buildup board | substrate as described in (15), a hole is made to single-sided or double-sided wiring board, single-sided or double-sided metal clad laminated board, metal foil of carrier foil, plate-shaped carrier of metal foil with carrier, or resin, The manufacturing method of the buildup board | substrate which further includes the process of conducting plating on the side surface and bottom surface of the said hole.

(17) The manufacturing method of the buildup board | substrate as described in (15) or (16) WHEREIN: The metal foil which comprises the said single-sided or double-sided wiring board, the metal foil which comprises the single-sided or double-sided metal clad laminated board, and the metal foil with carrier The manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil one or more times.

(18)-(17) including the process of contacting and laminating | stacking the resin plate side of the metal foil with a carrier in any one of (1)-(7) which adhere | attached metal foil on single side | surface on the wiring-formed surface. The manufacturing method of the buildup board | substrate in any one.

(19) The process of laminating | stacking resin on the surface in which wiring was formed, and contacting and laminating | stacking one metal foil of the metal foil with a carrier as described in any one of (1)-(7) which contact | adhered metal foil to both sides to the said resin was added. The manufacturing method of the buildup board | substrate in any one of (15)-(17) to include.

(20) At least one of the said resin is a prepreg, The manufacturing method of the buildup board | substrate in any one of (15)-(19) characterized by the above-mentioned.

(21) The manufacturing method of the buildup wiring board which further includes the process of peeling and isolate | separating the plate-shaped carrier and metal foil of the said metal foil with a carrier in the manufacturing method of any one of (13)-(20). .

(22) The manufacturing method of the buildup wiring board as described in (21) which further includes the process of removing part or all of the metal foil which contacted the plate-shaped carrier by etching.

The buildup wiring board obtained by the manufacturing method as described in (23) (21) or (22).

(24) The manufacturing method of the printed circuit board containing the process of manufacturing a buildup board | substrate by the manufacturing method in any one of (13)-(20).

The manufacturing method of the printed circuit board containing the process of manufacturing a buildup wiring board by the manufacturing method as described in (25) (21) or (22).

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the metal foil with a carrier which inadvertent peeling does not arise between a metal foil and a plate-shaped carrier, and intentional peeling is possible.

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

In one Embodiment of the metal foil with a carrier which concerns on this invention, the metal foil with a carrier which consists of a plate-shaped carrier made of resin and the metal foil which contact | adhered to the one side or both sides, Preferably both sides of the carrier so that peeling is prepared is prepared. One structural example of the metal foil with a carrier which concerns on this invention is shown to FIG. 2 and FIG. In particular, at the beginning of FIG. 3, the metal foil 11 with a carrier in which the metal foil 11a is brought into close contact with each other on the both sides of the resin plate-shaped carrier 11c is peeled off. The plate-shaped carrier 11c and the metal foil 11a are bonded together using the silane compound 11b mentioned later.

Although structurally similar to CCL shown in FIG. 1, in the metal foil with a carrier of the present invention, the metal foil and the resin are finally separated and have a structure that can be easily peeled off. In this respect, since the CCL is not peeled off, the structure and the function are completely different.

Since the metal foil with a carrier used in the present invention must be peeled out sometime, excessively high adhesion is a problem. However, the adhesion of the plate-shaped carrier and the metal foil to the extent that the plate-shaped carrier and the metal foil are not peeled off in a chemical treatment process such as plating performed in the process of manufacturing a printed circuit board is used. need.

Moreover, in the manufacturing process of a multilayer printed wiring board, it heats by a lamination press process or a desmear process in many cases. Therefore, the heat history received by the metal foil with a carrier becomes stricter as the number of laminated sheets increases. Therefore, especially when considering application to a multilayer printed wiring board, it is preferable that the peeling strength of a metal foil and a plate-shaped carrier exists in the range mentioned above even after passing through the required heat history.

Therefore, in one Embodiment of this invention, the metal foil after heating at least one of 3 hours, 6 hours, or 9 hours at 220 degreeC, for example, presuming the heating conditions in the manufacturing process of a multilayer printed wiring board, It is preferable that the peeling strength of a plate-shaped carrier is 10 gf / cm or more, It is more preferable that it is 30 gf / cm or more, It is more preferable that it is 50 gf / cm or more, It is preferable that it is 200 gf / cm or less, It is 150 gf / cm or less More preferably, it is still more preferable that it is 80 gf / cm or less.

The peel strength after the heating at 220 ° C., in terms of being able to cope with a variety of laminated waters, shows that the peel strength satisfies the above-mentioned range in both after 3 hours and after 6 hours, or after 6 hours and 9 hours. It is preferable that all the peeling strengths after 3 hours, 6 hours, and 9 hours satisfy | fill the above-mentioned range.

Thus, after peeling strength of a metal foil and a plate-shaped carrier in such a range after the heat processing in the manufacturing process of a multilayer printed wiring board, it does not peel at the time of conveyance or processing in the said manufacturing process, It can be easily peeled off by hand, ie mechanically peeled off.

Moreover, the copper foil with a carrier of this invention can be used also for the use used without going through the process of too much heat processing, for example, the use of the shield material etc. which form and form a mesh process.

From this viewpoint, in the metal foil with a carrier before heat processing in the manufacturing process of the above-mentioned multilayer printed wiring board, it is preferable that peeling strength of a metal foil and a plate-shaped carrier is 10 gf / cm or more, and it is more preferable that it is 30 gf / cm or more. On the other hand, it is more preferable that it is 50 gf / cm or more, It is preferable that it is 200 gf / cm or less, It is more preferable that it is 150 gf / cm or less, It is further more preferable that it is 80 gf / cm or less. By making the peeling strength of a metal foil and a plate-shaped carrier into such a range, it cannot peel at the time of conveyance or processing, and can peel easily with a human hand.

In this invention, peeling strength is measured based on the 90 degree peeling strength measuring method prescribed | regulated to JIS C6481.

Hereinafter, the specific structural requirements of each material for realizing such peeling strength are demonstrated.

Although there is no restriction | limiting in particular as resin used as a plate-shaped carrier, Although a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a sheet paper, etc. can be used, It is preferable that it is a thermosetting resin. Moreover, prepreg can also be used. It is preferable that the prepreg before bonding with metal foil is in the state of B stage. The coefficient of linear expansion of the prepreg (C stage) is 12-18 (x 10 ^-6 / deg. C) and 16.5 (x 10 ^-6 / deg. C) of copper foil which is a constituent material of the substrate, or 17.3 (x 10 of SUS press plate). ^-6 / ° C), it is advantageous in that the positional shift of the circuit due to a phenomenon (scaling change) different from that at the time of designing the substrate size before and after the press hardly occurs. In addition, as a synergistic effect of these advantages, it is possible to produce a multilayer ultra-thin coreless substrate. The prepreg used here may be the same as the prepreg which comprises a circuit board, or may differ.

It is preferable that this plate-shaped carrier has a high glass transition temperature Tg from a viewpoint of maintaining the peeling strength after heating in the optimal range, for example, it is 120-320 degreeC, Preferably it is 170-240 degreeC glass transition temperature Tg. . In addition, glass transition temperature Tg is made into the value measured by DSC (differential scanning calorimetry).

Moreover, it is preferable that the thermal expansion rate of resin is within +10% and -30% of the thermal expansion rate of metal foil. Thereby, the position shift of the circuit resulting from the thermal expansion difference of metal foil and resin can be prevented effectively, the occurrence of defective products can be reduced, and a yield can be improved.

Although the thickness of a plate-shaped carrier does not have a restriction | limiting in particular, It may be rigid or flexible, but when too thick, it adversely affects the heat distribution in a hot press, and when too thin, it will bend and will not flow through the manufacturing process of a printed wiring board, and it is 5 normally 50 micrometers or more and 900 micrometers or less are preferable, and 100 micrometers or more and 400 micrometers or less are more preferable.

As metal foil, although copper or copper alloy foil is typical, foil, such as aluminum, nickel, zinc, can also be used. In the case of copper or copper alloy foil, an electrolytic foil or a rolled foil can be used. Metal foil is not limited, but considering the use as a wiring of a printed circuit board, it is common to have thickness of 1 micrometer or more, Preferably it is 5 micrometers or more, and 400 micrometers or less, Preferably it is 120 micrometers or less. When a metal foil is affixed on both surfaces of a plate-shaped carrier, metal foil of the same thickness may be used and metal foil of a different thickness may be used.

Various surface treatment may be given to the metal foil to be used. For example, metal plating for the purpose of imparting heat resistance (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 Etc.), chromate treatment (to include at least one alloy element such as Zn, P, Ni, Mo, Zr, Ti, etc. in the chromate treatment liquid) to impart rust resistance and discoloration resistance, surface roughness adjustment Roughening treatment (e.g. copper electrodeposition, Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co Copper plating, such as alloy plating, Cu-As alloy plating, and Cu-As-W alloy plating, etc.) is mentioned. Not only the roughening treatment affects the peel strength of the metal foil and the plate-shaped carrier, but also the chromate treatment greatly affects it. Although chromate treatment is important from the viewpoint of rust prevention property and discoloration resistance, since the tendency which raises peeling strength significantly can be seen, it is also meaningful as an adjustment means of peeling strength.

In the conventional CCL, since the peel strength of resin and copper foil is high, it is desirable, for example, to make the matt surface (M surface) of electrolytic copper foil into an adhesive surface with resin, and to chemically carry out surface treatment, such as a roughening process. And the adhesive force improvement by the physical anchor effect is aimed at. Moreover, also in the resin side, in order to improve the adhesive force with metal foil, various binder is added. As described above, in the present invention, unlike CCL, the metal foil and the resin need to be finally peeled off, and therefore, an excessively high peel strength is disadvantageous.

So, in one preferable embodiment of the metal foil with a carrier which concerns on this invention, in order to adjust the peeling strength of a metal foil and a plate-shaped carrier to the preferable range mentioned above, the surface roughness of a bonding surface is measured based on JISB0601-2001. It is represented by the ten-point average roughness (Rz jis) of one metal foil surface, and it is preferable to set it as 3.5 micrometers or less, and also 3.0 micrometers or less. However, reducing the surface roughness without limiting the number of hands causes a cost increase, so it is preferable to set it to 0.1 µm or more, and more preferably 0.3 µm or more. When using an electrolytic copper foil as metal foil, if it adjusts to such surface roughness, although either surface of a glossy surface (shiny surface, S surface) and rough surface (mat surface, M surface) can be used, it is preferable to use S surface. Adjustment to the surface roughness is easy. On the other hand, it is preferable that 10-point average roughness Rz jis of the surface of the side which is not in contact with the said carrier of the said metal foil is 0.4 micrometer or more and 10.0 micrometers or less.

Moreover, in one preferable embodiment of the metal foil with a carrier which concerns on this invention, the surface treatment for improving peeling strength, such as a roughening process, is not performed about the bonding surface with metal resin of resin. Moreover, in one preferable embodiment of the metal foil with a carrier which concerns on this invention, the binder for improving the adhesive force with metal foil is not added in resin.

Control of peeling strength may be used individually or in mixture of the silane compound represented by following Formula, or its hydrolysis generating substance, or the condensate of this hydrolysis generating substance (henceforth simply a silane compound). It is because adhesiveness falls suitably by bonding a plate-shaped carrier and metal foil using the said silane compound, and it becomes easy to adjust peeling strength to the above-mentioned range.

[Formula 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 at least one hydrogen group is any of those hydrocarbon groups substituted with halogen atoms, R ³ And R ⁴ is 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 at least one hydrogen 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. When no alkoxy group is present and a hydrocarbon group is selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or when a substituent is composed of only one of these hydrocarbon groups in which at least one hydrogen atom is substituted with a halogen atom, the adhesion between the plate carrier and the surface of the metal foil It tends to be excessively low. Moreover, the said silane compound is a hydrocarbon group chosen from the group which consists of an alkyl group, a cycloalkyl group, and an aryl group, or it is necessary to have at least one of these hydrocarbon groups in which one or more hydrogen atoms were substituted by the halogen atom. When the said hydrocarbon group does not exist, it is because there exists a tendency for the adhesiveness of a plate-shaped carrier and the surface of a metal foil to rise. In addition, the alkoxy group which concerns on this invention shall contain the alkoxy group in which one or more hydrogen atoms were substituted by the halogen atom.

In order to adjust the peeling strength of a plate-shaped carrier and metal foil to the above-mentioned range, it is preferable that the said silane compound has three alkoxy groups and the said hydrocarbon group (it contains the hydrocarbon group by which one or more hydrogen atoms were substituted by the halogen atom). Do. When this is said by the said formula, both of R <^3> and R <^4> become an alkoxy group.

Alkoxy groups include, but are not limited to, methoxy groups, ethoxy groups, n- or iso-propoxy groups, n-, iso- or tert-butoxy groups, n-, iso- or neo-pentoxy groups, n-hexoxy groups, Linear, branched, or cyclic C1-C20, preferably C1-C10, more preferably C1-C5 alkoxy, such as a cyclohexoxy group, n-heptoxy group, and n-octoxy group The group can be mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Alkyl groups include, but are not limited to, methyl, ethyl, n- or iso-propyl groups, n-, iso- or tert-butyl groups, n-, iso- or neo-pentyl groups, n-hexyl groups, n-jade Linear or branched C1-C20, preferably C1-C10, more preferably C1-C5 alkyl groups, such as a methyl group and an n-decyl group, are mentioned.

Although it is not limited to a cycloalkyl group, C3-C10, Preferably it is a C5-C7 cycloalkyl group, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group Can be mentioned.

Examples of the aryl group include aryl groups 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., tolyl group, xylyl group), 1- or 2-naphthyl group, and anthryl group. have.

At least one hydrogen atom may be substituted with a halogen atom in these hydrocarbon groups, for example, may be substituted with 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 neo-pentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane: alkyl substituted phenyltrimethoxysilane (e.g. p- (methyl) phenyl Trimethoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyl Triethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, alkyl substituted phenyltriethoxysilane (e.g. p- (methyl) phenyltriethoxysilane), (3, 3,3-trifluoropropyl) trimethoxysilane, tridecafluorooctyltriethoxysilane, methyltrichlorosil , Dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, their hydrolysis products, and condensates of these hydrolysis products, and the like. . Among these, propyl trimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of the availability.

The metal foil with a carrier can be manufactured by bringing a plate-shaped carrier and metal foil into close contact with a hot press. For example, it can manufacture by apply | coating the said silane compound to the bonding surface of metal foil and / or plate-shaped carrier as needed, and then hot-press-laminating the resin plate-shaped carrier of B stage with respect to the bonding surface of metal foil.

The silane compound can be used in the form of an aqueous solution. In order to improve the solubility in water, alcohol, such as methanol and ethanol, can also be added. The addition of alcohol is particularly effective when using a highly hydrophobic silane compound. The aqueous solution of the silane compound promotes hydrolysis of the alkoxy group by stirring, and condensation of the hydrolysis product is accelerated when the stirring time is long. Generally, using the silane compound which hydrolysis and condensation advanced through sufficient stirring time tends to peel the peeling strength of metal foil and a plate-shaped carrier. Therefore, peeling strength can be adjusted by adjustment of stirring time. Although it is not limited, As stirring time after melt | dissolving a silane compound in water, it can be set as 1 to 100 hours, for example, and can be made to 1 to 30 hours typically. Naturally, there is also a method of using without stirring.

The higher the concentration of the silane compound in the aqueous solution of the silane compound tends to lower the peel strength of the metal foil and the plate-shaped carrier, and the peel strength can be adjusted by adjusting the concentration of the silane compound. Although it is not limited, the density | concentration in the aqueous solution of a silane compound can be 0.01-10.0 volume%, and can be 0.1-5.0 volume% typically.

There is no restriction | limiting in particular in pH of the aqueous solution of a silane compound, Even if it is an acidic side or an alkaline side, it can use. For example, it can use at pH of the range of 3.0-10.0. It is preferable to set it as the pH of the range of 5.0-9.0 which is neutral vicinity from a viewpoint that a special pH adjustment is unnecessary, and it is more preferable to set it as the pH of the range of 7.0-9.0.

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

In addition, the surface of a metal foil or resin is measured with apparatuses, such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), and Si detects If it is, it can be inferred that a silane compound exists in the surface of metal foil or resin.

Moreover, from another viewpoint, this invention provides the use of the above-mentioned metal foil with a carrier.

Firstly, a multilayer metal-clad laminate comprising laminating resin on at least one metal foil side of the above-described metal foil with a carrier, and then laminating the resin or metal foil repeatedly one or more times, for example, 1 to 10 times. A method for producing is provided.

Secondly, the resin is laminated on the metal foil side of the metal foil with a carrier described above, and then the resin, the single-sided or double-sided metal-coated laminate, or the metal foil with a carrier of the present invention, or the metal foil is one or more times, for example, 1 to 10. There is provided a method for producing a multilayer metal-clad laminate comprising laminating repeatedly.

In the manufacturing method of the said multilayer metal coating laminated board, the process of peeling and separating the plate-shaped carrier and metal foil of the said metal foil with a carrier can be further included.

Furthermore, after peeling and isolate | separating the said plate-shaped carrier and metal foil, the process of removing part or all of metal foil by an etching can further be included.

Fourth, the resin is laminated on the metal foil side of the metal foil with a carrier as described above, and then the resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, or the metal foil with a carrier of the present invention, or the metal foil at least once, For example, the manufacturing method of the buildup board | substrate which includes laminating | stacking repeatedly 1-10 times is provided.

Fifth, the manufacturing method of the buildup board | substrate which includes the process of laminating | stacking one or more layers of buildup wiring layers on the metal foil side of the metal foil with a carrier mentioned above is provided. At this time, the buildup wiring layer can be formed using at least one of a subtractive method, a full additive method, or a semiadditive method.

The subtractive method refers to a method of selectively removing unnecessary portions of 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 to form a conductor pattern. The full additive method is a method of forming a conductor pattern by electroless plating or / and electrolytic plating without using metal foil for the conductor layer, and the semi-additive method is electroless on a seed layer made of metal foil, for example. It is a method of obtaining a conductor pattern by etching a metal seed, electroplating, etching, or both together, forming a conductor pattern, and then etching and removing an unnecessary seed layer.

In the manufacturing method of the said buildup board | substrate, a hole is made to single-sided or double-sided wiring board, single-sided or double-sided metal clad laminated board, metal foil of carrier foil, plate-shaped carrier of metal foil with carrier, or resin, and the side and bottom of the said hole It may further comprise a process of conducting plating on. Further, the 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 metal foil with carrier is further performed. It may also include.

In the manufacturing method of said buildup board | substrate, the process of laminating | stacking a metal foil on single surface on the surface in which wiring was formed, and also laminating | stacking the carrier side of the metal foil with a carrier which concerns on this invention may be included. Moreover, the process of laminating | stacking resin on the wiring-formed surface and laminating | stacking the metal foil with a carrier which concerns on this invention which adhere | attached the metal foil on both surfaces to the said resin may also be included.

In addition, "wiring formed surface" means the part in which the wiring was formed in the surface which appears every time in the process of building up, and a buildup board | substrate includes the thing of a final product, and the thing in the middle.

In the manufacturing method of said buildup board | substrate, you may further include the process of peeling and isolate | separating the plate-shaped carrier and metal foil of the said metal foil with a carrier.

Furthermore, after peeling and separating said plate-shaped carrier and metal foil, you may further include the process of removing part or whole surface of metal foil by an etching.

Moreover, in the manufacturing method of the above-mentioned multilayer metal clad laminated board, and the manufacturing method of a buildup board | substrate, each layer can be laminated | stacked by performing thermocompression bonding. This thermocompression bonding may be performed every time one layer of one layer is laminated | stacked, may be carried out after laminating | stacking to some extent, and may be carried out by gathering at last.

Hereinafter, as a specific example of the use mentioned above, the manufacturing method of the coreless buildup board | substrate using the copper foil 11 with a carrier which made copper foil adhere to both surfaces of the plate-shaped carrier 11c of the resin plate which concerns on this invention is illustrative. Explain. In this method, after the build-up layer 16 is laminated | stacked on both sides of the copper foil 11 with a carrier as needed, both surfaces copper foil is peeled from the copper foil 11 with a carrier (refer FIG. 3).

For example, resin as an insulating layer, a 2-layer circuit board, and resin as an insulating layer are piled up on the metal foil side of the metal foil with a carrier of this invention in order, and the metal foil side is made to contact a resin plate on it further, The buildup board | substrate can be manufactured by overlapping the metal foil of the metal foil with a carrier of this invention in order.

Moreover, as another method, resin as an insulating layer and metal foil as a conductor layer are laminated | stacked in order to the at least one metal foil side of the metal foil with a carrier which contact | adhered metal foil to the both surfaces or single side | surface of the resin plate-shaped carrier 11c in order. . Next, you may include the process of half-etching the whole surface of metal foil and adjusting thickness as needed. Next, laser processing is performed at a predetermined position of the laminated metal foil to form a via hole penetrating the metal foil and the resin, and a desmear treatment is performed to remove smear in the via hole, and then the entire or part of the via hole bottom, side, and metal foil. Electroless plating is performed to form an interlayer connection, and electrolytic plating is further performed as necessary. Plating resists may be formed in advance on the portions of the metal foil where electroless plating or electrolytic plating is not necessary before each plating is performed. In addition, in the case where the adhesion between the electroless plating, the electrolytic plating, the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically harmonized in advance. If a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the metal foil, the electroless plating portion, and the electrolytic plating portion by etching. In this way, a build-up substrate is obtained. The process from lamination of resin and copper foil to circuit formation may be repeated a plurality of times to further form a multilayer buildup substrate.

Moreover, you may laminate | stack on the outermost surface of this buildup board | substrate by making the resin side of the metal foil of the metal foil with a carrier adhere | attached one side of this invention, and laminating | stacking, and after laminating | stacking a resin plate once, metal foil will be attached to both surfaces of this invention. You may laminate | stack and make one metal foil of the metal foil with a carrier adhered to contact.

Here, as the resin plate used for manufacturing a buildup board | substrate, the prepreg containing a thermosetting resin can be used preferably.

Moreover, by another method, resin as an insulating layer, for example, prepreg or photosensitive resin, on the exposed surface of the metal foil of the laminated body obtained by bonding a metal foil, for example, copper foil, to the single side | surface or both surfaces of the plate-shaped carrier of this invention. Laminated. Thereafter, via holes are formed at predetermined positions of the resin. When using a prepreg, for example as resin, via hole can be implemented by laser processing. What is necessary is just to perform the desmear process which removes the smear in this via hole after laser processing. Moreover, when photosensitive resin is used as resin, resin of a via hole formation part can be removed by the photolithographic method. Next, electroless plating is performed on the via hole bottom part, the side surface, and the whole surface or part of resin, and an interlayer connection is formed, and electroplating is performed further as needed. Plating resists may be formed in advance on the portions of the resin where electroless plating or electrolytic plating is not required before each plating. In addition, when the adhesiveness of electroless plating, electrolytic plating, plating resist, and resin is inadequate, you may chemically coordinate the surface of resin previously. If a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the electroless plating portion or the electrolytic plating portion by etching. In this way, a build-up substrate is obtained. It is good also as a multilayer buildup board | substrate, carrying out the process from lamination of resin to circuit formation in multiple times repeatedly.

Moreover, you may laminate | stack to the outermost surface of this buildup board | substrate by contacting the resin side of the laminated body which contact | adhered metal foil to the single side | surface of this invention, or the resin side of the metal foil with carrier which adhere | attached metal foil to single side | surface, and laminating resin once After that, you may laminate | stack by contacting one metal foil of the laminated body which contact | adhered metal foil to both surfaces of this invention, or one metal foil of the metal foil with carrier which closely contacted metal foil to both surfaces.

About the coreless buildup board | substrate manufactured in this way, a wiring is formed in the surface through a plating process and / or an etching process, and a buildup wiring board is completed by peeling-separating between carrier resin and copper foil. After peeling separation, wiring may be formed with respect to the peeling surface of a metal foil, and the metal foil whole surface may be removed by etching, and may be a buildup wiring board. Moreover, a printed circuit board is completed by mounting electronic components in a buildup wiring board. Moreover, even if an electronic component is mounted directly on the coreless buildup board | substrate before resin peeling, a printed circuit board can be obtained.

Example

Although an experimental example is shown as an Example and a comparative example of this invention below, these experimental examples are provided in order to understand this invention and its advantage better, and it does not intend that invention is limited.

Experimental Example 1

A plurality of electrolytic copper foils (thickness: 12 µm) were prepared, and nickel-zinc (Ni-Zn) alloy plating treatment and chromate (Cr-Zn) under the following conditions for the shiny (S) surface of each electrolytic copper foil. Chromate) treatment, and the 10-point average roughness (measured according to Rz jis: JIS B 0601: 2001) of the bonded surface (here, S surface) is set to 1.5 µm, and then a prepreg manufactured by Mitsubishi Gas Chemical Co., Ltd. is used as the resin. (BT resin) was bonded together with the S surface of the said electrolytic copper foil, the hot press process was performed at 190 degreeC for 100 minutes, and the copper foil with a carrier was manufactured.

(Nickel-zinc alloy plating)

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

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

pH 3.1

Liquid temperature 40 ℃

Current density 0.1 to 10 A / dm 2

Plating time 0.1 to 10 seconds

(Chromate processing)

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

Liquid temperature 55 ℃

Current density 0.1 to 10 A / dm 2

Plating time 0.1 to 10 seconds

About some electrolytic copper foil, after apply | coating the aqueous solution of a silane compound to the said S surface using a spray coater, after drying the copper foil surface in 100 degreeC air, it bonded together with the prepreg. Table 1 shows the types of the silane compounds, the stirring time before dissolving the silane compound 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 with respect to the conditions for use of the silane compound.

Moreover, assuming that some of the copper foils with a carrier are subjected to a heat history during further heat treatment such as circuit formation with respect to the copper foils with a carrier, the conditions described in Table 1 (here, at 220 ° C. for 3 hours) Heat treatment was performed.

The peeling strength of the copper foil with a carrier obtained by hot press, and the copper foil in the copper foil with a carrier after heat-processing further, and plate-shaped carrier (resin after heating) were measured. Each result is shown in Table 1.

In addition, in order to evaluate peel workability, the work time (time / piece) by a human hand per unit number was evaluated, respectively. The results are shown in Table 2.

Experimental Examples 2 to 18

Copper foil, resin (prepreg), and some shown in Table 1 used the silane compound, and manufactured copper foil with a carrier in the same procedure as Experimental example 1. In some experimental examples, the heat treatment of the conditions shown in Table 1 was further performed. Evaluation similar to Experimental Example 1 was performed about each. The results are shown in Tables 1 and 2.

In addition, the classification of the bonding surface of copper foil, the conditions of surface treatment, surface roughness Rz jis, the use condition of a silane compound, the kind of prepreg, and the lamination conditions of copper foil and a prepreg are as Table 1 shown.

In the surface treatment conditions of the processed surface of copper foil, the specific conditions of an epoxy silane (treatment) and a roughening process are the following.

(Epoxysilane treatment)

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

pH5.0 to 9.0

Stirred at room temperature for 12 hours

Treatment method: After apply | coating a process liquid using a spray coater, a process surface is dried for 5 minutes in 100 degreeC air.

(Harmony processing)

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

H ₂ SO ₄ concentration 50-100 g / ℓ

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

Liquid temperature 40 ℃

Current density 40-100 A / dm 2

Plating time 0.1 to 30 seconds

<Experimental Examples 19-20>

Copper foil, resin (prepreg), and some shown in Table 3 used the silane compound, and manufactured copper foil with a carrier in the same procedure as Experimental example 1. Furthermore, the heat processing on the conditions shown in Table 3 was performed. Evaluation similar to Experimental Example 1 was performed about the copper foil with a carrier obtained in this way. The results are shown in Tables 3 and 4.

Moreover, S surface was used as the bonding surface of copper foil, and the surface was chromate-treated on the conditions mentioned above. In addition, the surface roughness Rz jis of copper foil, the kind of prepreg, the use condition of the silane compound for surface treatment of a prepreg, and lamination conditions of copper foil and a prepreg are as Table 3 shown.

According to the table, even if the silane compound is processed on the surface of copper foil or the surface of a prepreg, it turns out that the equivalent result was obtained in the peeling strength of the laminated body after that, the peeling strength after heating, and peeling workability. .

(Build-up wiring board)

Thus, FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nikko Niseki Kinzoku Co., Ltd., JTC12 µm (product name)) were superimposed on both sides of the copper foil with a carrier thus prepared in order. And hot pressing were performed under the heating conditions shown in each table by the pressure of 3 Mpa, and the 4-layer copper clad laminated board was manufactured.

Next, the hole of 100 micrometers in diameter penetrating the copper foil on the surface of the said 4-layer copper clad laminated board, and the insulating layer (hardened prepreg) below was drilled using a laser processing machine. Then, copper plating is performed by electroless copper plating and electro copper plating on the copper foil surface on the copper foil with a carrier exposed to the bottom part of the said hole, and the copper foil of the side surface of the said hole, and the said four-layer copper clad laminated board surface. The electrical connection was formed between copper foil on copper foil with a carrier, and copper foil on the surface of a four-layer copper clad laminated board. Next, a part of copper foil on the surface of a four-layer copper clad laminated board was etched using the ferric chloride type etching liquid, and the circuit was formed. In this way, a four-layer build-up substrate was obtained.

Subsequently, in the said 4-layer buildup board | substrate, two sets of 2-layer buildup wiring boards were obtained by peeling and isolate | separating the plate-shaped carrier and copper foil of the said copper foil with a carrier.

Subsequently, the copper foil of the side in close contact with the plate-shaped carrier on the two sets of two-layer build-up wiring boards was etched to form wiring, thereby obtaining two sets of two-layer build-up wiring boards.

As for each experiment example, several four-layer buildup board | substrate was manufactured, and the adhesion degree of the prepreg and copper foil which comprise the copper foil with a carrier in a buildup board | substrate manufacturing process about each visually confirmed, Table 1, In Table 3, in the buildup wiring board using the copper foil with a carrier manufactured on the conditions by which peeling strength and the peeling strength after heating were evaluated as "S" and "G", resin of copper foil with a carrier at the time of buildup (plate-shaped carrier) It was peeled off without breaking. However, about the conditions evaluated as "G", there existed some copper foils peeling from a plate-shaped carrier without peeling operation at the time of a buildup as described also in Tables 1 and 3.

Moreover, about the conditions evaluated as "N", resin was broken in the peeling operation of the copper foil in the copper foil with a carrier at the time of buildup, or resin remained on the copper foil surface without peeling.

Moreover, about the conditions evaluated as "-", although resin peeled without destroying at the time of peeling operation of the copper foil in the copper foil with a carrier at the time of buildup, the copper foil peeled without the peeling operation in that case.

11 metal foil with carrier
11a metal foil
11b silane compound
11c plate carrier
16 Buildup Floor

Claims (1)

Metal foil with a carrier as described in the description of the invention.

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