WO2013183607A1 - Carrier-attached metal foil - Google Patents

Description

Metal foil with carrier

The present invention relates to a metal foil with a carrier. More specifically, the present invention relates to a metal foil with a carrier used in the production of a single-sided or two-layer multilayer board or an ultra-thin coreless substrate used for a printed wiring board.

A typical example of a multilayer laminate is a printed circuit board. Generally, a printed circuit board uses a dielectric material called “prepreg” obtained by impregnating a synthetic resin plate, a glass plate, a glass nonwoven fabric, paper or the like with a synthetic resin as a basic constituent material. . Further, a sheet such as copper or copper alloy foil having electrical conductivity is bonded to the side facing the prepreg. The laminated body thus assembled is generally called a CCL (Copper Clad Laminate) material. The surface of the copper foil in contact with the prepreg is usually a mat surface in order to increase the bonding strength. A foil made of aluminum, nickel, zinc or the like may be used instead of the copper or copper alloy foil. Their thickness is about 5 to 200 μm. This commonly used CCL (Copper Clad Laminate) material is shown in FIG.

Patent Document 1 proposes a metal foil with a carrier composed of a synthetic resin plate-shaped carrier and a metal foil that is mechanically peelably adhered to at least one surface of the carrier. Describes that it can be used for the assembly of printed wiring boards. It was shown that the peel strength between the plate-like carrier and the metal foil is preferably 1 gf / cm to 1 kgf / cm. According to the metal foil with a carrier, since the copper foil is supported over the entire surface by the synthetic resin, generation of wrinkles on the copper foil during lamination can be prevented. In addition, since the metal foil with carrier is in close contact with the synthetic resin without gaps, when the surface of the metal foil is plated or etched, it can be put into the chemical solution for plating or etching. . Furthermore, since the linear expansion coefficient of the synthetic resin is at the same level as the copper foil that is a constituent material of the substrate and the prepreg after polymerization, the circuit is not misaligned, resulting in fewer defective products, It has the outstanding effect that a yield can be improved.

JP 2009-272589 A

The copper foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to the reduction of the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield, but the board for the specific application of the metal foil with the carrier There is no mention of a configuration that takes into account temporary adhesion between the carrier and the metal foil and subsequent peeling, and there remains room for improvement.

For example, in applications that are used without going through too many heat processing steps, such as shield materials that are formed by applying mesh processing, before the metal foil and the synthetic resin are in close contact with each other It is important that it does not peel carelessly and can be intentionally peeled off at the interface between the metal foil and the synthetic resin when performing a peeling operation. That is, in order to avoid inadvertent peeling, if the peel strength of both is excessively increased, this time, when the metal foil and the synthetic resin are peeled, the resin portion is destroyed, and the resin content is on the surface of the metal foil. It may remain and is not preferred.

Therefore, the present invention seeks a useful condition for allowing the plate-like carrier and the metal foil to be peeled in close contact with each other, and further provides a metal foil with a carrier capable of intentional peeling at the interface between the metal foil and the plate-like carrier. The issue is to provide.

As a result of earnest research on the above-mentioned problems, the present inventors have inadvertently placed the metal foil and the plate carrier between the metal foil and the plate carrier by setting the peel strength between them to a certain range. It has been found that no peeling occurs and intentional peeling is possible, and the present invention has been completed.

That is, the present invention is as follows.
(1) A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is detachably adhered to at least one surface of the carrier, and is 220 ° C. for 3 hours, 6 hours, or 9 hours. The metal foil with a carrier whose peeling strength of metal foil and a plate-shaped carrier after at least 1 heating is 10 gf / cm or more and 200 gf / cm or less.
(2) The metal foil with a carrier according to (1), wherein the resin plate-like carrier contains a thermosetting resin.
(3) The resin-made plate-shaped carrier is a metal foil with a carrier according to (1) or (2), which is a prepreg.
(4) The metal plate with a carrier according to (2) or (3), wherein the resinous plate-shaped carrier has a glass transition temperature Tg of 120 to 320 ° C.
(5) The metal foil with a carrier according to any one of (1) to (4), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 μm or less.
(6) The metal foil with a carrier according to any one of (1) to (5), wherein a peel strength between the metal foil and the plate-like carrier before the heating 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 the carrier have the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, 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 one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
The metal foil with a carrier according to any one of (1) to (6), wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product shown in the above are used alone or in combination.
(8) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then the resin or the metal foil is repeatedly laminated one or more times. A method for producing a multilayer metal-clad laminate comprising:
(9) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to ( 7) A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier according to any one of 1) or a metal foil repeatedly one or more times.
(10) In the method for producing a multilayer metal-clad laminate according to (8) or (9), the multilayer metal-clad laminate further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier. A manufacturing method of a board.
(11) The method for producing a multilayer metal-clad laminate comprising the step of removing a part or all of the separated and separated metal foil by etching in the production method according to (10).
(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 buildup substrate, comprising a step of forming one or more buildup wiring layers on at least one metal foil side of the metal foil with carrier according to any one of (1) to (7).
(14) The buildup wiring layer manufacturing method according to (13), wherein the buildup wiring layer is formed using at least one of a subtractive method, a full additive method, and a semi-additive method.
(15) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, (1) A method for producing a build-up substrate, comprising repeatedly laminating a metal foil with a carrier or a metal foil according to any one of (7) at least once.
(16) In the method for manufacturing a buildup board according to (15), a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, or a resin The manufacturing method of the buildup board | substrate which further includes the process of drilling a hole in and carrying out conductive plating to the side and bottom face of the said hole.
(17) In the method for manufacturing a buildup board according to (15) or (16), 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 with carrier The manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least 1 of the metal foil which comprises foil once or more.
(18) including a step of contacting and laminating the resin plate side of the metal foil with carrier according to any one of (1) to (7), wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. (15) The method for manufacturing a build-up substrate according to any one of (17) to (17).
(19) One metal foil of the metal foil with a carrier according to any one of (1) to (7), wherein a resin is laminated on the surface on which the wiring is formed, and the metal foil is adhered to both sides of the resin. (15) The method for manufacturing a buildup substrate according to any one of (15) to (17), further including a step of laminating the layers.
(20) The method for manufacturing a buildup substrate according to any one of (15) to (19), wherein at least one of the resins is a prepreg.
(21) The buildup wiring according to any one of (13) to (20), further comprising a step of peeling and separating the plate-like carrier and the metal foil of the metal foil with carrier. A manufacturing method of a board.
(22) The method for manufacturing a buildup wiring board according to (21), further comprising a step of removing a part or all of the metal foil adhered to the plate carrier by etching.
(23) A build-up wiring board obtained by the manufacturing method according to (21) or (22).
(24) A method for producing a printed circuit board, comprising a step of producing a build-up substrate by the production method according to any one of (13) to (20).
(25) A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to (21) or (22).

According to the present invention, it is possible to provide a metal foil with a carrier that does not cause inadvertent peeling between the metal foil and the plate-like carrier and can be intentionally peeled off. .

An example of the configuration of CCL is shown. The structural example of the metal foil with a carrier which concerns on this invention is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined on both surfaces of the resin board) is shown.

In one embodiment of a metal foil with a carrier according to the present invention, a metal foil with a carrier comprising a resin-made plate-like carrier and a metal foil that is detachably adhered to one or both sides, preferably both sides of the carrier, is prepared. To do. One structural example of the metal foil with a carrier according to the present invention is shown in FIGS. In particular, the metal foil 11 with a carrier in which the metal foil 11a is detachably adhered to both surfaces of a resin-made plate carrier 11c is shown at the beginning of FIG. The plate-like carrier 11c and the metal foil 11a are bonded together using a silane compound 11b described later.

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

Since the metal foil with carrier used in the present invention must be peeled off eventually, it is inconvenient that the adhesiveness is excessively high, but the plate-like carrier and the metal foil are chemicals such as plating performed in the printed circuit board manufacturing process. Adhesiveness that does not peel in the processing step is necessary.

Also, in the process of manufacturing a multilayer printed wiring board, heat treatment is often performed in a lamination press process or a desmear process. Therefore, the heat history that the metal foil with a carrier receives becomes severer as the number of laminated layers increases. Therefore, when considering application to a multilayer printed wiring board in particular, it is desirable that the peel strength between the metal foil and the plate-like carrier is in the above-described range even after passing through a required thermal history.

Therefore, in one embodiment of the present invention, assuming the heating conditions in the manufacturing process of the multilayer printed wiring board, for example, the metal foil after at least one heating at 220 ° C. for 3 hours, 6 hours, or 9 hours The peel strength of the plate-like carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and even more preferably 50 gf / cm or more, while it is 200 gf / cm or less. Preferably, it is 150 gf / cm or less, and more preferably 80 gf / cm or less.

Regarding the peel strength after heating at 220 ° C., the peel strength was described above in both 3 hours and 6 hours, or both 6 hours and 9 hours from the viewpoint of being able to cope with various lamination numbers. It is preferable to satisfy the range, and it is further preferable that all peel strengths after 3 hours, 6 hours, and 9 hours satisfy the above-described range.

As described above, after the heat treatment in the manufacturing process of the multilayer printed wiring board, the peeling strength between the metal foil and the plate-like carrier is set in such a range so that the peeling does not occur at the time of transportation or processing in the manufacturing process. It can be easily peeled off manually after the heat treatment, that is, mechanically peeled off.

Furthermore, the copper foil with a carrier of the present invention can be used for applications that are used without passing through many heat processing steps, such as a shield material formed by applying mesh processing.

From this viewpoint, in the metal foil with a carrier before the heat treatment in the manufacturing process of the multilayer printed wiring board described above, the peel strength between the metal foil and the plate-like carrier is preferably 10 gf / cm or more, and preferably 30 gf / cm. More preferably, it is more preferably 50 gf / cm or more, while it is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and 80 gf / cm or less. Even more preferred. By setting the peel strength of the metal foil and the plate-like carrier in such a range, it can be easily peeled off manually, while being not peeled off during transport or processing.

In the present invention, the peel strength is measured in accordance with a 90 degree peel strength measuring method defined in JIS C6481.

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

The resin that serves as the plate-like carrier is not particularly limited, and phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used, but a thermosetting resin is preferable. A prepreg can also be used. The prepreg before being bonded to the metal foil is preferably in a B-stage state. The linear expansion coefficient of the prepreg (C stage) is 12 to 18 (× 10 ⁻⁶ / ° C.), 16.5 (× 10 ⁻⁶ / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 (× 10 ⁻⁶ / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer 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 preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimum range, 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).

Also, it is desirable that the thermal expansion coefficient of the resin is within + 10% and −30% of the thermal expansion coefficient of the metal foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the metal foil and the resin, thereby reducing the occurrence of defective products and improving the yield.

The thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin, it will bend and will not flow through the printed wiring board manufacturing process. Therefore, it is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

As the metal foil, copper or copper alloy foil is a typical one, but foil of aluminum, nickel, zinc or the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used. Although not limited, the metal foil generally has a thickness of 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less, considering use as a wiring of a printed circuit board. When metal foil is affixed on both surfaces of the plate-like carrier, metal foils having the same thickness may be used, or metal foils having different thicknesses may be used.

The metal foil used may be subjected to various surface treatments. 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 (including the case where one or more alloy elements such as Zn, P, Ni, Mo, Zr and Ti are contained in the chromate treatment solution) for imparting rust prevention and discoloration resistance, surface roughness (For example, copper electrodeposition grains, Cu—Ni—Co alloy plating, Cu—Ni—P alloy plating, Cu—Co alloy plating, Cu—Ni alloy plating, Cu—Co alloy plating, And copper alloy plating such as Cu—As alloy plating and Cu—As—W alloy plating). The roughening treatment not only affects the peel strength between the metal foil and the plate carrier, but also the chromate treatment has a great influence. Chromate treatment is important from the viewpoint of rust prevention and discoloration resistance, but since it tends to significantly increase the peel strength, it is also meaningful as a means for adjusting the peel strength.

In conventional CCL, since it is desired that the peel strength between the resin and the copper foil is high, for example, the matte surface (M surface) of the electrolytic copper foil is used as an adhesive surface with the resin, and surface treatment such as roughening treatment is performed. Thus, the adhesive strength is improved by the chemical and physical anchoring effects. On the resin side, various binders are added to increase the adhesive strength 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, it is disadvantageous that the peel strength is excessively high.

Therefore, in a preferred embodiment of the metal foil with a carrier according to the present invention, the surface roughness of the bonded surface is JIS B 0601: in order to adjust the peel strength between the metal foil and the plate-like carrier to the preferred range described above. Expressed by the ten-point average roughness (Rz jis) of the metal foil surface measured according to 2001, it is preferably 3.5 μm or less, more preferably 3.0 μm or less. However, reducing the surface roughness indefinitely takes time and increases costs, so it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When electrolytic copper foil is used as the metal foil, it is possible to use either a glossy surface (shiny surface, S surface) or a rough surface (matte surface, M surface) by adjusting to such a surface roughness. However, it is easier to adjust the surface roughness by using the S-plane. On the other hand, the ten-point average roughness (Rz jis) of the surface of the metal foil that does not contact the carrier is preferably 0.4 mμ 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 bonding surface of the metal foil with the resin. Moreover, in preferable one Embodiment of 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.

The peel strength is adjusted by using a silane compound represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a silane compound) alone or in combination. Also good. This is because by sticking the plate-like carrier and the metal foil together using the silane compound, the adhesiveness is appropriately lowered and the peel strength can be easily adjusted to the above-described range.

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, 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 one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)

The silane compound must have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much. The silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have at least one. This is because when the hydrocarbon group does not exist, the adhesion between the plate-like carrier and the metal foil surface tends to increase. The alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.

In adjusting the peel strength between the plate-like carrier and the metal foil to the above-mentioned range, the silane compound has three alkoxy groups and the hydrocarbon group (a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom). It is preferable to have one). In terms of the above formula, both R ³ and R ⁴ are alkoxy groups.

Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group and the like, straight chain, branched or cyclic carbon number of 1-20, preferably carbon number of 1-10, more preferably carbon number of 1- 5 alkoxy groups.
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 group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, and n-hexyl. A linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as a group, n-octyl group and n-decyl group.

Examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, which have 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. An alkyl group is mentioned.

The aryl group includes a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, etc., having 6 to 20, preferably 6 to 14 carbon atoms. An aryl group is mentioned.

In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, 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 neo-pentyl. Trimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl-substituted phenyltrimethoxysilane (eg, p- (methyl) phenyltrimethoxysilane), methyltriethoxysilane, ethyl Triethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxy Silane, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane (eg, p- (methyl) phenyltriethoxysilane), (3,3,3-trifluoropropyl) trimethoxysilane, and trideca Fluorooctyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, their hydrolysis products, and condensates of these hydrolysis products Etc. Among these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of availability.

The metal foil with carrier can be manufactured by bringing a plate-like carrier and metal foil into close contact with each other by hot pressing. For example, after applying the silane compound to the bonding surface of the metal foil and / or the plate-like carrier as necessary, the B-stage resin plate-like carrier is hot to the bonding surface of the metal foil. It can be manufactured by press lamination.

The silane compound can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a highly hydrophobic silane compound is used. By stirring the aqueous solution of the silane compound, hydrolysis of the alkoxy group is promoted, and when the stirring time is long, condensation of the hydrolysis product is promoted. In general, the peel strength between the metal foil and the plate carrier tends to decrease when a silane compound that has undergone hydrolysis and condensation after a sufficient stirring time has been used. Therefore, the peel strength can be adjusted by adjusting the stirring time. Although not limited, the stirring time after the silane compound is dissolved in water can be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is a method of using without stirring.

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

The pH of the aqueous solution of the silane compound is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is required, the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .

As conditions for hot pressing for producing a metal foil with a carrier, when a prepreg is used as a plate-like carrier, it is preferable to perform hot pressing 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 was measured with a scanning electron microscope or the like equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis). If detected, it can be inferred that a silane compound is present on the surface of the metal foil or resin.

Furthermore, from another viewpoint, this invention provides the use of the metal foil with a carrier mentioned above.
First, a multilayer metal comprising laminating a resin on at least one metal foil side of the above-described metal foil with carrier, and then laminating the resin or the metal foil repeatedly one or more times, for example, 1 to 10 times. A method for producing a tension laminate is provided.

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

The above-described method for producing a multilayer metal-clad laminate can further include a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier.

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

Fourth, the resin is laminated on the metal foil side of the metal foil with carrier, and then the resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil. Provided is a method for manufacturing a build-up substrate, which includes repeatedly laminating at least once, for example, 1 to 10 times.

Fifth, there is provided a method for manufacturing a buildup board including a step of laminating one or more buildup wiring layers on the metal foil side of the metal foil with carrier described above. At this time, the build-up wiring layer can be formed by using at least one of a subtractive method, a full additive method, and a semi-additive method.

The subtractive method is a method of forming a conductor pattern by 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. Point to. The full additive method is a method of forming a conductor pattern by electroless plating and / or electrolytic plating without using a metal foil for the conductor layer. The semi-additive method is an electroless method on a seed layer made of metal foil, for example. In this method, a conductor pattern is formed by using metal deposition and electrolytic plating, etching, or a combination thereof, and then an unnecessary seed layer is removed by etching.

In the manufacturing method of the above build-up board, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, or a resin, The method may further include conducting conductive plating on the side surface and the bottom surface of the hole. In addition, the step of forming 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 performed once. It can further include performing the above.

The manufacturing method of the build-up board may further include a step of bringing a metal foil into close contact with one surface on the surface on which the wiring is formed, and further laminating the carrier side of the metal foil with a carrier according to the present invention. . Moreover, it is 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 surface on which the wiring is formed and the metal foil is adhered to both sides of the resin.
The “surface on which the wiring is formed” means a portion where wiring is formed on the surface that appears every time a buildup is performed, and the buildup substrate includes both a final product and an intermediate product.

The manufacturing method of the build-up substrate may further include a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil.

Furthermore, it is possible to further include a step of removing a part or the whole surface of the metal foil by etching after peeling and separating the plate-like carrier and the metal foil.

In addition, in the manufacturing method of the above-mentioned multilayer metal-clad laminate and the manufacturing method of a buildup board, each layer can be laminated | stacked by performing thermocompression bonding. This thermocompression bonding may be performed every time one layer is stacked, may be performed after being laminated to some extent, or may be performed collectively at the end.

Hereinafter, as a specific example of the above-described application, a method for producing a coreless build-up board using the carrier-attached copper foil 11 in which the copper foil is adhered to both surfaces of the plate-like carrier 11c of the resin plate according to the present invention will be exemplarily described. . In this method, after the required number of buildup layers 16 are laminated on both sides of the copper foil with carrier 11, the copper foils on both sides are peeled from the copper foil with carrier 11 (see FIG. 3).

For example, on the metal foil side of the metal foil with a carrier of the present invention, a resin as an insulating layer, a two-layer circuit board, a resin as an insulating layer are stacked in order, and the metal foil side is in contact with the resin plate on it, Furthermore, a buildup board | substrate can be manufactured by laminating | stacking the metal foil of the metal foil with a carrier of this invention in order.

As another method, a resin or conductor layer as an insulating layer is provided on at least one metal foil side of the metal foil with a carrier in which the metal foil is adhered to both surfaces or one surface of the resinous plate-like carrier 11c. Are laminated in order. Next, if necessary, a step of half-etching the entire surface of the metal foil to adjust the thickness may be included. 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 after applying a desmear process for removing smear in the via hole, the bottom of the via hole, the side surface, and the metal foil Electroless plating is performed on the entire surface or a part of the substrate to form an interlayer connection, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the metal foil where electroless plating or electrolytic plating is unnecessary before performing each plating. In addition, when the electroless plating, the electrolytic plating, or the adhesion between the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. When 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 and the electroless plating portion and the electrolytic plating portion by etching. Thereby, a build-up substrate is obtained. The steps from the lamination of the resin and the copper foil to the circuit formation may be repeated a plurality of times to form a multilayer build-up substrate.
Furthermore, on the outermost surface of this buildup substrate, the resin side of the metal foil of the metal foil with a carrier in which the metal foil is adhered to one side of the present invention may be contacted and laminated, or a resin plate is once laminated. Later, one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces of the present invention may be brought into contact with each other and laminated.

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

As another method, a resin as an insulating layer such as a prepreg or a photosensitive layer is formed on the exposed surface of a metal foil of a laminate obtained by laminating a metal foil such as a copper foil on one or both sides of the plate carrier of the present invention. Laminating resin. Thereafter, a via hole is formed at a predetermined position of the resin. For example, when a prepreg is used as the resin, the via hole can be formed by laser processing. After the laser processing, desmear treatment for removing smear in the via hole is preferably performed. When a photosensitive resin is used as the resin, the resin in the via hole forming portion can be removed by a photolithography method. Next, electroless plating is performed on the bottom and side surfaces of the via holes, the entire surface or a part of the resin to form interlayer connections, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the resin where electroless plating or electrolytic plating is unnecessary before performing each plating. Further, when the adhesion between electroless plating, electrolytic plating, plating resist and resin is insufficient, the surface of the resin may be chemically roughened 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. Thereby, a build-up substrate is obtained. The steps from resin lamination to circuit formation may be repeated a plurality of times to form a multilayered build-up substrate.
Further, the outermost surface of this build-up substrate is laminated by contacting the resin side of the laminate in which the metal foil is closely attached to one side of the present invention, or the resin side of the metal foil with a carrier having the metal foil closely attached to one side. Alternatively, after laminating the resin once, one metal foil of the laminate in which the metal foil is adhered to both surfaces of the present invention, or one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces May be laminated in contact with each other.

For the coreless build-up board manufactured in this way, the wiring is formed on the surface through the plating process and / or the etching process, and further, the build-up wiring is separated and separated between the carrier resin and the copper foil. The board is completed. Wiring may be formed on 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. Furthermore, a printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, a printed circuit board can be obtained even if an electronic component is mounted directly on a coreless buildup substrate before resin peeling.

Experimental examples are shown below as examples and comparative examples of the present invention, but these experimental examples are provided for better understanding of the present invention and its advantages, and are intended to limit the invention. is not.

<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) were performed on the shiny (S) surface of each electrolytic copper foil under the following conditions. (Chromate) treatment, the ten-point average roughness (measured in accordance with JIS B 0601: 2001) of the bonded surface (here, S surface) is 1.5 μm, and the resin is Mitsubishi Gas Chemical Co., Ltd. A company-prepared prepreg (BT resin) was bonded to the S surface of the electrolytic copper foil and hot-pressed at 190 ° C. for 100 minutes to prepare a copper foil with a carrier.

(Nickel-zinc alloy plating)
Ni concentration 17g / L (added as NiSO ₄ )
Zn concentration 4g / L (added as ZnSO ₄ )
pH 3.1
Liquid temperature 40 ℃
Current density 0.1-10A / dm ²
Plating time 0.1 to 10 seconds

(Chromate treatment)
Cr concentration 1.4g / 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 0.1-10A / dm ²
Plating time 0.1 to 10 seconds

For some electrolytic copper foils, an aqueous solution of a silane compound is applied to the S surface using a spray coater, and then the copper foil surface is dried in air at 100 ° C., and then bonded to a prepreg. went. Regarding the use conditions of the silane compound, Table 1 shows the type of silane compound, the stirring time from when the silane compound is dissolved in water to before application, the concentration of the silane compound in the aqueous solution, the alcohol concentration in the aqueous solution, and the pH of the aqueous solution. Show.

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

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

Also, in order to evaluate the peeling workability, the work time (hour / piece) by hand per unit number was evaluated. The results are shown in Table 2.

<Experimental Examples 2 to 18>
Copper foil with a carrier shown in Table 1 was prepared in the same procedure as in Experimental Example 1 using a silane compound as a copper foil and a resin (prepreg). In some experimental examples, heat treatment under the conditions shown in Table 1 was further performed. Each was evaluated in the same way as in Experimental Example 1. The results are shown in Tables 1 and 2.

The types of copper foil bonding surfaces, surface treatment conditions and surface roughness Rz jis, silane compound usage conditions, prepreg types, and copper foil and prepreg lamination conditions are as shown in Table 1. is there.

In the surface treatment conditions of the treated surface of the copper foil, specific conditions for epoxysilane (treatment) and roughening treatment are as follows.

(Epoxysilane treatment)
Treatment liquid: 3-glycidoxypropyltrimethoxysilane 0.9 volume% aqueous solution pH 5.0 to 9.0
Stirred at room temperature for 12 hours Treatment method: After applying the treatment liquid using a spray coater, the treated surface is dried in air at 100 ° C. for 5 minutes.

(Roughening treatment)
Cu concentration 20 g / L (added as CuSO ₄ )
H ₂ SO ₄ concentration 50 ~ 100g / L
As concentration 0.01-2.0 g / L (added as arsenite)
Liquid temperature 40 ℃
Current density 40-100A / dm ²
Plating time 0.1-30 seconds

<Experimental Examples 19 to 20>
A copper foil with a carrier shown in Table 3 was prepared in the same procedure as in Experimental Example 1 using a silane compound as a copper foil and a resin (prepreg). Further, heat treatment was performed under the conditions shown in Table 3. 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.

In addition, the S surface was used as the bonding surface of the copper foil, and the surface was chromated under the above-described conditions. In addition, the surface roughness Rz cis of the copper foil, the type of prepreg, the use conditions of the silane compound for the surface treatment of the prepreg, and the lamination conditions of the copper foil and the prepreg are as shown in Table 3.

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

(Build-up wiring board)
FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., JTC 12 μm (product name)) are sequentially stacked on both sides of the copper foil with a carrier thus produced. A four-layer copper clad laminate was produced by hot pressing under the heating conditions shown in each table under the pressure of.

Next, a 100 μm diameter hole penetrating the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine. Subsequently, electroless copper plating on the copper foil surface on the copper foil with carrier exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate, and copper plating by electrolytic copper plating The 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. In this way, a four-layer buildup substrate was obtained.

Subsequently, in the 4-layer build-up board, the two-layer build-up wiring boards were obtained by peeling off and separating the plate-like carrier of the copper foil with carrier and the copper foil.

Subsequently, the copper foil that was in close contact with the plate-like carrier on the two sets of two-layer build-up wiring boards was etched to form a wiring to obtain two sets of two-layer build-up wiring boards. .

In each experimental example, a plurality of four-layer build-up substrates were prepared, and for each, the degree of adhesion between the prepreg and the copper foil constituting the copper foil with carrier in the build-up substrate manufacturing process was confirmed visually. In the build-up wiring board using the copper foil with a carrier produced under the conditions where the peel strength and the peel strength after heating are evaluated as “S” and “G” in Table 3, the resin of the copper foil with the carrier at the time of build-up The (plate-like carrier) could be peeled without being destroyed. However, with respect to the conditions evaluated as “G”, as described in Tables 1 and 3, there were some cases where the copper foil was peeled off from the plate-shaped carrier without a peeling operation during build-up.
As for the condition evaluated as “N”, the resin was destroyed at the time of build-up during the peeling operation of the copper foil in the carrier-attached copper foil, or the resin remained on the copper foil surface without being peeled off.
As for the conditions evaluated as “-”, the resin was peeled off without being destroyed during the copper foil peeling operation in the carrier-added copper foil during build-up, but the copper foil was removed without peeling operation. Sometimes peeled off.

11 Metal foil 11a with carrier 11a Metal foil 11b Silane compound 11c Plate carrier 16 Build-up layer

Claims (25)

A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is releasably adhered to at least one surface of the carrier, and is at 220 ° C. for 3 hours, 6 hours, or 9 hours. The metal foil with a carrier whose peeling strength of metal foil and a plate-shaped carrier after one heating is 10 gf / cm or more and 200 gf / cm or less. The metal foil with a carrier according to claim 1, wherein the resinous plate-like carrier contains a thermosetting resin. The metal foil with a carrier according to claim 1 or 2, wherein the resinous plate-like carrier is a prepreg. The metal foil with a carrier according to claim 2 or 3, wherein the resin plate carrier has a glass transition temperature Tg of 120 to 320 ° C. The metal foil with a carrier according to any one of claims 1 to 4, wherein a ten-point average roughness (Rz cis) of a side surface in contact with the carrier of the metal foil is 3.5 µm or less. The metal foil with a carrier according to any one of claims 1 to 5, wherein a peel strength between the metal foil and the plate-like carrier before the heating is 10 gf / cm or more and 200 gf / cm or less. The plate-like carrier and metal foil that make up the metal foil with the carrier have the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, 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 one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
The metal foil with a carrier according to any one of claims 1 to 6, wherein the silane compound, a hydrolysis product thereof, and a condensate of the hydrolysis product shown in the above are bonded together using a single compound or a combination of plural compounds. A multilayer comprising laminating a resin on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 7, and then laminating the resin or the metal foil repeatedly one or more times. A method for producing a metal-clad laminate. A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 7, and then a resin, a single-sided or double-sided metal-clad laminate, or any one of claims 1 to 7 A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier according to one item or the metal foil repeatedly at least once. 10. The method for producing a multilayer metal-clad laminate according to claim 8 or 9, further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier. 11. The method for producing a multilayer metal-clad laminate according to claim 10, comprising a step of removing a part or all of the separated and separated metal foil by etching. A multilayer metal-clad laminate obtained by the production method according to any one of claims 8 to 11. A method for manufacturing a buildup substrate, comprising a step of forming one or more buildup wiring layers on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 7. The buildup wiring layer according to claim 13, wherein the buildup wiring layer is formed using at least one of a subtractive method, a full additive method, and a semiadditive method. A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 7, and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, A method for producing a build-up substrate, comprising: laminating the metal foil with a carrier according to any one of 7 to 7 or the metal foil repeatedly one or more times. In the manufacturing method of the buildup board | substrate of Claim 15, a hole is provided in the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the metal foil of the metal foil with carrier, the plate-like carrier of the metal foil with carrier, or the resin. A method for manufacturing a build-up substrate, further comprising the steps of opening and conducting conductive plating on the side surface and bottom surface of the hole. The method for manufacturing a buildup board according to claim 15 or 16, wherein 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 constituting the metal foil with carrier A method for manufacturing a build-up substrate, further comprising performing the step of forming a wiring on at least one of the foils once or more. The step of contacting and laminating the resin plate side of the metal foil with carrier according to any one of claims 1 to 7, wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. 18. The method for manufacturing a buildup substrate according to any one of items 1 to 17. The metal foil with a carrier according to any one of claims 1 to 7, wherein a resin is laminated on the surface on which the wiring is formed, and the metal foil is adhered to both sides of the resin. The method for manufacturing a build-up substrate according to any one of claims 15 to 17, further comprising a step of laminating the layers. The method for manufacturing a buildup substrate according to any one of claims 15 to 19, wherein at least one of the resins is a prepreg. The build-up wiring board manufacturing method according to any one of claims 13 to 20, further comprising a step of peeling and separating the plate-like carrier and the metal foil of the metal foil with carrier. Method. 22. The method for manufacturing a buildup wiring board according to claim 21, further comprising a step of removing a part or all of the metal foil adhered to the plate carrier by etching. A build-up wiring board obtained by the manufacturing method according to claim 21 or 22. A method for manufacturing a printed circuit board, comprising a step of manufacturing a build-up substrate by the manufacturing method according to any one of claims 13 to 20. A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to claim 21 or 22.

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