TWI565371B - Attached metal foil - Google Patents

Description

With carrier metal foil

The present invention relates to a metal foil with a carrier. More specifically, it relates to a carrier-attached metal foil for producing a single-layered or two-layer multilayered laminate or an extremely thin hollow substrate for a printed wiring board.

A representative example of a multilayer laminate is a printed circuit board. In general, a printed circuit board is a basic constituent material called a "prepreg" obtained by impregnating a synthetic resin with a base material such as a synthetic resin sheet, a glass plate, a glass nonwoven fabric, or a paper. Further, a sheet such as a conductive copper or copper alloy foil is bonded to the side opposite to the prepreg. The laminate thus assembled is generally referred to as a CCL (Copper Clad Laminate) material. Usually, the surface of the copper foil that is in contact with the prepreg is set to be a matte surface in order to increase the bonding strength. There are also cases where a foil of aluminum, nickel, zinc or the like is used instead of a copper or copper alloy foil. These thicknesses are about 5 to 200 μm. The commonly used CCL (Copper Clad Laminate) material is shown in Fig. 1.

Patent Document 1 proposes a plate-shaped carrier made of a synthetic resin and a metal foil with a metal foil which is adhered to at least one surface of the carrier by mechanical peeling, and the metal foil for the carrier is described. The content of the assembly of the printed wiring board. Further, it is revealed that the peel strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. By the metal foil with a carrier, the copper foil is supported over the entire surface of the synthetic resin, so that wrinkles in the copper foil in the laminate can be prevented. Moreover, since the metal foil of the metal foil with a carrier is in close contact with the synthetic resin without a gap, When the surface of the metal foil is plated or etched, it can be put into a gold plating or etching solution. Further, since the linear expansion coefficient of the synthetic resin is equivalent to the copper foil as the constituent material of the substrate and the prepreg after the overlap, the positional deviation of the circuit is not caused, so that the number of defective products is reduced and the number of defective products can be increased. The effect of excellent yield.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-272589

The copper foil with a carrier described in the patent document 1 is an epoch-making invention that contributes greatly to the reduction of the manufacturing cost by simplifying the manufacturing steps of the printed circuit board and improving the yield, but does not mention the carrier metal foil. There is still room for improvement in the temporary adhesion of the plate-shaped carrier and the metal foil in the specific use and the subsequent peeling.

For example, in applications such as use that has not been subjected to a large number of heating processes, for example, a masking material formed by performing mesh processing, it is important that the adhered metal foil and the synthetic resin are not accidentally peeled off before the peeling operation. Further, when the peeling operation is performed, the interface between the metal foil and the synthetic resin can be intentionally peeled off. In other words, when the peel strength between the two is excessively increased in order to avoid accidental peeling, when the metal foil is peeled off from the synthetic resin, the resin portion is broken and the resin component remains on the surface of the metal foil. good.

Accordingly, an object of the present invention is to provide a carrier metal foil which can be used for peeling off a plate-shaped carrier and a metal foil, and further provides a metal foil which can be intentionally peeled off at the interface between the metal foil and the plate-shaped carrier.

The present inventors have made an effort to study the above problems, and as a result, it has been found that the peeling strength between the metal foil and the plate-shaped carrier is within a certain range, and no accidental peeling occurs between the metal foil and the plate-shaped carrier. Deliberate stripping is performed to complete the present invention.

That is, the present invention is as follows.

(1) A carrier-attached metal foil comprising a plate-shaped carrier made of a resin and a metal foil which is detachably adhered to at least one side of the carrier, and is carried out at 220 ° C for 3 hours, 6 hours or 9 hours. After at least one type of heating, the peeling strength of the metal foil and the plate-shaped carrier is 10 gf/cm or more and 200 gf/cm or less.

(2) The carrier-attached metal foil according to (1), wherein the resin-made plate-shaped carrier contains a thermosetting resin.

(3) The carrier-attached metal foil according to (1) or (2), wherein the plate-shaped carrier made of the above resin is a prepreg.

(4) The carrier metal foil according to (2) or (3), wherein the plate-shaped carrier made of the above resin has a glass transition temperature Tg of 120 to 320 °C.

(5) The carrier-attached metal foil according to any one of (1) to (4), wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(6) The carrier-attached metal foil according to any one of (1) to (5), wherein the peeling strength of the metal foil before the heating and the plate-shaped carrier is 10 gf/cm or more and 200 gf/cm or less.

(7) The carrier-attached metal foil according to any one of (1) to (6), wherein the plate-shaped carrier and the metal foil constituting the carrier-attached metal foil are used singly or in combination of a plurality of decanes represented by the following formula a compound, a hydrolyzate thereof, and a condensate of the hydrolyzate,

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms substituted by a halogen atom; Any hydrocarbon group).

(8) A method of producing a multilayer metal-clad laminate comprising: at least one metal foil side build-up resin of the carrier-attached metal foil of any one of (1) to (7), and then repeating the lamination of the resin or the metal foil once the above.

(9) A method of producing a multilayer metal-clad laminate comprising: the metal foil side-layer resin of the carrier-attached metal foil according to any one of (1) to (7), and then repeating the laminated resin, single-sided or double-sided The metal-clad laminate, or the carrier-attached metal foil or the metal foil of any one of (1) to (7), is used once or more.

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

(11) A method of producing a multi-layer metal-clad laminate according to (10), comprising the step of removing a part or all of the metal foil separated by peeling by etching.

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

(13) A method of producing a build-up substrate, comprising the step of forming one or more build-up wiring layers on the metal foil side of the laminate of any one of (1) to (7).

(14) The method for producing a build-up substrate according to (13), wherein the build-up wiring layer is used in a subtractive method, a full additive method, or a semi-additive method. Formed by at least one.

(15) A method of producing a build-up substrate, comprising: at least one metal foil side build-up resin of the carrier-attached metal foil according to any one of (1) to (7), and then repeating the laminated resin, one-sided or double-sided The wiring substrate, the single-sided or double-sided metal-clad laminate, and the carrier-attached metal foil or metal foil according to any one of (1) to (7) are one or more times.

(16) The method for producing a build-up substrate according to (15), further comprising the steps of: a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, and a carrier The plate-shaped carrier of the metal foil or the resin is perforated, and the side surface and the bottom surface of the hole are electrically plated.

(17) The method for producing a build-up substrate according to (15) or (16), further comprising the step of: performing the following steps on the metal foil of the single-sided or double-sided wiring substrate described above, forming one-sided or double-sided coating At least one of the metal foil of the metal laminate and the metal foil constituting the carrier metal foil forms wiring.

(18) The method for producing a build-up substrate according to any one of (15) to (17), comprising the step of: attaching a carrier having any one of (1) to (7) in which a metal foil is adhered to one side The resin sheet side of the metal foil is laminated on the surface on which the wiring is formed.

(19) The method for producing a build-up substrate according to any one of (15) to (17), further comprising the step of: laminating a resin on a surface on which the wiring is formed, and adhering the metal foil to both sides (1) A metal foil of the carrier-attached metal foil of any one of (7) is laminated with the resin to be laminated.

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

(21) A method of producing a build-up wiring board according to any one of (13) to (20), further comprising: stripping the plate-shaped carrier of the carrier-attached metal foil from the metal foil And the steps of separation.

(22) The method for producing a build-up wiring board according to (21), which further comprises the step of removing a part or all of the metal foil adhered to the plate-shaped carrier by etching.

(23) A build-up wiring board obtained by the production method of (21) or (22).

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

(25) A method of manufacturing a printed circuit board comprising the manufacture of (21) or (22) Method of manufacturing a build-up wiring board.

According to the present invention, it is possible to provide a carrier-attached metal foil which does not cause accidental peeling between the metal foil and the plate-shaped carrier and which can be intentionally peeled off.

11‧‧‧With carrier metal foil

11a‧‧‧metal foil

11b‧‧‧ decane compounds

11c‧‧‧plate carrier

16‧‧‧Additional

Fig. 1 shows an example of the configuration of a CCL.

Fig. 2 is a view showing an example of the structure of a metal foil with a carrier of the present invention.

Fig. 3 is a view showing an example of assembly of a multilayer CCL using the copper foil with a carrier of the present invention (a form in which a copper foil is bonded to both sides of a resin sheet).

In one embodiment of the metal foil with a carrier of the present invention, a plate-shaped carrier made of resin and a metal foil which is detachably adhered to one or both sides (preferably double-sided) of the carrier is prepared. A carrier metal foil is formed. One of the structures of the metal foil with a carrier of the present invention is shown in Figs. 2 and 3. In particular, in the first drawing of Fig. 3, the metal foil 11a is detachably adhered to the carrier-attached metal foil 11 which is formed on both sides of the resin-made plate-shaped carrier 11c. The plate-shaped carrier 11c and the metal foil 11a are bonded together using the following decane compound 11b.

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

The metal foil with a carrier used in the present invention is finally peeled off, so that the adhesion is too high, which is a problem, but the plate-shaped carrier and the metal foil must have a chemical liquid processing step such as plating performed during the production process of the printed circuit board. The degree of adhesion without peeling.

Moreover, in the manufacturing process of a multilayer printed wiring board, in many cases, laminated laminated The heat treatment is carried out in the step of making or in the desmear step. Therefore, the more the thermal history of the metal foil attached to the carrier is, the stronger the number of layers. Therefore, especially in consideration of application to a multilayer printed wiring board, it is preferable that the peeling strength of the metal foil and the plate-shaped carrier is within the above range after the required heat history.

Therefore, in an embodiment of the present invention, a multilayer printed wiring board is assumed The heating condition in the production process, for example, after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours, the peel strength of the metal foil and the plate-shaped carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm. The above is more preferably 50 gf/cm or more, and is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, still more preferably 80 gf/cm or less.

Regarding the peel strength after heating at 220 ° C, it can correspond to a variety of laminates. In view of the above, it is preferred that the peel strength satisfies the above range, and further preferably after 3 hours, 6 hours, and 9 hours, in both after 3 hours and after 6 hours, or after 6 hours and 9 hours. The total peel strength satisfies the above range.

Thus, by heating the gold in the manufacturing steps of the multilayer printed wiring board The peeling strength of the foil and the plate-shaped carrier is within such a range, and is not peeled off during transportation or processing in the production step, and can be easily peeled off by hand after heat treatment, that is, mechanically Stripped.

Furthermore, the copper foil with a carrier of the present invention can also be used without extensive heat processing. The use of the step, such as the use of a masking material formed by mesh processing, is used.

In this regard, the heating portion in the manufacturing process of the above multilayer printed wiring board In the metal foil with a carrier, the peeling strength of the metal foil and the plate-shaped carrier is preferably 10 gf/cm or more, more preferably 30 gf/cm or more, still more preferably 50 gf/cm or more, and on the other hand, it is preferably It is 200 gf/cm or less, more preferably 150 gf/cm, and still more preferably 80 gf/cm or less. By setting the peeling strength of the metal foil and the plate-shaped carrier to such a range, it is not peeled off at the time of conveyance or processing, and can be easily peeled off by hand.

In the present invention, the peel strength is based on 90 degree peeling as specified in JIS C6481. Determined by the strength measurement method.

Hereinafter, specific constituent elements of each material for achieving such peel strength Be explained.

The resin to be a plate-shaped carrier is not particularly limited, and a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, rosin or the like can be used, and a thermosetting resin is preferable. Also, a prepreg can be used. The prepreg before bonding with the metal foil may be in the B-stage state. If the linear expansion coefficient of the prepreg (C stage) is 12 to 18 (×10 ^-6 /°C), it is 16.5 (×10 ^-6 /°C) or SUS pressed plate of the copper foil as a constituent material of the substrate. 17.3 (×10 ^-6 /°C) is substantially equal, so that it is less advantageous in terms of positional deviation caused by a phenomenon in which the size of the substrate before and after pressing differs from the size at the time of design (scale change). Further, as a synergistic effect of these advantages, it is also possible to produce a very thin multilayer hollow substrate. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board.

The board is maintained from the viewpoint of maintaining the peel strength after heating to an optimum range. The carrier is preferably a glass transition temperature Tg having a relatively high glass transition temperature Tg, for example, 120 to 320 ° C, preferably 170 to 240 ° C. Further, the glass transition temperature Tg is a value measured by DSC (Differential Scanning Calorimetry).

Further, it is preferable that the thermal expansion coefficient of the resin is +10% of the thermal expansion coefficient of the metal foil. And within -30%. Thereby, the positional deviation of the circuit caused by the difference in thermal expansion between the metal foil and the resin can be effectively prevented, and the occurrence of defective products can be reduced, and the yield can be improved.

The thickness of the plate-shaped carrier is not particularly limited, and rigidity or softness may be used, but if If it is thick, it will adversely affect the heat distribution during hot pressing. On the other hand, if it is too thin, it will bend and the manufacturing process of the printed wiring board cannot be performed. In this respect, it is usually 5 μm or more and 1000 μm or less. It is preferably 50 μm or more and 900 μm or less, more preferably 100 μm or more and 400 μm or less.

As a metal foil, a representative copper or copper alloy foil, aluminum, nickel, or A foil such as zinc. In the case of copper or copper alloy foil, an electrolytic foil or a calendered foil can be used. The metal foil is not limited, and is usually 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less, in consideration of the use as a wiring of a printed circuit board. In the case where a metal foil is attached to both sides of the plate-shaped carrier, a metal foil of the same thickness may be used, or a metal foil of a different thickness may be used.

Various surface treatments can also be applied to the metal foil 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.) To adjust the surface roughness by chromate treatment (including one or more alloying elements such as Zn, P, Ni, Mo, Zr, Ti, etc. in the chromate treatment liquid) to impart rust resistance or discoloration resistance. Roughening treatment (for example, using copper electrodeposited particles or Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu-As plating) Alloys, copper-plated alloys such as Cu-As-W alloys). The roughening treatment of course affects the peel strength of the metal foil and the plate-shaped carrier, and the chromate treatment also has a large influence. Although the chromate treatment is important from the viewpoint of rust preventive property and discoloration resistance, it is observed that the peel strength is remarkably increased, and therefore it is also useful as a means for adjusting the peel strength.

In the previous CCL, it is preferable that the peeling strength of the resin and the copper foil is high, so Further, by using, for example, a matte surface (M surface) of an electrolytic copper foil as a surface treatment with a resin and a roughening treatment, the adhesion of the chemical and physical anchor effect is enhanced. . Further, various adhesives and the like are added to the resin side to enhance the adhesion to the metal foil. As described above, unlike the CCL, the metal foil and the resin must be finally peeled off, so that the peel strength is too high, which is disadvantageous.

Therefore, in a preferred embodiment of the metal foil with a carrier of the present invention, In order to adjust the peel strength of the metal foil and the plate-shaped carrier to the above preferred range, in accordance with JIS The ten-point average roughness (Rz jis) of the surface of the metal foil measured in B 0601:2001 indicates the surface roughness of the bonding surface, and is preferably 3.5 μm or less, and more preferably 3.0 μm or less. However, it takes time and effort to reduce the surface roughness without limitation, and it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When an electrolytic copper foil is used as the metal foil, if it is adjusted to such surface roughness, a glossy surface (shiny surface, S surface) and a rough surface (matt surface, M) can be used. Any of the faces, but it is easier to adjust to the above surface roughness using the S face. On the other hand, the ten-point average roughness (Rz jis) of the surface of the metal foil which is not in contact with the carrier is preferably 0.4 μm or more and 10.0 μm or less.

Further, in a preferred embodiment of the metal foil with a carrier of the present invention, the surface treatment for improving the peel strength such as the roughening treatment of the bonding surface of the metal foil and the resin is not performed. Further, in a preferred embodiment of the metal foil with a carrier of the present invention, an adhesive for enhancing the adhesion to the metal foil is not added to the resin.

For the adjustment of the peeling strength, a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product (hereinafter, simply referred to as a decane compound) may be used alone, or a plurality of kinds may be used in combination. The reason for this is that the plate-shaped carrier and the metal foil are bonded together by using the decane compound, and the adhesion is easily lowered to adjust the peel strength to the above range.

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are replaced by a halogen atom; Any hydrocarbon group)

The decane compound must have at least one alkoxy group. In the case where an alkoxy group is not present, and only a hydrocarbon group selected from a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrogen atom having one or more hydrogen atoms substituted by a halogen atom constitutes a substituent There is a tendency that the adhesion between the plate-shaped carrier and the surface of the metal foil is excessively lowered. Further, the decane compound must have at least one hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted by a halogen atom. The reason for this is that in the case where the hydrocarbon group is not present, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to increase. Further, in the invention of the present invention, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted by a halogen atom.

In order to adjust the peeling strength of the plate-shaped carrier and the metal foil to the above range, the decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (including a hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom). When the above formula is described, both of R3 and R4 are alkoxy groups.

The alkoxy group is not limited, and examples thereof include a methoxy group, an ethoxy group, a n- or iso-propoxy group, a n-, iso- or tert-oxy group, a n-, iso- or neopentyloxy group, and a n-hexyloxy group. The linear, branched or cyclic carbon number such as cyclohexyloxy, n-heptyloxy and n-octyloxy is 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms. Alkoxy group.

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

The alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal group, an iso- or a third-order group, a normal, an iso- or neopentyl group, a n-hexyl group, an n-octyl group, and a n-decyl group. The linear or branched carbon number is 1 to 20, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

The cycloalkyl group is not limited, and examples thereof include a carbon number of 3 to 10, preferably a carbon number of 5 to 7 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Cycloalkyl.

Examples of the aryl group include a phenyl group and an alkyl group-substituted phenyl group (for example, a tolyl group, An aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as xylyl), 1- or 2-naphthyl or anthracenyl.

One or more hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Preferred examples of the decane compound include methyltrimethoxydecane, ethyltrimethoxydecane, n- or isopropyltrimethoxydecane, n-, iso- or tert-tris-trimethoxydecane, and Iso- or neopentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, phenyltrimethoxydecane; alkyl-substituted phenyltrimethoxynonane (for example , p-(methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or isopropyltriethoxydecane, n-, iso- or tertiary-based Ethoxy decane, pentyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane, alkyl substituted benzene Triethoxy decane (for example, p-(methyl)phenyltriethoxydecane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluorooctyltriethoxy Decane, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, trimethylfluorodecane, dimethyldibromodecane, Diphenyldibromodecane, the hydrolyzed product, and the condensate of the hydrolyzed product, and the like. Among these, from the viewpoint of easiness of acquisition, propyltrimethoxydecane, methyltriethoxydecane, hexyltrimethoxydecane, phenyltriethoxydecane, and decyltrimethyl are preferred. Oxydecane.

The carrier-attached metal foil can be produced by adhering a plate-shaped carrier to a metal foil by hot pressing. For example, the decane compound may be applied to the bonding surface of the metal foil and/or the plate-shaped carrier as needed, and the bonding surface of the metal foil may be thermally laminated to form a resin-made plate-shaped carrier of the B-stage.

The decane compound can be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is especially effective when a highly hydrophobic decane compound is used. The aqueous solution of the decane compound promotes hydrolysis of the alkoxy group by stirring, and if the stirring time is long, the condensation of the hydrolyzed product can be promoted. Usually, there is a decane compound which is hydrolyzed and condensed by a sufficient stirring time to cause a metal foil and a plate carrier. The tendency of the peel strength to decrease. Therefore, the peel strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the decane compound in water is not limited, and may be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is also a method of using without stirring.

If the concentration of the decane compound in the aqueous solution of the decane compound is higher, The tendency to lower the peel strength of the metal foil and the plate-shaped carrier can be adjusted by adjusting the concentration of the decane compound. The concentration of the decane compound in the aqueous solution is not limited, and may 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 decane compound is not particularly limited, and it is acidic or alkaline. Sex can be used. For example, it can be used at a pH of from 3.0 to 10.0. From the viewpoint of not requiring a special pH adjustment, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH value in the range of 7.0 to 9.0.

As a condition for producing hot pressing of the metal foil with a carrier, when a prepreg is used as the plate-shaped carrier, it is preferably at a pressure of 30 to 40 kg/cm ² , which is higher than the glass transition temperature of the prepreg. The temperature is hot pressed.

Furthermore, it is equipped with XPS (X-ray photoelectron spectroscopy device), EPMA (electricity) The surface of the metal foil or the resin is measured by a scanning electron microscope such as a beamlet microanalyzer and an EDX (energy dispersive X-ray analysis). When Si is detected, it is presumed that a decane compound exists on the surface of the metal foil or the resin.

Further, in another aspect, the present invention provides a carrier metal as described above The use of foil.

First, there is provided a method for producing a multilayer metal-clad laminate comprising: laminating at least one metal foil side of the above-mentioned carrier-attached metal foil, and then repeatedly laminating the resin or the metal foil once or more, for example, 1 to 10 times.

Secondly, a method for manufacturing a multi-layer metal-clad laminate is provided, which comprises: The above-mentioned metal foil side laminated resin with a carrier metal foil is then repeatedly laminated resin, single or double The metal-clad laminate, or the metal foil with a carrier of the present invention, or the metal foil is once or more, for example, 1 to 10 times.

In the method for producing a multilayer metal-clad laminate, the step of separating and separating the plate-shaped carrier with the carrier-attached metal foil from the metal foil may be further included.

Further, the method further includes the step of removing the part or all of the metal foil by etching after separating the plate-shaped carrier from the metal foil and separating the metal foil.

Thirdly, there is provided a method for producing a build-up substrate comprising: laminating a resin on a metal foil side of the above-mentioned carrier metal foil, and then repeating a laminated resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate The plate, or the metal foil with a carrier of the present invention, or the metal foil is once or more, for example, 1 to 10 times.

Fourthly, there is provided a method for producing a build-up substrate comprising the step of laminating one or more build-up wiring layers on the metal foil side of the above-mentioned carrier metal foil. At this time, the build-up wiring layer can be formed using at least one of a subtractive method, a full additive method, or a semi-additive method.

The subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a metal foil on a metal clad laminate or a wiring board (including a printed wiring board or a printed circuit board) by etching or the like. The full additive method is a method of forming a conductor pattern by electroless plating or/and electroplating without using a metal foil as a conductor layer, and the semi-additive method is applied to, for example, a seed layer composed of a metal foil. A method of obtaining a conductor pattern by performing electroless metal deposition, plating, etching, or both to form a conductor pattern, and then etching the unnecessary seed layer to remove the conductor pattern.

In the method for manufacturing the build-up substrate, the method further includes the steps of: a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, and a plate-shaped metal foil with a carrier The carrier or the resin is opened, and conduction plating is performed on the side and the bottom surface of the hole. Furthermore, the method further includes the following steps: forming the metal foil of the single-sided or double-sided wiring substrate, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the structure At least one of the metal foils to which the carrier metal foil is attached forms a wiring.

In the method for manufacturing the build-up substrate, the method further includes the steps of: The metal foil is adhered to one surface, and the carrier side of the metal foil with a carrier of the present invention is laminated on the surface on which the wiring is formed. Further, the method further includes the step of laminating a resin on the surface on which the wiring is formed, and laminating the metal foil of the present invention to which the metal foil is adhered to the resin.

In addition, the "surface on which the wiring is formed" means a portion where wiring is formed on the surface of each appearance during the layering process, and the final product and its intermediate materials are included as the build-up substrate.

In the method for manufacturing the build-up substrate, the above-mentioned attached carrier may be further included The step of separating and separating the plate-shaped carrier of the metal foil from the metal foil.

Furthermore, the method further includes the steps of: forming the above-mentioned plate-shaped carrier and metal foil After peeling and separating, one part or the entire surface of the metal foil is removed by etching.

Furthermore, the method for manufacturing the above multilayer metal-clad laminate and the manufacture of the build-up substrate In the method, the layers can be laminated to each other by thermocompression bonding. The thermocompression bonding can be carried out when each layer is laminated, and can be layered to a certain extent and then uniformly performed, or can be uniformly performed at one time.

Hereinafter, as a specific example of the above-described use, the present invention is exemplarily explained. A method for producing a hollow build-up substrate with a copper foil-attached carrier copper foil 11 on both sides of a plate-shaped carrier 11c of a resin plate. In this method, after a desired number of buildup layers 16 are laminated on both sides of the carrier copper foil 11, the double-sided copper foil is peeled off from the carrier copper foil 11 (see Fig. 3).

For example, in the metal foil side of the metal foil with a carrier of the present invention, they are sequentially overlapped as The resin of the insulating layer, the two-layer circuit board, and the resin as the insulating layer are formed thereon by sequentially contacting the metal foil of the metal foil with a carrier of the present invention in such a manner that the metal foil side is in contact with the resin sheet. Layer substrate.

Further, as another method, on both sides of the resin-made plate-shaped carrier 11c or At least one metal foil side of a metal foil with a metal foil adhered to one side, sequentially laminated as an insulation A layer of resin and a metal foil as a conductor layer. Then, the step of adjusting the thickness by half etching the entire surface of the metal foil as needed may be included. Then, laser processing is performed on a specific position of the laminated metal foil to form a through hole penetrating the metal foil and the resin, and the desmear treatment for removing the dross in the through hole is performed, and the bottom, the side surface and the metal foil of the through hole are formed. Electroless plating is performed on the entire surface or a part of the layer to form an interlayer connection, and electroplating is performed as needed. It is also possible to form a plating resist in advance on each portion of the metal foil which is not subjected to electroless plating or electroplating. Further, in the case where the adhesion between the electroless plating, the electroplating, and the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Then, an unnecessary portion of the metal foil, the electroless plating portion, and the plating portion is removed by etching, thereby forming a circuit. Thereby, a build-up substrate is obtained. It is also possible to repeat the steps of laminating the resin from the copper foil to the circuit to form a plurality of layers of the build-up substrate.

Further, the outermost surface of the build-up substrate may be laminated on the resin side of the metal foil with the metal foil attached to the metal foil on one side of the present invention, or may be laminated after temporarily laminating the resin sheet. A metal foil with a metal foil attached to the metal foil is bonded to the metal foil to form a layer.

Here, as the resin sheet for producing the build-up substrate, it is preferably used. A prepreg of a thermosetting resin.

Further, as another method, a resin layer as an insulating layer is laminated on the exposed surface of the metal foil of the laminate obtained by laminating a metal foil (for example, a copper foil) on one side or both sides of the plate-shaped carrier of the present invention. Dip or photosensitive resin. Thereafter, a through hole is formed at a specific position of the resin. In the case of using, for example, a prepreg as a resin, the through holes can be formed by laser processing. After the laser processing, the desmear treatment for removing the dross in the through hole may be performed. Further, in the case where a photosensitive resin is used as the resin, the resin forming the portion of the through hole can be removed by photolithography. Then, the bottom surface of the through hole, the side surface, and the entire surface or part of the resin are subjected to electroless plating to form an interlayer connection, and further plating is performed as needed. It is also possible to form a plating resist on the resin before electroplating or electroplating. Also, in electroless plating, electroplating, plating resists and trees When the adhesion of the grease is insufficient, the surface of the resin may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Then, an unnecessary portion of the electroless plating portion or the plating portion is removed by etching, thereby forming an electric circuit. Thereby, a build-up substrate is obtained. It is also possible to repeat the steps from the lamination of the resin to the formation of the circuit to form a plurality of layers of the build-up substrate.

Further, the outermost surface of the build-up substrate may be laminated on the resin side of the laminate in which the metal foil is adhered to the single surface of the present invention, or the resin side of the metal foil with the metal foil adhered to the metal foil on one side, or may be laminated. After laminating the resin, the metal foil of one of the laminates with the metal foil adhered to the double-sided layer of the present invention or a metal foil with a metal foil adhered to the metal foil on both sides is laminated.

The hollow build-up substrate thus produced is subjected to a plating step and/or an etching step Wiring is formed on the surface, and the carrier resin and the copper foil are peeled off and separated, thereby completing the build-up wiring board. The wiring may be formed on the peeled surface of the metal foil after the separation and separation, and the entire surface of the metal foil may be removed by etching to form a build-up wiring board. Further, the printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, a printed circuit board can also be obtained by directly mounting an electronic component on the hollow build-up substrate before resin peeling.

[Examples]

In the following, the experimental examples are shown as examples and comparative examples of the present invention, but the experimental examples are provided to better understand the present invention and its advantages, and are not intended to limit the invention.

<Experimental Example 1>

A plurality of electrolytic copper foils (thickness: 12 μm) were prepared, and the light (S) surface of each of the electrolytic copper foils was subjected to nickel-zinc (Ni-Zn) alloy treatment and chromate (Cr-Zn chromic acid) under the following conditions. After the salt treatment, the ten-point average roughness (Rz jis, measured according to JIS B 0601:2001) of the bonding surface (here, the S surface) is set to 1.5 μm, and the Mitsubishi Gas Chemical Co., Ltd. The produced 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)

(chromate treatment)

After applying an aqueous solution of a decane compound to the S surface using a spray coater on a plurality of electrolytic copper foils, the surface of the copper foil was dried in air at 100 ° C, and then bonded to the prepreg. Regarding the use conditions of the decane compound, the type of the decane compound, the stirring time before the coating of the decane compound in water until the coating, the concentration of the decane compound in the aqueous solution, the concentration of the alcohol in the aqueous solution, and the pH of the aqueous solution are shown in Table 1.

Further, it is assumed that a heat history is applied to a plurality of copper foil-attached copper foils for further heat treatment of the copper foil-forming circuit or the like, and the conditions described in Table 1 (here, at 220 ° C for 3 hours) are performed. Heat treatment.

The peel strength of the copper foil with a carrier obtained by hot pressing and the copper foil in the copper foil with a carrier after heat processing and the plate-shaped carrier (heated resin) was measured. Each result Shown in Table 1.

Moreover, in order to evaluate the peeling workability, the manual work time (time/number) required per unit number was evaluated. The results are shown in Table 2.

<Experimental Example 2~18>

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

Further, the type of the bonding surface of the copper foil, the surface treatment conditions and the surface roughness Rz jis, the use conditions of the decane compound, the type of the prepreg, and the laminate conditions of the copper foil and the prepreg are as shown in Table 1. Show.

Among the surface treatment conditions of the treated surface of the copper foil, the specific conditions of the epoxy decane (treatment) and the roughening treatment are as follows.

(epoxy decane treatment)

Treatment liquid: 3-glycidoxypropyltrimethoxydecane 0.9% by volume aqueous solution

pH 5.0~9.0

Stirring at room temperature for 12 hours

Treatment method: After the treatment liquid was applied using a spray coater, the treated surface was dried in air at 100 ° C for 5 minutes.

(roughening treatment)

Plating time 0.1~30 seconds

<Experimental Examples 19 to 20>

A copper foil with a carrier was produced in the same manner as in Experimental Example 1 using the copper foil, the resin (prepreg) shown in Table 3, and a part of the decane compound. Further, heat treatment under the conditions shown in Table 3 was carried out. The same evaluation as in Experimental Example 1 was carried out with respect to the thus obtained carrier copper foil. The results are shown in Tables 3 and 4.

Further, the S surface was used as a bonding surface of the copper foil, and the surface was subjected to chromate treatment under the above conditions. Further, the surface roughness Rz jis of the copper foil, the kind of the prepreg, the use conditions of the decane compound used for the surface treatment of the prepreg, and the lamination conditions of the copper foil and the prepreg are shown in Table 3.

According to the table, it is understood that the decane compound can be treated on the surface of the copper foil or the surface of the prepreg can be obtained in the same manner as the peel strength of the laminate, the peel strength after heating, and the peeling workability. result.

(Additional wiring board)

The FR-4 prepreg (manufactured by Nanya Plastics Co., Ltd.) and copper foil (manufactured by JX Nippon Steel Co., Ltd., JTC12μm (product name)) are sequentially superposed on both sides of the copper foil with the carrier thus produced, to 3 MPa. The pressure was hot pressed under the heating conditions shown in the respective tables to prepare a four-layer copper clad laminate.

Then, a hole of 100 μm in diameter of the copper foil penetrating the surface of the above-mentioned four-layer copper clad laminate and the insulating layer (hardened prepreg) therethrough was opened using a laser processing machine. Then, copper plating is performed on the surface of the copper foil on the copper foil with the carrier exposed on 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 by electroless copper plating or electroplating copper. An electrical connection is formed between the copper foil on the copper foil with the carrier and the copper foil on the surface of the four-layer copper clad laminate. Then, one portion of the copper foil on the surface of the four-layer copper clad laminate was etched using an iron (III) chloride-based etching solution to form an electric circuit. Thus, four layers of build-up substrates were obtained.

Then, in the four-layer build-up substrate, the plate-shaped carrier with the carrier copper foil was peeled off from the copper foil to separate, and two sets of two-layer build-up wiring boards were obtained.

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

In each of the experimental examples, a plurality of four-layer build-up substrates were produced, and the adhesion between the prepreg and the copper foil constituting the carrier-attached copper foil in the step of fabricating the build-up substrate was visually confirmed. As a result, Tables 1 and 3 were used. The peeling strength and the peeling strength after heating were evaluated as the build-up wiring sheets of the carrier-attached copper foil produced under the conditions of "S" and "G". When the layer was formed, the resin (plate-shaped carrier) with the carrier copper foil was not broken. And can be peeled off. However, as for the conditions of the evaluation of "G", as described in Tables 1 and 3, there is also a case where the copper foil is peeled off from the plate-shaped carrier without a peeling operation at the time of layer formation.

Further, regarding the condition of evaluation of "N", the resin was broken during the peeling operation of the copper foil in the copper foil with a carrier, or the resin was left on the surface of the copper foil at the time of layering.

Further, in the case of the evaluation of "-", the resin was peeled off during the peeling operation of the copper foil in the copper foil with a carrier at the time of layering, but there was a case where the copper foil was peeled off without a peeling operation.

Claims (31)

A carrier-attached metal foil comprising a plate-shaped carrier made of resin and a metal foil which is detachably adhered to at least one side of the carrier, and is heated at 220 ° C for at least one of 3 hours, 6 hours or 9 hours. After that, the peeling strength of the metal foil and the plate-shaped carrier is 10 gf/cm or more and 200 gf/cm or less, and the ten-point average roughness (Rz jis) of the surface of the metal foil which is not in contact with the plate-shaped carrier is 0.4 μm or more. And 10.0 μm or less. The carrier-attached metal foil according to claim 1, wherein the resin-made plate-shaped carrier contains a thermosetting resin. The carrier-attached metal foil according to claim 1 or 2, wherein the resin-made plate-shaped carrier is a prepreg. The carrier-attached metal foil according to claim 2, wherein the resin-made plate-shaped carrier has a glass transition temperature Tg of 120 to 320 °C. The carrier metal foil according to claim 1 or 2, wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. The carrier-attached metal foil according to claim 1 or 2, wherein the metal foil before the heating has a peel strength of 10 gf/cm or more and 200 gf/cm or less. The carrier-attached metal foil according to claim 1 or 2, wherein the plate-shaped carrier and the metal foil constituting the carrier-attached metal foil are used singly or in combination of a plurality of decane compounds represented by the following formula, hydrolyzed products thereof, The condensate of the hydrolyzate is laminated, (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms substituted by a halogen atom; Any hydrocarbon group). A method for producing a multi-layer metal-clad laminate comprising at least one metal foil side-layer resin of the carrier-attached metal foil according to any one of claims 1 to 7, and then repeating the lamination of the resin or the metal foil once or more. A method for manufacturing a multi-layer metal-clad laminate comprising: a metal foil side-layer resin with a carrier metal foil according to any one of claims 1 to 7, and then repeating a laminated resin, a single-sided or double-sided metal-clad coating The laminated metal sheet or the metal foil with a carrier or the metal foil of any one of the above claims 1 to 7 is more than one time. The method for producing a multi-layer metal-clad laminate according to claim 8 or 9, further comprising the step of separating the plate-shaped carrier with the carrier metal foil and separating the metal foil. A method of producing a multi-layer metal-clad laminate according to claim 10, which comprises the step of removing a part or all of the metal foil separated by peeling by etching. A multi-layer metal-clad laminate obtained by the manufacturing method of any one of claims 8 to 11. A method of producing a build-up substrate, comprising the step of forming one or more build-up wiring layers on the metal foil side of the laminate of any one of claims 1 to 7. The method for manufacturing a build-up substrate according to claim 13, wherein the build-up wiring layer is used in a subtractive method, a full additive method or a semi-additive method. Formed by at least one. A method for producing a build-up substrate, comprising: at least one metal foil side build-up resin of a carrier metal foil according to any one of claims 1 to 7, and then repeating the laminated resin, single-sided or double-sided wiring substrate , single or double-sided metal-clad laminate, patent application scope The carrier metal foil or metal foil of any one of items 1 to 7 is more than one time. A method for manufacturing a build-up substrate, comprising: laminating a resin on a side of a metal foil with a carrier metal foil, and then repeating a laminated resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, and a metal foil with the carrier Or a metal foil of one or more times; the metal foil with a carrier is composed of a resin-made plate-shaped carrier and a metal foil which is detachably adhered to at least one side of the carrier, and the carrier-attached metal foil is carried out at 220 ° C for 3 hours. After at least one of 6 hours or 9 hours is heated, the peeling strength of the metal foil and the plate-shaped carrier is 10 gf/cm or more and 200 gf/cm or less; and the manufacturing method of the build-up substrate further includes the following steps: single-sided or double-sided A wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, a plate-shaped carrier with a carrier metal foil, or a resin is opened, and the side surface and the bottom surface of the hole are electrically plated. The method for producing a build-up substrate according to claim 16, wherein the resin-made plate-shaped carrier satisfies one or two or three items (A) to (C): (A) the resin The plate-shaped carrier contains a thermosetting resin, (B) the plate-shaped carrier made of the resin is a prepreg, and (C) the plate-shaped carrier made of the resin has a glass transition temperature Tg of 120 to 320 °C. The method for producing a build-up substrate according to claim 16 or 17, wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. The method for producing a build-up substrate according to claim 16 or 17, wherein the peeling strength of the metal foil before the heating and the plate-shaped carrier is 10 gf/cm or more and 200 gf/cm or less. The method for producing a build-up substrate according to claim 16 or 17, wherein the plate-shaped carrier and the metal foil constituting the carrier-attached metal foil are used alone or in combination with a plurality of decane compounds represented by the following formula and hydrolyzed. The product and the condensate of the hydrolyzate are laminated. (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms substituted by a halogen atom; Any hydrocarbon group). The method for producing a build-up substrate according to any one of claims 15 to 17, further comprising the step of performing the following steps: forming a metal foil of the single-sided or double-sided wiring substrate, forming a single-sided or double At least one of the metal foil of the metal-clad laminate and the metal foil constituting the carrier-attached metal foil forms a wiring. The method of manufacturing a build-up substrate according to claim 21, which comprises the step of: contacting a side of a resin sheet with a carrier metal foil according to any one of claims 1 to 7 in which the metal foil is adhered to one side. Laminated on the surface on which the wiring is formed. The method for manufacturing a build-up substrate according to claim 21, further comprising the steps of: laminating a resin on a surface on which the wiring is formed, and adhering to the first to seventh aspects of the patent application of the metal foil on both sides A metal foil of the carrier-attached metal foil is laminated in contact with the resin. The method for producing a build-up substrate according to any one of claims 15 to 17, wherein at least one of the resins is a prepreg. A method for producing a build-up wiring board according to any one of claims 13 to 24, further comprising a plate-shaped carrier of the metal foil with a carrier The step of separating from the metal foil and separating it. The method of manufacturing a build-up wiring board according to claim 25, further comprising the step of removing a part or all of the metal foil adhered to the plate-shaped carrier by etching. A build-up wiring board obtained by the manufacturing method of claim 25 or 26. A method of manufacturing a printed circuit board, comprising the step of manufacturing a build-up substrate by the manufacturing method of any one of claims 13 to 24. A method of manufacturing a printed circuit board comprising the steps of manufacturing a build-up wiring board by the manufacturing method of claim 25 or 26. A method for producing a resin-made plate-shaped carrier, comprising: a step of preparing a carrier-attached metal foil according to any one of claims 1 to 7, and peeling off the resin-made plate-shaped carrier from the carrier-supported metal foil step. A method for producing a build-up substrate, comprising: a step of preparing a metal foil with a carrier according to any one of claims 1 to 7 and a step of peeling the metal foil from the metal foil with the carrier.