TWI618814B - Surface treatment metal foil, laminate, printed wiring board, semiconductor package, electronic device, and printed wiring board manufacturing method - Google Patents

Abstract

The present invention provides a metal foil which is physically peeled off when the metal foil is bonded to a resin substrate by providing a release layer of the metal foil, thereby removing the metal foil from the resin substrate. In the step, the metal foil can be removed at a preferred cost without damaging the contour of the surface of the metal foil transferred onto the surface of the resin substrate, and the resins having different resin components can be bonded to each other with good adhesion. . The metal foil of the present invention has a surface treatment layer on at least one surface, and the water contact angle of the side surface of the surface treatment layer is 90 degrees or more.

Description

Surface treatment metal foil, laminate, printed wiring board, semiconductor package, electronic device, and printed wiring board manufacturing method

The present invention relates to a method of producing a surface-treated metal foil, a laminate, a printed wiring board, a semiconductor package, an electronic device, and a printed wiring board.

The mainstream method of forming a circuit for forming a printed wiring board and a semiconductor package substrate is a subtractive method. However, due to further fine wiring in recent years, M-SAP (Modified Semi-Additive Process) or half of the surface profile of the metal foil is used. New process methods such as addition methods have arisen.

In the new circuit forming process, as an example of the semi-additive method of the surface profile of the metal foil used in the latter, the following method is exemplified. In other words, first, the entire surface of the metal foil laminated on the resin substrate is etched, and the surface of the etched substrate on which the surface contour of the metal foil is transferred is opened by laser or the like, and the opening for conducting the opening is applied. Electrolytic copper plating layer, covering the surface of the electroless copper plating with a dry film, removing the dry film of the circuit forming portion by UV exposure and development, performing electrolytic copper plating on the electroless copper plating surface not covered by the dry film, and drying the film After the peeling, the electroless copper plating layer is etched (flashing, rapid etching) by an etching solution containing sulfuric acid or hydrogen peroxide water, thereby forming a fine circuit (Patent Document 1 and Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-196863

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-242975

However, in the semi-additive method using the contour of the surface of the metal foil, the metal is favorably transferred to the surface of the resin substrate without damaging the contour of the surface of the metal foil, and the metal is preferably used at a preferable cost. There is still room for research in terms of foil removal.

In addition, in recent years, research and development of a technique for producing a laminated body by laminating a resin laminated circuit or a resin has been conducted. In this case, in the case where a sufficient adhesion between the build-up layer such as a circuit or a resin and the resin is not obtained, it is necessary to make the resin on one side have irregularities and to improve the adhesion due to the anchoring effect. There are physical processing, chemical processing, and the like for leaving the unevenness on the surface of the cured resin, but depending on the physical properties or chemical properties of the resin, such methods are not suitable. Therefore, further development is desired for a technique in which a resin or a resin is added to a resin with good adhesion.

As a result of intensive studies, the present inventors have found that the metal foil has a specific water-repellent surface by providing a surface treatment layer such as a release layer on the surface of the metal foil, thereby bonding the metal foil to the resin substrate. The metal foil can be physically peeled off from the resin substrate. And found: By physically peeling the metal foil from the resin substrate as described above, in the step of removing the metal foil from the resin substrate, the contour of the surface of the metal foil transferred to the surface of the resin substrate can be prevented from being damaged. In the case of the metal foil, the metal foil is removed at a preferred cost. Further, it has been found that the metal foil having a specific water-repellent surface is bonded to the resin substrate to be cured, and then the metal foil is removed, and the outline is transferred to the surface of the resin substrate, whereby the resin base can be removed. The material and the build-up layer are laminated with good adhesion.

The present invention, which is completed based on the above findings, is a surface-treated metal foil having a surface treatment layer on at least one surface, and a water contact angle of the side surface of the surface treatment layer is 90 degrees or more.

In one embodiment of the metal foil of the present invention, the kurtosis Rku defined by JIS B 0601 on the side surface of the surface treatment layer is 2.0 to 4.0.

In another embodiment of the present invention, the surface treatment layer includes the release layer, and the release layer has the resin substrate when the resin substrate is bonded to the metal foil from the side of the release layer. Peelable.

In still another embodiment of the surface-treated metal foil of the present invention, the release layer is used alone or in combination of several kinds of aluminate compounds, titanate compounds, zirconates, and the like, which are represented by the following formulas. a product, a condensate of the hydrolyzate, (R ¹ ) _m -M-(R ² ) _n

(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 with a halogen atom; Any one of the hydrocarbon groups, M is any one of Al, Ti, Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one R ¹ is an alkoxy group; Furthermore, m+n is the valence of M, that is, 3 in the case of Al and 4 in the case of Ti and Zr.

In still another embodiment of the surface-treated metal foil of the present invention, the mold release layer is used singly or in combination of a plurality of decane compounds represented by the following formula, a hydrolyzed product thereof, and a condensate of the hydrolyzed product.

(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 with a halogen atom; Any of the hydrocarbon groups in the group, 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 Any one of these groups substituted with a halogen atom).

In still another embodiment of the surface-treated metal foil of the present invention, the release layer is formed by using a compound having two or less sulfhydryl groups in the molecule.

In still another embodiment of the surface-treated metal foil of the present invention, the metal foil and the release layer are provided with a coating selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling layer. Processing one or more layers of the group consisting of layers.

In still another embodiment, the surface-treated metal foil of the present invention comprises the above-mentioned selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer. A surface of one or more layers of the group is provided with a resin layer.

In still another embodiment of the surface-treated metal foil of the present invention, a resin layer is provided on the surface of the release layer side.

In still another embodiment of the surface-treated metal foil of the present invention, the resin layer is followed by a resin, a primer, or a resin in a semi-hardened state.

In still another embodiment, the surface-treated metal foil of the present invention has a thickness of 5 to 210 μm.

In still another embodiment of the surface-treated metal foil of the present invention, the metal foil is a copper foil.

In still another aspect, the present invention provides a laminate comprising the surface-treated metal foil of the present invention and a resin substrate provided on the release layer side of the surface-treated metal foil.

In one embodiment of the laminate of the present invention, the resin substrate is a prepreg or a thermosetting resin.

In still another aspect, the present invention is a printed wiring board comprising the surface treated metal foil of the present invention.

In another aspect, the present invention is a semiconductor package comprising the printed wiring board of the present invention.

In another aspect, the invention is an electronic device comprising the printed wiring board of the invention or the semiconductor package of the invention.

In another aspect, the present invention provides a method of producing a printed wiring board, comprising: a step of bonding a resin substrate to a surface-treated metal layer of the present invention from the surface treatment layer side; The surface-treated metal foil is peeled off from the above resin substrate, and a step of transferring a resin substrate having a surface profile of the metal foil on the peeling surface; and a step of forming a circuit on the peeling surface side of the resin substrate on which the surface profile is transferred.

In one embodiment, the method for producing a printed wiring board according to the present invention is a circuit-plated pattern or a printed pattern formed on the peeling surface side of the resin substrate on which the surface profile is transferred.

In another aspect, the present invention provides a method of producing a printed wiring board, comprising: a step of bonding a resin substrate to a surface-treated metal layer of the present invention from the surface treatment layer side; a step of peeling the surface-treated metal foil from the resin substrate to obtain a resin substrate on which the surface profile of the metal foil is transferred on the release surface; and setting the peeling surface side of the resin substrate on which the surface profile is transferred Steps to add layers.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the resin constituting the layered layer contains a liquid crystal polymer or polytetrafluoroethylene.

The resin substrate can be physically peeled off by attaching the metal foil to the resin substrate by providing the release layer of the metal foil, so that the step of removing the metal foil from the resin substrate can be performed without damaging the transfer. The metal foil is removed at a preferred cost in the case of the contour of the surface of the metal foil on the surface of the resin substrate. Further, it is possible to provide a buildup layer on the resin substrate with good adhesion.

Fig. 1 shows a schematic example of a semi-additive method using a contour of a copper foil.

(surface treatment metal foil)

The surface-treated metal foil of the present invention has a surface treatment layer on at least one surface, that is, on one surface or both surfaces, and the water contact angle of the side surface of the surface treatment layer is 90 degrees or more. Furthermore, in the surface-treated metal foil of the present invention, the surface-treated layer includes a release layer, and the release layer has the resin when the resin substrate is bonded to the metal foil from the side of the release layer. The substrate can be peeled off. By providing a surface-treated layer such as a release layer on the surface of the metal foil, the metal foil has a water-repellent surface having a water contact angle of 90 degrees or more, and as a result, when the metal foil is bonded to the resin substrate, The metal foil can be physically peeled off from the resin substrate. Further, by physically peeling the metal foil from the resin substrate, in the step of removing the metal foil from the resin substrate, the contour of the surface of the metal foil transferred to the surface of the resin substrate can be prevented from being damaged. The metal foil is removed at a preferred cost. Further, the metal foil having the water-repellent surface having a water contact angle of 90 degrees or more is bonded to the resin substrate to be cured, and then the metal foil is removed to transfer the contour to the surface of the resin substrate. It is possible to laminate a circuit or a resin or the like on a resin substrate with good adhesion.

Since the surface-treated metal foil has a water-repellent surface having a water contact angle of 90 degrees or more, the peeling property after bonding the metal foil and the resin substrate can be favorably maintained, and the metal foil can be peeled off with good adhesion. The surface of the resin substrate on which the uneven contour of the surface of the metal foil is transferred is layered with a circuit or a resin.

If the water contact angle of the water-repellent surface of the surface-treated metal foil is less than 90 degrees, the peeling strength when the metal foil is bonded to the resin becomes excessively high. The water contact angle of the water-repellent surface of the metal foil is preferably 90 degrees or more, more preferably 110 degrees or more. Moreover, when the water contact angle of the water-repellent surface of the surface-treated metal foil is 120 degrees or less, it is preferable that the metal foil is not naturally peeled off and the peeling property is within an appropriate range.

Further, the uneven shape of the surface of the surface-treated metal foil is also important as a factor affecting the peel strength. When the kurtosis Rku of the surface of the metal foil on which the release layer is provided is in the range of 2.0 to 4.0, it is possible to achieve good mold release property of the metal foil and good adhesion of the circuit or resin provided after peeling off the metal foil. The closeness.

In addition, in the present specification, the "surface", the "surface of the metal foil", and the "metal foil surface" are provided with a roughened layer, a heat-resistant layer, a rust-proof layer, and a chromate-treated layer on the surface of the metal foil. In the case of a surface treatment layer such as a decane coupling treatment layer or a release layer, it means a surface (the outermost surface) after the surface treatment layer is provided.

Furthermore, the release layer may also be provided on both sides of the metal foil. Moreover, the bonding can also be performed by crimping and bonding. Further, the release layer may be provided on both sides of the metal foil.

The metal foil (also referred to as a green foil) is not particularly limited, and a copper foil, an aluminum foil, a nickel foil, a copper alloy foil, a nickel alloy foil, an aluminum alloy foil, a stainless steel foil, an iron foil, an iron alloy foil, or the like can be used.

The thickness of the metal foil (raw foil) is not particularly limited, and can be, for example, 5 to 105 μm. Further, the thickness of the metal foil is preferably from 9 to 70 μm, more preferably from 12 to 35 μm, still more preferably from 18 to 35 μm, in terms of easy peeling from the resin substrate.

Hereinafter, the copper foil will be described as an example of a metal foil (raw foil). The method for producing the copper foil (raw foil) is not particularly limited, and for example, an electrolytic copper foil can be produced under the following electrolysis conditions.

Electrolytic conditions for electrolytic foil:

Cu: 30~190g/L

H ₂ SO ₄ : 100~400g/L

Chloride ion (Cl ^- ): 60 to 200 ppm by mass

Animal glue: 1~10ppm

Electrolyte temperature: 25~80°C

Electrolysis time: 10~300 seconds (adjusted according to copper thickness and current density)

Current density: 50~150A/dm ²

Electrolyte line speed: 1.5~5m/sec

In the present invention, the removal of the metal foil from the resin substrate means that the metal foil is removed from the resin substrate by chemical treatment such as etching, or the resin substrate is physically peeled off from the metal foil by peeling or the like. When the resin substrate is removed after being bonded to the surface-treated metal foil of the present invention as described above, the resin substrate and the surface-treated metal foil are separated from the release layer. In this case, a part of the peeling layer, the roughened particles of the following metal foil, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may remain on the peeling surface of the resin substrate, but it is preferably In the absence of residue.

In the surface-treated metal foil of the present invention, when the resin substrate is bonded to the metal foil from the side of the release layer, the peel strength is preferably 200 gf/cm or less. When the control is carried out in this manner, the physical peeling of the resin substrate becomes easy, and the contour of the surface of the metal foil is more favorably transferred to the resin substrate. The peel strength is more preferably 150 gf/cm or less, still more preferably 100 gf/cm or less, still more preferably 50 gf/cm or less, and typically 1 to 200 gf/cm, and more typically 1 to 150 gf/cm.

Next, the release layer which can be used in the present invention will be described.

(1) decane compound

The decane compound having a structure represented by the following formula, or a hydrolyzate thereof, or a condensate of the hydrolyzate (hereinafter, abbreviated as a decane compound) is used alone or in combination to form a release layer. When the surface-treated metal foil is bonded to the resin substrate, the adhesion is suitable. The degree of peeling can be adjusted to the above range.

formula:

(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 with a halogen atom; Any of the hydrocarbon groups in the group, 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 Any one of the groups substituted with a halogen atom)

The decane compound must have at least one alkoxy group. Substituting a hydrocarbon group in a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom, in the absence of an alkoxy group In the case of a base, there is a tendency that the adhesion between the resin substrate and 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 groups in which one or more hydrogen atoms are substituted with a halogen atom. This is because when the hydrocarbon group is not present, the adhesion between the resin substrate and the metal foil tends to increase. Further, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

In order to adjust the peeling strength of the resin substrate and the metal foil to the above range, the decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (hydrocarbon groups containing one or more hydrogen atoms substituted with a halogen atom) ). In the above formula, it is meant that both R ³ and R 4 are alkoxy groups.

The alkoxy group is not limited, and examples thereof include a methoxy group, an ethoxy group, a normal or isopropoxy group, a n-, iso- or tert-butoxy 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 carbon. 5 alkoxy groups.

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 may, for example, be a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a n-, iso- or neopentyl group, a n-hexyl group, an n-octyl group or a n-decyl group. The linear or branched carbon number is from 1 to 20, preferably from 1 to 10 carbon atoms, more preferably from 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, an alkyl group-substituted phenyl group (for example, tolyl group, xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. The aryl group.

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

Preferred examples of the decane compound include methyltrimethoxydecane, ethyltrimethoxydecane, n- or isopropyltrimethoxynonane, n-, iso- or tert-butyltrimethoxydecane, and Iso- or neopentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, phenyltrimethoxydecane;alkyl-substituted phenyltrimethoxynonane (for example, Methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or isopropyltriethoxydecane, n-, iso- or tert-butyltriethoxy Decane, Butyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane, alkyl substituted phenyl triethoxy decane ( For example, p-(methyl)phenyltriethoxydecane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluorooctyltriethoxydecane, methyltrichlorodecane, Dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, trimethylfluorodecane, dimethyldibromodecane, diphenyldibromodecane, hydrolyzed products thereof, and the like A condensate of a hydrolyzed product or the like. Among these, from the viewpoint of easiness of obtaining, propyltrimethoxydecane, methyltriethoxydecane, hexyltrimethoxydecane, phenyltriethoxydecane, decyltrimethoxy is preferred. Base decane.

In the step of forming the release layer, 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 particularly 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 hydrolyzate is promoted. In general, when a decane compound which is sufficiently subjected to hydrolysis and condensation after a sufficient stirring time is used, the peel strength of the resin substrate and the metal foil tends 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.

When the concentration of the decane compound in the aqueous solution is high, the peel strength of the metal foil and the plate-shaped carrier tends to decrease, and the peel strength can be adjusted by adjusting the concentration of the decane compound.

Further, by increasing the concentration of the decane compound in the aqueous solution of the decane compound, it is known to further improve the water repellency. The concentration of the decane compound in the decane compound in the aqueous solution can be set to 8 ~15% by volume. If the concentration is less than 8% by volume, insufficient water repellency (specifically, there is a case where the water contact angle is less than 90 degrees), and when it exceeds 15% by volume, the decane compound is poorly dissolved. When the metal foil and the resin substrate are laminated, there is a possibility that bulging occurs due to the unreacted decane compound.

Further, it is preferred to carry out the drying step twice after applying the decane compound to the treated surface of the metal foil. The first drying is carried out only for the purpose of drying the aqueous solution of the decane compound. In the second drying, the OH group (hydroxy group) is eliminated by completely eliminating the condensation reaction for the hydroxyl group in the decane compound which is not completely subjected to the condensation reaction, and the water repellency is improved. The first drying can be carried out at 80 to 120 ° C for 10 seconds to 2 minutes, and the second drying can be carried out at 120 to 200 ° C for 30 seconds to 5 minutes.

Further, in the case of using a water-alcohol mixed solution of a decane compound, in order to uniformly dissolve the poorly water-soluble decane compound, the concentration of the alcohol in the solution is preferably from 20 to 80% by volume. If the concentration of the alcohol in the solution is less than 20% by volume, the decane compound is not dissolved. When the amount exceeds 80% by volume, the hydrolysis reaction becomes incomplete, so that the decane compound is directly hydrolyzed and remains. The water content is lowered, and the contact angle of water becomes small.

The pH of the aqueous solution of the decane compound is not particularly limited and can be utilized on 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 viewpoint of not requiring special pH adjustment, it is preferably a pH in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH in the range of 7.0 to 9.0.

(2) Compounds having two or less sulfhydryl groups in the molecule

The release layer is formed by using a compound having two or less sulfhydryl groups in the molecule, and even if the resin substrate is bonded to the metal foil by interposing the release layer, the adhesion is moderately lowered, and the adjustment is possible. Section peel strength.

However, when a compound having three or more mercapto groups in the molecule or a salt thereof is interposed between the resin substrate and the metal foil and bonded thereto, the peel strength is not satisfied. The reason is considered to be that if there are excessive sulfhydryl groups in the molecule, there are excessively generated sulfur bonds, disulfide bonds or polysulfide bonds by chemical reaction of sulfhydryl groups with each other, or sulfhydryl groups and plate-shaped carriers, or sulfhydryl groups and metal foils. A strong three-dimensional crosslinked structure is formed between the resin substrate and the metal foil, whereby the peel strength is increased. Such an example is disclosed in Japanese Laid-Open Patent Publication No. 2000-196207.

Examples of the compound having two or less mercapto groups in the molecule include a mercaptan, a dithiol, a sulfuric acid or a salt thereof, a dithiocarboxylic acid or a salt thereof, sulfuric acid or a salt thereof, and disulfuric acid or As the salt, at least one selected from the group consisting of these can be used.

A thiol group having a fluorenyl group in the molecule is represented, for example, by R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group.

The dithiol type has two indenyl groups in the molecule, and is represented, for example, by R(SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the two sulfhydryl groups may be bonded to the same carbon, respectively, or may be bonded to carbon or nitrogen which are different from each other.

The hydroxy group of the thiocarboxylic acid-based organic carboxylic acid is substituted with a fluorenyl group, and is represented, for example, by R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the sulfuric acid can also be used in the form of a salt. Further, a compound having two thiocarboxylic acid groups can also be used.

The two oxygen atoms in the carboxyl group of the dithiocarboxylic acid-based organic carboxylic acid are substituted with a sulfur atom, and are represented, for example, by R-(CS)-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the dithiocarboxylic acid can also be used in the form of a salt. Further, a compound having two dithiocarboxylic acid groups can also be used.

The hydroxyl group of the sulfuric acid-based organic sulfonic acid is substituted with a fluorenyl group, and is represented, for example, by R(SO ₂ )-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, sulfuric acid can also be used in the form of a salt.

The two hydroxyl groups of the disulfonic acid-based organic disulfonic acid are each substituted with a fluorenyl group, for example, represented by R-((SO ₂ )-SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the two sulfonic acid groups may be bonded to the same carbon, respectively, or may be bonded to carbons different from each other. Further, disulfuric acid can also be used in the form of a salt.

Here, as the preferred aliphatic hydrocarbon group for R, an alkyl group or a cycloalkyl group may be mentioned, and the hydrocarbon group may include either or both of a hydroxyl group and an amine group.

Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a normal or an iso-pentyl group, a n-hexyl group, a n-octyl group, and a positive group. The linear or branched carbon number such as a mercapto group is 1 to 20, preferably a carbon number of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms.

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

Further, examples of the preferred aromatic hydrocarbon group for R include a phenyl group, a phenyl group substituted by an alkyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group. ~20, preferably 6 to 14 aryl groups, which may comprise either or both of a hydroxyl group and an amine group.

Further, as a preferred heterocyclic group for R, there may be mentioned imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, benzothiazole, and may contain either or both of a hydroxyl group and an amine group. By.

A preferred example of a compound having two or less sulfhydryl groups in the molecule can be listed. Take: 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1-hexanol, 1-octylmercaptan, 1-dodecanethiol, 10 -hydroxy-1-dodecyl mercaptan, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol , thiobenzoic acid, 4-amino thiophenol, p-toluene thiol, 2,4-dimethyl benzene thiol, 3-mercapto-1,2,4-triazole, 2-mercaptobenzothiazole. Among these, from the viewpoint of water solubility and waste treatment, 3-mercapto-1,2-propanediol is preferred.

In the step of forming the release layer, a compound having two or less mercapto groups in the molecule 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 particularly effective when a compound having two or less mercapto groups in a molecule having high hydrophobicity is used.

When the concentration of the compound having two or less sulfhydryl groups in the molecule is high in the aqueous solution, the peel strength of the resin substrate and the metal foil tends to decrease, and the concentration of the compound having two or less sulfhydryl groups in the molecule can be adjusted. Adjust the peel strength.

Further, by increasing the concentration of the compound having two or less sulfhydryl groups in the aqueous solution in the aqueous solution, the water repellency can be further improved. The concentration of the compound having two or less sulfhydryl groups in the molecule in the aqueous solution can be set to 8 to 15% by volume. If the concentration is less than 8% by volume, insufficient water repellency (specifically, there is a case where the water contact angle is less than 90 degrees), and when it exceeds 15% by volume, two or less molecules are generated in the molecule. The compound of the sulfhydryl group is poorly dissolved, and when the metal foil and the resin substrate are laminated, there is a tendency to bulge due to the unreacted compound.

Further, it is preferred to apply a drying step twice after coating a compound having two or less sulfhydryl groups in the molecule on the treated surface of the metal foil. The first drying is carried out only for the purpose of drying an aqueous solution of a compound having two or less sulfhydryl groups in the molecule. The second drying is done by adjusting The arrangement of compounds having two or less sulfhydryl groups in the molecule of the surface of the metal foil has an effect of improving water repellency. The first drying can be carried out at 80 to 120 ° C for 10 seconds to 2 minutes, and the second drying can be carried out at 120 to 200 ° C for 30 seconds to 5 minutes.

Further, in the case of using a water-alcohol mixed solution of a compound having two or less sulfhydryl groups in the molecule, in order to uniformly dissolve a compound having two or less sulfhydryl groups in a water-insoluble molecule, the alcohol in the solution The concentration is preferably from 20 to 80% by volume. If the concentration of the alcohol in the solution is less than 20% by volume, the compound having two or less sulfhydryl groups in the molecule does not dissolve, and in the case of more than 80% by volume, it is densely disposed in the molecule of the surface of the metal foil. The arrangement of the compound having two or less sulfhydryl groups is disordered, the water repellency is lowered, and the contact angle of water becomes small.

The pH of the aqueous solution of the compound having two or less sulfhydryl groups in the molecule is not particularly limited, and it can be used on 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 viewpoint of not requiring special pH adjustment, it is preferably a pH in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH in the range of 7.0 to 9.0.

(3) Metal alkoxide

The aluminate compound, the titanate compound, the zirconate compound, or the hydrolyzate thereof, or the condensate of the hydrolyzate may be used alone or in combination (hereinafter, abbreviated as The metal alkoxide) constitutes a release layer. The resin substrate and the metal foil are bonded to each other by interposing the release layer, whereby the adhesion is appropriately lowered, and the peel strength can be adjusted.

(R ¹ ) _m -M-(R ² ) _n

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 a group in which one or more hydrogen atoms are substituted with a halogen atom Any one of the hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one R ¹ is an alkoxy group. Furthermore, m+n is the valence of M, that is, 3 in the case of Al and 4 in the case of Ti and Zr.

The metal alkoxide must have at least one alkoxy group. Substituting a hydrocarbon group in a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom, in the absence of an alkoxy group In the case of a base, there is a tendency that the adhesion between the resin substrate and the metal foil is excessively lowered. Further, the metal alkoxide must have any one of 0 to 2 hydrocarbon groups selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms substituted with a halogen atom. a hydrocarbon group. The reason for this is that when three or more of the hydrocarbon groups are present, the adhesion between the resin substrate and the metal foil tends to be excessively lowered. Further, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom. The metal alkoxide preferably has two or more alkoxy groups, one or two of the above hydrocarbon groups (containing one or more hydrogen atoms) in terms of adjusting the peeling strength of the resin substrate and the metal foil to the above range. A hydrocarbon group substituted with a halogen atom).

Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a normal or an iso-pentyl group, a n-hexyl group, a n-octyl group, and a positive group. The linear or branched carbon number such as a mercapto group is 1 to 20, preferably a carbon number of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms.

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

Further, examples of the preferred aromatic hydrocarbon group for R ² include a phenyl group, an alkyl group-substituted phenyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group. 6 to 20, preferably 6 to 14, aryl groups, which may comprise either or both of a hydroxyl group and an amine group. One or more hydrogen atoms of the hydrocarbon groups may be substituted with a halogen atom, and for example, may be substituted with a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds include trimethoxy aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or isopropyl dimethoxy aluminum, ortho, x or Tributyldimethoxyaluminum, n-, iso- or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, phenyldimethoxy Aluminium-substituted phenyldimethoxyaluminum (for example, p-(methyl)phenyldimethoxyaluminum), dimethylmethoxyaluminum, triethoxyaluminum, methyldiethoxyaluminum , ethyldiethoxyaluminum, n- or isopropyldiethoxyaluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyl Alkyl ethoxylated aluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl substituted phenyldiethoxyaluminum (for example, p-(methyl)phenyldiethoxyaluminum), Methyl ethoxylated aluminum, aluminum triisopropoxide, aluminum aluminum diisopropoxide, aluminum aluminum diisopropoxide, normal or isopropyl diethoxy aluminum, positive, different or third Aluminum diisopropoxide, aluminum pentyl diisopropoxide, aluminum hexyl diisopropoxide, Aluminium diisopropoxide, aluminum decyl diisopropoxide, aluminum phenyl diisopropoxide, aluminum substituted with alkyl phenyl diisopropoxide (for example, p-(methyl)phenyl diisopropyloxide Base aluminum), dimethyl isopropoxide aluminum, (3,3,3-trifluoropropyl)dimethoxy aluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, two Methylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, hydrolyzed products thereof, and hydrolyzed products thereof Condensate, etc. Among these, from the viewpoint of easiness of acquisition, trimethoxy aluminum, triethoxy aluminum, and aluminum triisopropoxide are preferred.

Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyl Titanium trimethoxy, n-, iso- or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl substituted phenyl Trimethoxytitanium (for example, p-(meth)phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, Ortho- or isopropyl triethoxytitanium, n-, iso- or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, fluorenyl Triethoxytitanium, phenyltriethoxytitanium, alkyl substituted phenyltriethoxytitanium (for example, p-(meth)phenyltriethoxytitanium), dimethyldiethoxytitanium, tetra Titanium isopropoxide, titanium methyl triisopropoxide, titanium triisopropoxide, titanium or n-butyl triethoxyoxide, n-, iso- or tert-butyl triisopropoxide titanium, Titanyl triisopropoxide, titanium hexyl triisopropoxide, titanium octyl triisopropoxide, titanium decyl triisopropoxide, titanium phenyl triisopropoxide, alkyl substituted phenyl tri Titanium isopropoxide (for example, p-(meth)phenyl triisopropoxytitanium), dimethyl Titanium diisopropoxide, titanium (3,3,3-trifluoropropyl)trimethoxy, and tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, three Methyl chlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, hydrolyzed products thereof, and condensates of the hydrolyzed products thereof . Among these, from the viewpoint of easiness of acquisition, tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium are preferable.

As a preferable example of the zirconate compound, tetramethoxy zirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or isopropyltrimethoxyzirconium, ortho, iso- or tert-butyl can be mentioned. Trimethyl zirconium, n-, iso- or neopentyltrimethoxy zirconium, hexyltrimethoxy zirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl substituted phenyl Trimethoxy zirconium (for example, p-(methyl)phenyltrimethoxyzirconium), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, N- or isopropyltriethoxy zirconium, n-, iso- or tert-butyltriethoxy zirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, fluorenyl Triethoxy zirconium, phenyltriethoxy zirconium, alkyl substituted phenyl triethoxy zirconium (for example, p-(methyl)phenyltriethoxy zirconium), dimethyldiethoxyzirconium, tetra Zirconium isopropoxide, zirconium methyl triisopropoxide, zirconium ethyl triisopropoxide, zirconium n- or isopropyl triethoxy, n-, iso- or tert-butyl triisopropoxy zirconium, Ziryl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triisopropoxy zirconium, decyl triisopropoxy zirconium, phenyl triisopropoxy zirconium, alkyl substituted phenyl tri Zirconium isopropoxide (for example, p-(meth)phenyltriisopropoxytitanium), zirconium dimethyldisisopropoxide, (3,3,3-trifluoropropyl)trimethoxyzirconium, and Trifluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldibromozirconium, Zirconium diphenyl dibromide, a hydrolyzed product thereof, and a condensate of the hydrolyzed product. Among these, from the viewpoint of easiness of acquisition, tetramethoxy zirconium, tetraethoxy zirconium, and tetraisopropoxy zirconium are preferable.

In the step of forming the release layer, the metal alkoxide may 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 particularly effective when a metal alkoxide having a higher hydrophobicity is used.

When the concentration of the metal alkoxide in the aqueous solution is high, the peel strength of the resin substrate and the metal foil tends to decrease, and the peel strength can be adjusted by adjusting the metal alkoxide concentration.

Further, by increasing the concentration of the metal alkoxide in the aqueous solution, it is known to further improve the water repellency. The concentration of the metal alkoxide in the aqueous solution can be set to 8 to 15% by volume. If the concentration is less than 8% by volume, there is insufficient water repellency (specifically, there is a case where the water contact angle is less than 90 degrees), and when it exceeds 15% by volume, the metal alkoxide is poorly dissolved. When the metal foil and the resin substrate are laminated, there is a tendency to bulge due to the unreacted compound.

Further, it is preferred to carry out the drying twice after applying the metal alkoxide on the treated surface of the metal foil. Drying step. The first drying is carried out only for the purpose of drying the aqueous solution of the metal alkoxide. In the second drying, the OH group (hydroxy group) is eliminated by completely eliminating the condensation reaction for the hydroxyl group in the metal alkoxide which is not completely subjected to the condensation reaction, and the water repellency is improved. The first drying can be carried out at 80 to 120 ° C for 10 seconds to 2 minutes, and the second drying can be carried out at 120 to 200 ° C for 30 seconds to 5 minutes.

Further, in the case of using a water-alcohol mixed solution of a metal alkoxide, in order to uniformly dissolve the metal alkoxide which is hardly soluble in water, the concentration of the alcohol in the solution is preferably from 20 to 80% by volume. If the concentration of the alcohol in the solution is less than 20% by volume, the metal alkoxide does not dissolve. In the case of more than 80% by volume, the hydrolysis reaction becomes incomplete, so that the metal alkoxide is not hydrolyzed. Direct residue, water repellency is reduced, and the contact angle of water becomes smaller.

The pH of the aqueous solution of the metal alkoxide is not particularly limited and can be utilized on 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 viewpoint of not requiring special pH adjustment, it is preferably a pH in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH in the range of 7.0 to 9.0.

(4) Others

A known release material such as a oxime release agent or a resin film having releasability can be used for the release layer.

In the surface-treated metal foil of the present invention, a group selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer may be disposed between the metal foil and the release layer. One or more layers in the middle. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium. And other elements (may be any form of metal, alloy, oxide, nitride, sulfide, etc.). Specific examples of the chromate-treated layer include a chromate treatment layer treated with an aqueous solution of chromic acid anhydride or potassium dichromate, or a chromate treatment treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Layers, etc.

The roughening treatment layer can be formed, for example, by the following treatment.

[spherical roughening]

The spherical roughening particles are formed using a copper roughening plating bath described below composed of Cu, H ₂ SO ₄ , and As.

. Liquid composition 1

CuSO ₄ . 5H ₂ O 78~196g/L

Cu 20~50g/L

H ₂ SO ₄ 50~200g/L

Arsenic 0.7~3.0g/L

(electrolytic plating temperature 1) 30~76°C

(current condition 1) current density 35~105A/dm ² (above the limit current density of the bath)

(plating time 1) 1~240 seconds

Then, in order to prevent the peeling of the roughened particles and to improve the peeling strength, the coating was performed by a copper electrolytic bath composed of sulfuric acid or copper sulfate. The coating plating conditions are described below.

. Liquid composition 2

CuSO ₄ . 5H ₂ O 88~352g/L

Cu 22~90g/L

H ₂ SO ₄ 50~200g/L

(electrolytic plating temperature 2) 25~80°C

(Current condition 2) Current density: 15~32A/dm ² (Unlimited bath current limit)

(plating time 1) 1~240 seconds

Further, as the heat-resistant layer and the rust-preventive layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements of the group of bismuth, or may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, A metal layer or an alloy layer composed of one or more elements selected from the group consisting of platinum group elements, iron, and lanthanum. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements of the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The above nickel-zinc alloy layer may also contain 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc in addition to unavoidable impurities. The total amount of zinc and nickel attached to the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the adhesion amount of zinc (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-containing zinc alloy layer or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² .

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer in which the deposition amount is 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and the adhesion amount. The nickel alloy layer may also be composed of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt, which is a tin layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² . Any of the components. Further, in the heat-resistant layer and/or the rust-preventive layer, the total adhesion amount of nickel or a nickel alloy to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, in the heat-resistant layer and/or the rust-preventive layer, [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] is preferably 0.25 to 10, more preferably 0.33 to 3.

Further, a known decane coupling agent can be used as the decane coupling agent used in the decane coupling treatment, and for example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxy propyl trimethyl group can also be used. Oxydecane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N- 3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer may be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amine decane coupling agent referred to herein may also be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl- 2-Aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, amine Propyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl) 3-aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-amino Ethyl- 3-aminopropyl)trimethoxynonane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl) Trimethoxy decane, aminophenyl trimethoxy decane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyl Tris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane , 3-(2-N-benzylaminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N- Diethyl-3-aminopropyl)trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxy Decane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyl A decane coupling agent in a group consisting of trimethoxy decane.

The decane coupling treatment layer is preferably 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/in terms of ruthenium atom. The range of m ² is set. In the case of the above range, the adhesion between the resin substrate and the metal foil can be further improved.

Further, the surface of the metal foil, the roughened particle layer, the heat-resistant layer, the rustproof layer, the decane coupling treatment layer, the chromate treatment layer or the release layer can be subjected to International Publication No. WO2008/053878, and JP-A-2008-111169 No. Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, Japanese Special Opening Surface treatment as described in 2013-19056.

A resin layer may also be provided on the surface of the surface-treated metal foil of the present invention. The resin layer is usually disposed on the release layer.

The resin layer on the surface of the surface-treated metal foil may be a resin, that is, an adhesive, or a primer, or an insulating resin layer may be used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no adhesive feeling even when the surface is touched with a finger, and the insulating resin layer can be stacked and stored, and further, if subjected to heat treatment, a curing reaction occurs. The resin layer on the surface of the surface-treated metal foil is preferably a resin layer which exhibits a moderate peel strength (for example, 2 gf/cm to 200 gf/cm) when it comes into contact with the release layer. Moreover, it is preferable to use the unevenness of the surface of the metal foil, and it is difficult to produce a resin which may cause a bulging void or a bubble. For example, when the resin layer is provided on the surface of the metal foil, it is preferred to use a resin viscosity of 10000 mPa. s (25 ° C) or less, more preferably the resin viscosity is 5000 mPa. A resin layer is provided with a resin having a low viscosity such as s (25 ° C) or less. By providing the resin layer between the insulating substrate laminated with the surface-treated metal foil and the surface-treated metal foil, the resin layer follows the surface of the metal foil even when an insulating substrate which is difficult to follow the unevenness of the surface of the metal foil is used. Therefore, it is possible to make it difficult to generate voids or bubbles between the surface-treated metal foil and the insulating substrate, which is effective.

Further, the resin layer on the surface of the surface-treated metal foil may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer on the surface of the surface-treated metal foil may further contain a thermoplastic resin. The resin layer on the surface of the surface-treated metal foil may include a known resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, the resin layer on the surface of the surface-treated metal foil may be, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, Japanese Patent Publication No. WO2009/084533, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. Japanese Patent No. 3,612,594, Japanese Patent Laid-Open No. 2002-179772, Japanese Laid-Open Patent Publication No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Publication No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3,949,676, Japanese Patent No. 4,174,415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. Hei. No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. The materials described in WO2011/068157 and JP-A-2013-19056 (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material) The method of forming a resin layer and/or forming a device is formed.

(layered body, semiconductor package, electronic equipment)

A resin substrate can be provided on the release layer side of the surface-treated metal foil of the present invention to produce a laminate. The laminate can utilize a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate ring An epoxy resin, a glass cloth-paper composite substrate epoxy resin, a glass cloth-glass non-woven composite substrate epoxy resin, and a glass cloth substrate epoxy resin are used to form a resin substrate. The resin substrate may be a prepreg or a thermosetting resin. Further, a printed wiring board can be produced by forming a circuit by processing the metal foil on the surface of the laminated body. Further, a printed circuit board can be produced by mounting electronic components on a printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted in this manner. Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using a printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted. Further, the above-mentioned "printed circuit board" also includes a circuit-formed substrate for semiconductor packaging. Further, an electronic component can be mounted on a circuit-formed substrate for semiconductor packaging to fabricate a semiconductor package. Further, an electronic device can be fabricated using the semiconductor package.

(Manufacturing method of printed wiring board)

The method for producing a printed wiring board according to the present invention includes the step of bonding a resin substrate to the surface of the release layer of the surface-treated metal foil of the present invention; and treating the surface-treated metal foil by etching. a step of peeling off the resin substrate to obtain a resin substrate on which the surface profile of the metal foil is transferred, and a step of forming a circuit on the peeling surface side of the resin substrate on which the surface profile is transferred. According to this configuration, the resin substrate is physically peeled off when the metal foil is provided with the release layer and the metal foil is bonded to the resin substrate, and the step of removing the metal foil from the resin substrate is not possible. The metal foil is removed at a preferred cost in the case of damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. In this manufacturing method, a circuit can be formed using a plating pattern. In this case, after the plating pattern is formed, a desired wiring can be formed by using the plating pattern to form a printed wiring board. Further, the circuit can be formed using a printed pattern. In this case, For example, a printed wiring board can be formed by forming a desired printed circuit using the printed pattern by using an inkjet ink containing a conductive paste or the like to form a printed pattern.

Furthermore, the method for producing a printed wiring board according to the present invention includes the step of bonding a resin substrate to the surface of the release layer of the surface-treated metal foil of the present invention; and etching the surface without etching. a step of peeling the metal foil from the resin substrate to obtain a resin substrate on which the surface profile of the metal foil is transferred on the peeling surface; and adding the peeling surface side of the resin substrate to which the surface profile is transferred The steps of the layer. According to this configuration, the resin substrate is physically peeled off when the metal foil is provided with the release layer and the metal foil is bonded to the resin substrate, and the step of removing the metal foil from the resin substrate is not possible. The metal foil is removed at a preferred cost in the case of damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. Further, by transferring to a specific surface shape of the resin substrate, even if the resin component of the resin substrate differs from the resin component of the buildup layer, the two can be bonded together with good adhesion.

Here, the resin constituting the build-up layer provided on the surface of the resin substrate is bonded to each other without any treatment (the resin constituting the build-up layer and the resin substrate described above) The untreated surfaces are bonded to each other, and are stretched and peeled off. The strength (tensile strength) at this time may be 500 g/cm ² or less.

Here, "additional layer" means a layer having a conductive layer, a wiring pattern, a circuit, and a resin. The shape of the resin may also be a layer. Further, the above conductive layer, wiring pattern or circuit, and resin may be provided in any manner.

The build-up layer can be produced by providing a conductive layer, a wiring pattern, a circuit, and a resin on the side of the release surface of the resin substrate on which the surface profile of the metal foil is transferred on the release surface. As a method of forming a conductive layer, a wiring pattern or a circuit, a semi-additive method, a full additive method, a subtractive method, a partial addition method can be used. A well-known method such as law.

The buildup layer may also have several layers, and may have a plurality of conductive layers, wiring patterns or circuits, and a resin (layer).

The plurality of conductive layers, wiring patterns or circuits may also be electrically insulated by a resin. After forming a through hole and/or a blind hole in the resin by a laser and/or a drill, a through plating such as copper plating may be formed on the through hole and/or the blind hole, thereby electrically insulating. The plurality of conductive layers, wiring patterns or circuits are electrically connected.

Further, a surface-treated metal foil provided with a release layer on the surface may be attached to both sides of the resin substrate from the side of the release layer, after which the surface-treated metal foil is removed, and the surface-treated metal foil is removed. The surface profile is transferred to both sides of the resin substrate, and a circuit, a wiring pattern, or a buildup layer is provided on both surfaces of the resin substrate, thereby manufacturing a printed wiring board.

The resin, the resin layer, and the resin substrate described in the present specification can be used as the resin constituting the layered layer, and a known resin, a resin layer, a resin substrate, an insulator, a prepreg, and a glass cloth impregnated with a resin can be used. Substrate and the like. The resin may also contain inorganic and/or organic materials. Further, the resin constituting the buildup layer may be formed of a material having a low relative dielectric constant such as LCP (liquid crystal polymer) or polytetrafluoroethylene. In recent years, with the expansion of high-frequency products, the trend of introducing a material having a low relative dielectric constant such as LCP (liquid crystal polymer) or polytetrafluoroethylene (Teflon: registered trademark) into a structure of a printed substrate has become active. At this time, since these materials are thermoplastic, shape change cannot be avoided during hot press processing, and in the substrate configuration using LCP (liquid crystal polymer) or a single component of polytetrafluoroethylene, there is a substantial amount in which the production yield is not improved. The subject of production. In the above-described production method of the present invention, by using an epoxy resin-like thermosetting resin as a resin substrate and bonding it, it is possible to provide a high-frequency characteristic and prevent heating. A printed wiring board whose shape is deformed.

A fine circuit can be formed by using the metal foil of the present invention and by a semi-additive method. Fig. 1 shows a schematic example of a semi-additive method using a profile of a metal foil (e.g., copper foil). In the semi-additive method, the surface profile of the metal foil is used. Specifically, first, the surface-treated metal foil of the present invention is laminated on the resin substrate from the release layer side to form a laminate. Then, the metal foil of the laminate is removed or peeled off by etching. Then, the surface of the resin substrate on which the surface profile of the metal foil is transferred is washed with dilute sulfuric acid or the like, and then electroless copper plating is performed. Then, the surface of the resin substrate which does not form a circuit is covered with a dry film or the like, and the surface of the electroless copper plating layer which is not covered with the dry film is subjected to electric (electrolytic) copper plating. Thereafter, after the dry film is removed, the electroless copper plating layer formed in the portion where the circuit is not formed is removed, thereby forming a fine circuit. The fine circuit formed in the present invention is in close contact with the peeling surface of the resin substrate on which the surface profile of the metal foil of the present invention is transferred, so that the adhesion (peeling strength) is good.

Further, another embodiment of the semi-additive method is as follows.

The semi-additive method refers to a method in which thin electroless plating is performed on a resin substrate or a metal foil, and after forming a pattern, a conductor pattern is formed by electrolytic plating and etching. Therefore, an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a surface-treated metal foil of the present invention and a resin substrate; and self-releasing the surface-treated metal foil a step of laminating the resin substrate on the layer side; a step of removing or peeling off the surface-treated metal foil by etching the surface-treated metal foil and the resin substrate; and removing the resin from the surface-treated metal foil a step of providing a through hole or/and a blind hole in the peeling surface of the substrate; a step of desmear treatment of the region including the through hole or/and the blind hole; and cleaning the surface of the resin substrate with dilute sulfuric acid or the like for the resin substrate and the region including the through hole or/and the blind hole; And providing an electroless plating layer (for example, an electroless copper plating layer); providing a plating resist layer on the electroless plating layer; exposing the plating resist layer, and thereafter forming a circuit a step of removing the plating layer in the region; a step of providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in the region where the plating resist layer is removed, and a step of removing the plating resist layer; and The step of removing the electroless plating layer existing in the region other than the region where the circuit is formed by flash etching or the like.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a surface-treated metal foil of the present invention and a resin substrate; and self-releasing the surface-treated metal foil a step of laminating a resin substrate on the side; a step of removing or peeling the surface-treated metal foil by etching after laminating the surface-treated metal foil and the resin substrate; and forming a resin base by peeling off the surface-treated metal foil a peeling surface of the material, a step of washing the surface of the resin substrate with dilute sulfuric acid or the like, and an electroless plating layer (for example, an electroless copper plating layer); and a step of providing a plating resist layer on the electroless plating layer Exposing the above-mentioned plating resist layer, and thereafter, removing the plating resist layer in the region where the circuit is formed; a step of providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in the region where the plating resist layer is removed, and a step of removing the plating resist layer; and forming the circuit by flash etching or the like The step of removing the electroless plating layer present in the area outside the area.

By forming a circuit on the peeling surface of the resin substrate after the surface-treated metal foil is peeled off, a printed circuit forming substrate and a circuit forming substrate for semiconductor packaging can be produced. Further, a printed wiring board or a semiconductor package can be produced by using the circuit to form a substrate. Further, an electronic device can be produced using the printed wiring board or the semiconductor package.

On the other hand, another embodiment of the method for producing a printed wiring board of the present invention using the full additive method includes the steps of: preparing the surface-treated metal foil of the present invention and a resin substrate; and treating the metal foil on the surface a step of laminating a resin substrate from the release layer side; a step of removing or peeling the surface-treated metal foil by etching after laminating the surface-treated metal foil and the resin substrate; and peeling off the surface-treated metal foil a step of removing the surface of the resin substrate by using dilute sulfuric acid or the like; a step of providing a plating resist layer on the surface of the washed resin substrate; and exposing the plating resist layer Then, a step of removing the plating layer in the region where the circuit is formed; and providing an electroless plating layer in the region where the plating layer is removed to form the circuit (for example, it may be an electroless copper plating layer, and the thickness is not Electroplating layer); and The step of removing the above-mentioned plating resist layer.

Further, in the semi-additive method and the full-addition method, there is a case where the surface of the resin substrate is washed to exhibit an effect of easily providing an electroless plating layer. In particular, when the release layer remains on the surface of the resin substrate, part or all of the release layer is removed from the surface of the resin substrate by the cleaning, so that the surface of the resin substrate is washed by the surface of the resin substrate. It is easier to set the effect of the electroless plating layer. This washing can be carried out by using a known washing method (the type of liquid to be used, the temperature, the method of applying the liquid, etc.). Further, it is preferred to use a cleaning method which can remove part or all of the release layer of the present invention.

In this way, by the full-addition method, a circuit on which the surface of the resin substrate after the surface-treated metal foil is peeled off can be formed into a circuit to form a printed circuit-formed substrate or a circuit-formed substrate for semiconductor package. Further, a printed wiring board or a semiconductor package can be produced by forming a substrate using the circuit. Further, an electronic device can be produced by using the printed wiring board or the semiconductor package.

Further, the surface of the surface-treated metal foil is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis), and is detected. For Si, it is presumed that a decane compound is present on the surface of the surface-treated metal foil. Moreover, when the peel strength of the surface-treated metal foil and the resin substrate is 200 gf/cm or less, the above-described decane compound which can be used for the release layer of the present invention can be estimated.

Further, the surface of the surface-treated metal foil is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis) to detect S. When the peel strength of the surface-treated metal foil and the resin substrate is 200 gf/cm or less, it can be presumed that On the surface of the surface-treated metal foil, there is a compound having two or less sulfhydryl groups in the above-mentioned molecule which can be used for the release layer of the present invention.

Further, the surface of the surface-treated metal foil was measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis) to detect Al. When Ti, Zr, and the surface-treated metal foil and the resin substrate have a peel strength of 200 gf/cm or less, it is presumed that the above-mentioned release layer of the present invention can be used on the surface of the surface-treated metal foil. Metal alkoxide.

[Examples]

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

. Production of green foil (metal foil (copper foil) before surface treatment) The electrolytic green foil of the thickness described in Table 1 was produced under the following electrolysis conditions.

(electrolyte composition)

Cu 120g/L

H ₂ SO ₄ 100g/L

Chloride ion (Cl ^- ) 70ppm

Fish gelatin 6ppm

Electrolyte temperature 60 ° C

Current density 70A/dm ²

Electrolyte line speed 2m/sec

. Surface treatment

Then, as the surface treatment, each of the conditions shown below is subjected to roughening treatment, barrier treatment (heat treatment), rust prevention treatment, decane coupling treatment, and resin layer formation treatment on the M surface (matte surface) of the green foil. Each of the processes is performed in either or combination. Then, the conditions shown below form a release layer on the treated side surface of the copper foil. Furthermore, in the case where it is not specifically mentioned, each process is performed in this order. Further, in Table 1, the description of "None" in the column of each process indicates that the processes are not performed.

(1) roughening treatment

[spherical roughening]

The spherical roughening particles are formed using a copper roughening plating bath described below composed of Cu, H ₂ SO ₄ , and As.

. Liquid composition 1

CuSO ₄ . 5H ₂ O 78~118g/L

Cu 20~30g/L

H ₂ SO ₄ 12g/L

Arsenic 1.0~3.0g/L

(electrolytic plating temperature 1) 25~33 °C

(Current condition 1) Current density 78A/dm ² (above the limit current density of the bath)

(plating time 1) 1~45 seconds

Then, in order to prevent the peeling of the roughened particles and to improve the peeling strength, the coating was performed by a copper electrolytic bath composed of sulfuric acid or copper sulfate. The coating plating conditions are described below.

. Liquid composition 2

CuSO ₄ . 5H ₂ O 156g/L

Cu 40g/L

H ₂ SO ₄ 120g/L

(electrolytic plating temperature 2) 40 ° C

(Current condition 2) Current density: 20A/dm ² (Unlimited bath current limit)

(plating time 2) 1~60 seconds

(2) Barrier treatment (heat treatment)

(liquid composition)

Ni 13g/L

Zn 5g/L

pH 2

(electrolytic plating conditions)

Temperature 40 ° C

Current density 8A/dm ²

(3) Anti-rust treatment

(liquid composition)

CrO ₃ 2.5g/L

Zn 0.7g/L

Na ₂ SO ₄ 10g/L

pH 4.8

(zinc chromate conditions)

Temperature 54 ° C

Current density 0.7As/dm ²

(4) decane coupling treatment

(liquid composition)

Tetraethoxy decane content 0.4%

pH 7.5

Coating method spray of solution

(5) Formation of release layer

[Release layer A]

After applying a water-methanol mixed solution containing 8 vol% of a decane compound (n-propyltrimethoxydecane) in a volume ratio to a treated surface of a metal foil (copper foil) using a spray coater, the air was made in air at 100 ° C. The surface of the copper foil was dried for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a release layer A. The stirring time before the application of the decane compound in water to the coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer B]

After applying a water-methanol mixed solution containing 8 vol% of a decane compound (n-hexyltrimethoxydecane) in a volume ratio to a treated surface of a metal foil (copper foil) using a spray coater, copper was made in air at 100 ° C. The surface of the foil was dried for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a release layer B. The stirring time before the application of the decane compound in water to the coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer C]

In the use of a sprayer, 8 vol% of a decane compound (n-decyltrimethoxy) is contained by volume. After the water-methanol mixed solution of decane was applied to the treated surface of the metal foil (copper foil), the surface of the copper foil was dried in air at 100 ° C for 1 minute, and then heat treated in air at 150 ° C for 1 minute. A release layer C is formed. The stirring time before the application of the decane compound in water to the coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer D]

Applying a water-methanol mixed solution containing 8 vol% of a decane compound (dimethyl dimethoxy decane) in a volume ratio to a treated surface of a metal foil (copper foil) using a spray coater, in air at 100 ° C The surface of the copper foil was dried for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a release layer D. The stirring time before the application of the decane compound in water to the coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer E]

Applying a water-methanol mixed solution containing 8 vol% of a decane compound (trifluoropropyltrimethoxydecane) in a volume ratio to a treated surface of a metal foil (copper foil) using a spray coater, in air at 100 ° C The surface of the copper foil was dried for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a release layer E. The stirring time before the application of the decane compound in water to the coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer F]

Using sodium 1-dodecyl mercaptan sulfonate as a compound having 2 or less mercapto groups in the molecule, a water-methanol mixed solution of sodium 1-dodecanethiolsulfonate (1-dodecane sulfur) using a spray coater alcohol The sodium sulfonate concentration: 8 vol%) was applied to the treated surface of the metal foil (copper foil), and then the surface of the copper foil was dried in air at 100 ° C for 1 minute, and then heat treated in air at 150 ° C for 1 minute. The release layer F is formed. The methanol concentration in the solution was set to 40 vol% by volume, and the pH of the solution was set to 5 to 9.

[release layer G]

Using aluminum triisopropoxide as an aluminate compound as a metal alkoxide, a water-methanol mixed solution of triisopropoxy aluminum (a concentration of aluminum triisopropoxide: 8 vol%) was applied using a spray coater. The surface of the metal foil (copper foil) was treated, and then the surface of the copper foil was dried in air at 100 ° C for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a release layer G. The stirring time before the application of the aluminate compound in water to the coating was 2 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the solution was 5-9.

[release layer H]

Using a n-decyltriisopropoxide titanium as a titanate compound as a metal alkoxide, a water-methanol mixed solution of n-decyltriisopropoxide titanium (n-decyltriisopropoxy group) using a spray coater Titanium concentration: 8 vol%) was applied to a treated surface of a metal foil (copper foil), and then the surface of the copper foil was dried in air at 100 ° C for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a surface. Release layer H. The stirring time before the application of the titanate compound in water to the application was 24 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 5 to 9.

[release layer I]

Using n-propyltri-n-butoxyzirconium as a zirconate compound as a metal alkoxide, a water-methanol mixed solution of n-propyltri-n-butoxyzirconium (n-propyltri-n-butoxy group) using a spray coater Zirconium concentration: 8 vol%) was applied to a treated surface of a metal foil (copper foil), and then the surface of the copper foil was dried in air at 100 ° C for 1 minute, and then heat-treated in air at 150 ° C for 1 minute to form a surface. Release layer I. The stirring time before the application of the zirconate compound in water to the coating was 12 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 5 to 9.

(6) Resin layer formation treatment

In Example 1, after the release layer was formed, the resin layer was further formed under the following conditions.

(Resin Synthesis Example)

Add 3, 4, 3', 4 to a 2-liter three-necked flask equipped with a stainless steel crucible stir bar, a nitrogen inlet tube, and a stopcock, and a reflux cooler equipped with a spherical cooling tube. '-Biphenyltetracarboxylic dianhydride 117.68g (400mmol), 1,3-bis(3-aminophenoxy)benzene 87.7g (300mmol), γ-valerolactone 4.0g (40mmol), pyridine 4.8g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g, heated at 180 ° C for 1 hour, cooled to near room temperature, and then added 3, 4, 3', 4' -biphenyltetracarboxylic dianhydride 29.42g (100mmol), 2,2-bis{4-(4-aminophenoxy)phenyl}propane 82.12g (200mmol), NMP200g, toluene 40g, at room temperature After mixing for 1 hour, it was heated at 180 ° C for 3 hours to obtain a block copolymerized polyimine of 38% of a solid content. With respect to the block copolymerized polyimine, the following general formula (1): general formula (2) = 3:2, a number average molecular weight of 70,000, and a weight average molecular weight of 150,000.

The block copolymerized polyimine solution obtained in the synthesis example was further diluted with NMP to prepare a block copolymerized polyimine solution having a solid content of 10%. In the block copolymerized polyimine solution, bis(4-maleimide phenyl)methane (BMI-H, K.I Chemical Industry) is set as a solid component weight ratio of 35, and the block is The copolymerized polyimine is set to have a solid component weight ratio of 65 (ie, the weight of the bis(4-maleimidophenyl)methane solid component contained in the resin solution: the total amount of the block contained in the resin solution The polymerized polyimine solid content component weight = 35:65) was dissolved and mixed at 60 ° C for 20 minutes to prepare a resin solution. Thereafter, the resin solution was applied onto the release layer forming surface, dried in a nitrogen atmosphere at 120 ° C for 3 minutes, dried at 160 ° C for 3 minutes, and finally heat treated at 300 ° C for 2 minutes. A copper foil having a resin layer was produced. Further, the thickness of the resin layer was set to 2 μm.

(7) Various evaluations

. Evaluation of water contact angle

The water contact angle of the surface of the metal foil was measured by FACE CA-D manufactured by Kyowa Interface Science Co., Ltd. Ion exchange water having a water pH of 6 to 8 and a temperature of 25 ° C was measured. The contact angle was measured within 1 minute after dropping the droplet onto the surface of the metal foil.

. Determination of kurtosis (Rku)

The kurtosis (Rku) of the surface of the metal foil is laser-made by Olympus Co., Ltd. The micromirror OLS4100 was measured in accordance with the JIS B 0601 2001 standard mode. The measurement length was set to 258 μm. Further, the temperature at the time of measurement was set to 23 to 25 °C.

. Manufacturing of laminated bodies

Any one of the following resin substrates 1 to 3 was bonded to the release layer side surface of each surface-treated metal foil.

Substrate 1: GHPL-830 MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.

Substrate 2: 679-FG manufactured by Hitachi Chemical Co., Ltd.

Substrate 3: EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.

The temperature, pressure, and time of laminate pressing are recommended by the manufacturer of each substrate.

. Evaluation of the peelability of surface treated metal foil

With respect to the laminate, the normal peel strength at the time of peeling the resin substrate from the copper foil was measured by a tensile tester Autograph 100 in accordance with IPC-TM-650, and the peeling property of the surface-treated metal foil was evaluated by the following criteria.

A: Less than 2 gf/cm.

B: is in the range of 2 to 200 gf/cm.

C: more than 200 gf/cm.

. Evaluation of the failure mode of resin

The peeling surface of the resin substrate after peeling was observed with an electron microscope, and the failure mode of the resin (coagulation, interface, aggregation, and mixing of the interface) was observed. Regarding the failure mode of the resin, the "interface" indicates that the interface between the copper foil and the resin is peeled off, and "coagulation" indicates that the peel strength is too strong and the resin is broken. "Mixed presence" indicates that the "interface" and "aggregation" are mixed.

. Evaluation of circuit stripping and substrate bulging

Using a plating solution [liquid composition, Cu: 50 g/L, H ₂ SO ₄ : 50 g/L, Cl: 60 ppm), a copper plating pattern (line/gap) was formed on the peeling faces of the resin substrates 1 to 3 after the above peeling. = 50 μm / 50 μm) (Example 1). Moreover, a printing pattern (line/gap=50 μm/50 μm) was formed on the peeling surface of the resin substrate after the peeling by inkjet using an ink containing a conductive paste (Example 2). Further, a resin layer composed of a liquid crystal polymer (assuming a resin constituting the build-up layer) is laminated on the peeling surface of the peeled resin substrate (Example 3).

Then, it was confirmed by a reliability test (250 ° C ± 10 ° C × 1 hour heating test) whether or not circuit peeling or substrate bulging occurred. Further, the size of the evaluation sample was set to 250 mm × 250 mm, and each sample number was measured for three samples.

The person who did not have the circuit peeling and the substrate bulging was evaluated as "◎". Although a small amount of circuit peeling or substrate bulging occurs (three or less in one sample), if the position to be used is selected, it can be evaluated as "○" as a product user. Further, a large number (more than three in one sample) were peeled off or the substrate was bulged, and it was not evaluated as "x" as a product user.

The test conditions and evaluation results are shown in Table 1.

In each of Examples 1 to 13, the water contact angle of the surface of the surface treatment layer was 90 degrees or more, and the peeling property of the metal foil from the resin substrate was physically peeled off, and the peeling of the circuit and the occurrence of the substrate bulging were well suppressed. .

In Comparative Example 1, the water contact angle of the surface of the surface treatment layer was less than 90 degrees, and the peeling property of the metal foil from the resin substrate was poorly peeled off, and the occurrence of circuit peeling and substrate bulging could not be satisfactorily suppressed.

Claims (28)

A surface-treated metal foil having a surface treatment layer on at least one surface, and a water contact angle of the side surface of the surface treatment layer is 90 degrees or more. The surface-treated metal foil according to the first aspect of the invention, wherein the flank Rku defined by JIS B 0601 on the side surface of the surface treatment layer is 2.0 to 4.0. The surface-treated metal foil according to the first aspect of the invention, wherein the surface treatment layer includes a release layer, and the release layer has the resin when the resin substrate is bonded to the metal foil from the side of the release layer The substrate can be peeled off. The surface-treated metal foil according to the second aspect of the invention, wherein the surface treatment layer is provided with a release layer, and the release layer is such that the resin is bonded to the metal foil from the side of the release layer The substrate can be peeled off. The surface-treated metal foil according to the third aspect of the invention, wherein the mold release layer is used alone or in combination of several aluminate compounds, titanate compounds, zirconate compounds represented by the following formulas, and the like. a product obtained by hydrolyzing a product or a condensate of the hydrolyzate, (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is an alkoxy group or a halogen atom, and R ² is selected from an alkyl group and a ring. a hydrocarbon group in a group consisting of an alkyl group and an aryl group, or one or more hydrogen atoms substituted with any one of the groups of the halogen atom, M is any one of Al, Ti, Zr, and n is 0 , 1 or 2, m is an integer of 1 or more and a valence of M or less, at least one R ¹ is an alkoxy group; further, m + n is a valence of M, that is, 3 in the case of Al, In the case of Ti and Zr, it is 4). The surface-treated metal foil according to the fourth aspect of the invention, wherein the mold release layer is used alone or in combination of several aluminate compounds, titanate compounds, zirconate compounds represented by the following formulas, and the like. a product obtained by hydrolyzing a product or a condensate of the hydrolyzate, (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is an alkoxy group or a halogen atom, and R ² is selected from an alkyl group and a ring. a hydrocarbon group in a group consisting of an alkyl group and an aryl group, or one or more hydrogen atoms substituted with any one of the groups of the halogen atom, M is any one of Al, Ti, Zr, and n is 0 , 1 or 2, m is an integer of 1 or more and a valence of M or less, at least one R ¹ is an alkoxy group; further, m + n is a valence of M, that is, 3 in the case of Al, In the case of Ti and Zr, it is 4). The surface-treated metal foil according to the third aspect of the invention, wherein the release layer is used singly or in combination of a plurality of decane compounds represented by the following formula, a hydrolyzed product 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 with a halogen atom; Any of the hydrocarbon groups in the group, 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 Any one of these groups substituted with a halogen atom). The surface-treated metal foil according to the fourth aspect of the invention, wherein the release layer is used singly or in combination of a plurality of decane compounds represented by the following formula, a hydrolyzed product 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 with a halogen atom; Any of the hydrocarbon groups in the group, 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 Any one of these groups substituted with a halogen atom). The surface-treated metal foil according to claim 3, wherein the release layer is formed by using a compound having two or less sulfhydryl groups in the molecule. The surface-treated metal foil according to the fourth aspect of the invention, wherein the release layer is a compound having two or less sulfhydryl groups in the molecule. The surface-treated metal foil of claim 3, wherein between the metal foil and the release layer, a roughening layer, a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a decane are disposed between the metal foil and the release layer. Coupling one or more layers of the group consisting of layers. The surface-treated metal foil according to claim 4, wherein between the metal foil and the release layer, a roughening layer, a heat-resistant layer, a rustproof layer, and a chromate are provided. One or more layers of the group consisting of the treatment layer and the decane coupling treatment layer. The surface-treated metal foil according to claim 11, wherein the one or more selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane-coupled treatment layer; The surface of the layer is provided with a resin layer. The surface-treated metal foil according to claim 12, wherein the one or more selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer The surface of the layer is provided with a resin layer. The surface-treated metal foil according to any one of claims 3 to 14, wherein a resin layer is provided on a side surface of the release layer. The surface-treated metal foil according to claim 13 or 14, wherein the resin layer is followed by a resin, a primer or a resin in a semi-hardened state. The surface-treated metal foil according to claim 15 wherein the resin layer is followed by a resin, a primer or a resin in a semi-hardened state. The surface-treated metal foil according to any one of claims 1 to 14, which has a thickness of 5 to 210 μm. The surface-treated metal foil according to any one of claims 1 to 14, wherein the metal foil is a copper foil. A laminate comprising the surface-treated metal foil according to any one of claims 1 to 19, and a resin substrate provided on the release layer side of the surface-treated metal foil. The laminate according to claim 20, wherein the resin substrate is a prepreg or a thermosetting resin. A printed wiring board having a surface at any one of claims 1 to 19 Metal foil. A semiconductor package comprising the printed wiring board of claim 22 of the patent application. An electronic device comprising the printed wiring board of claim 22 or the semiconductor package of claim 23 of the patent application. A method of producing a printed wiring board, comprising the steps of: attaching a resin substrate to a surface-treated metal foil according to any one of claims 1 to 19; a step of removing the surface-treated metal foil from the resin substrate by etching to obtain a resin substrate on which the surface profile of the metal foil is transferred on the release surface; and the above-mentioned resin substrate to which the surface profile is transferred The step of forming the circuit on the peeling side. The method for producing a printed wiring board according to claim 25, wherein the circuit-formed pattern or printed pattern formed on the peeling surface side of the resin substrate on which the surface profile is transferred is formed. A method of producing a printed wiring board, comprising the steps of: attaching a resin substrate to a surface-treated metal foil according to any one of claims 1 to 19; a step of removing the surface-treated metal foil from the resin substrate by etching to obtain a resin substrate on which the surface profile of the metal foil is transferred on the release surface; and the above-mentioned resin substrate to which the surface profile is transferred The step of setting the layer on the peeling side. The manufacturing method of the printed wiring board of claim 27, wherein the above-mentioned increase is constituted The resin of the layer contains a liquid crystal polymer or polytetrafluoroethylene.