TW201540144A - Surface treatment copper foil, copper-clad lamination board, printed wiring board, electronic machine, circuit formation substrate and manufacturing method of semiconductor package and printed wiring board - Google Patents

Abstract

The present invention provides a surface treatment copper foil characterized in that when a resin substrate adheres onto a copper foil and then the copper foil is to be removed from the resin substrate, the copper foil can be removed at an excellent cost without performing an etching process and without damaging the contour of the surface of the copper foil transfer-printed on the surface of the resin substrate surface. The surface treatment copper foil of the present invention comprises: a copper foil having an uneven surface on which there is no coarse particle while an Rz measured according to JIS B0601(year of 1994) is 0.1-5.0 <mu>m, or a copper foil having coarse particles; and a mold release layer disposed on the surface of the copper foil having an uneven surface or on the surface of the copper foil having coarse particles, so as to peel off the resin substrate from the side of the mold release layer when the resin substrate adheres to the copper foil.

Description

Surface-treated copper foil, copper-clad laminate, printed wiring board, electronic device, circuit-formed substrate for semiconductor package, semiconductor package, and printed wiring board manufacturing method

The present invention relates to a surface-treated copper foil, a copper-clad laminate, a printed wiring board, an electronic device, a circuit-formed substrate for semiconductor packaging, a semiconductor package, and a method of manufacturing a printed wiring board.

In the circuit formation method of the printed wiring board and the semiconductor package substrate, the subtractive method is the mainstream. However, with the further fine wiring in recent years, M-SAP (Modified Semi-Additive Process) or half of the surface profile of the copper foil is used. New methods of construction such as the addition of the law have arisen.

Among these novel circuit formation methods, an example of a semi-additive method using the surface profile of the copper foil as the latter is as follows. In other words, first, the copper foil laminated on the resin substrate is etched over the entire surface, and the surface of the etched substrate on which the surface contour of the copper foil is transferred is opened by laser or the like, and electrolessness for conducting the opening portion is provided. The copper plating layer is coated with an electroless copper plating surface by a dry film, and the dry film of the circuit forming portion is removed by UV exposure and development, and the electroless copper plating surface not covered by the dry film is subjected to electroplating copper to carry out the dry film. After the peeling, the electroless copper plating layer is finally etched (rapid etching, rapid etching) using an etching solution containing sulfuric acid or hydrogen peroxide, thereby forming a fine circuit. In addition, in the present process example, the catalyst treatment for electroless copper plating, the pickling treatment for cleaning the surface of the copper, and the like are various, and the description thereof is omitted (Japanese Patent Document 1 and Japanese Patent Application No. 2).

[Previous Technical Literature] [Patent Literature]

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

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

In the semi-additive method using the outline of the surface of the copper foil, the copper foil laminated on the resin is usually etched. However, in terms of etching, the chemical liquid used, the drainage treatment, and the like are costly, and the load on the environment is also large. Further, in the case where the copper foil is removed by etching, depending on the type of the substrate and the etching conditions, the contour of the surface of the copper foil may be damaged. Therefore, the use of the etched copper foil is poorly removed.

As a result of intensive studies, the present inventors have found that a copper foil having surface irregularities or roughened particles can be provided with a release layer on the copper foil to bond the copper foil to the resin substrate. Physical peeling eliminates the need to perform etching in the step of removing the copper foil from the resin substrate, and does not damage the contour of the surface of the copper foil transferred onto the surface of the resin substrate, and the copper foil can be removed at a good cost.

The present invention based on the above findings is, in one aspect, a surface-treated copper foil comprising: a copper foil which does not have roughened particles, and has an Rz of 0.1 to 5.0 as measured according to JIS B0601 (1994). a copper foil having a surface unevenness of μm; and a release layer which is a release layer provided on a surface of the copper foil having surface unevenness, and is bonded to the copper foil from the release layer side to the resin substrate The above resin substrate can be peeled off.

In another aspect, the invention is a surface treated copper foil comprising: copper foil, It has roughened particles, and the release layer is provided on the roughened particle surface of the copper foil, and the resin substrate when the resin substrate is bonded to the copper foil from the release layer side is peelable.

In one embodiment of the surface treated copper foil of the present invention, the release layer is When the resin substrate is bonded to the copper foil in the lateral direction, the peel strength at the time of peeling off the resin substrate is 200 gf/cm or less.

In still another embodiment of the surface-treated copper foil of the present invention, the release layer is formed by using a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product, either alone or in combination.

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

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

In still another embodiment of the surface-treated copper foil of the present invention, the release layer is an aluminate compound, a titanate compound, a zirconate compound, or a hydrolyzate produced by the following formula, and the hydrolysis is formed. The condensate of the substance is used alone or in combination of a plurality of types, (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, and Zr, n is 0 or 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group. 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 copper foil of the present invention, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer are provided between the copper foil and the release layer. More than one layer in the group.

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

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

In still another embodiment of the surface-treated copper foil of the present invention, the surface-treated copper foil has a thickness of 9 to 70 μm.

Further, in still another embodiment of the surface-treated copper foil of the present invention, the surface-treated copper foil of the present invention can be used in a method for producing a printed wiring board, which has the following steps: a resin base from the side of the release layer a step of bonding the surface-treated copper foil to the surface, and obtaining a resin base on which the surface profile of the copper foil is transferred on the release surface by peeling the surface-treated copper foil from the resin substrate without etching. And a step of forming a circuit on the side of the peeling surface of the resin substrate to which the surface profile is transferred.

Further, in still another embodiment of the surface-treated copper foil of the present invention, the surface-treated copper foil of the present invention comprises: a copper foil which does not have roughened particles, and which is Rz measured according to JIS B0601 (1994). a copper foil having surface irregularities of 0.1 to 5.0 μm; and a release layer which is a release layer provided on a surface of the copper foil having surface irregularities, and which is bonded to the copper foil from the side of the release layer The resin substrate may be peeled off when the resin substrate is used, or may have a copper foil having roughened particles, and a release layer which is a release layer provided on the roughened particle surface of the copper foil, and The resin base material when the resin layer is bonded to the copper foil on the side of the release layer is peelable; and any one of the following (A) to (I) is satisfied.

(A) When the resin substrate is bonded to the copper foil from the release layer side, the peel strength when the resin substrate is peeled off is 200 gf/cm or less; (B) the release layer is represented by the following formula The decane compound, the hydrolyzate thereof, and the condensate of the hydrolyzate are used singly or in combination of two or more.

(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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. (C) the above-mentioned release layer is a compound having two or less mercapto groups in the molecule; (D) the above release layer is an aluminate represented by the following formula The compound, the titanate compound, the zirconate compound, the hydrolyzate, and the condensate of the hydrolyzate are used singly or in combination of two or more, (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, and Zr, n is 0 or 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group. m+n is a valence of M, that is, 3 in the case of Al, and 4 in the case of Ti and Zr; (E) is provided between the copper foil and the above-mentioned release layer. One or more layers of the heat-resistant layer, the rust-preventive layer, the chromate-treated layer, and the decane coupling treatment layer; (F) a resin layer is provided on the surface of the surface-treated copper foil; (G) is as described above ( In F), the resin layer is a resin for bonding, a primer or a resin in a semi-hardened state; (H) the surface-treated copper foil has a thickness of 9 to 70 μm; (I) a method for producing a printed wiring board, the manufacturing method The method comprises the steps of: bonding a resin substrate to the surface-treated copper foil from the side of the release layer; obtaining the surface-treated copper foil by not etching a step of peeling the resin substrate from the resin substrate, transferring a resin substrate having a surface profile of the copper foil on the release surface, and forming a circuit on the peeling surface side of the resin substrate having the surface profile transferred thereto .

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

The resin substrate of the copper-clad laminate of the present invention is a prepreg or a thermosetting resin.

Still another aspect of the invention is a printed wiring board using the surface treated copper foil of the present invention.

In still another aspect of the invention, a printed wiring board is manufactured using the surface treated copper foil of the present invention.

Still another aspect of the invention is a semiconductor package comprising the printed wiring board of the invention.

Yet another aspect of the invention is an electronic machine using the printed wiring board or semiconductor package of the present invention.

According to still another aspect of the invention, there is provided a method of producing a printed wiring board comprising: a step of bonding a resin substrate to the surface-treated copper foil of the present invention from the side of the release layer; and the surface-treated copper foil a step of removing the resin substrate from which the surface profile of the copper foil is transferred on the release surface without peeling off from the resin substrate; and the peeling of the resin substrate on which the surface profile is transferred The step of forming a circuit on the face side.

Further, in still another aspect of the invention, a resin substrate is obtained by laminating a resin substrate from the side of the release layer to the surface-treated copper foil of the present invention, and the surface-treated copper foil is not subjected to In the case of etching, the resin substrate is peeled off from the resin substrate and the surface profile of the copper foil is transferred onto the release surface.

The present invention provides a wheel which does not need to be etched and which does not damage the surface of the copper foil transferred onto the surface of the resin substrate when the copper foil is bonded to the resin substrate after the resin substrate is bonded to the copper foil. The surface treated copper foil can be removed from the copper foil at a good cost.

Fig. 1 is a schematic view showing a semi-additive method using a contour of a copper foil.

The surface-treated copper foil of the present invention comprises: a copper foil which is a copper foil having surface irregularities which does not have roughened particles and has an Rz of 0.1 to 5.0 μm as measured according to JIS B0601 (1994); and a release layer This is a release layer provided on the surface of the copper foil having the surface unevenness, and the resin substrate can be peeled off when the resin substrate is bonded to the copper foil from the release layer side. Further, the release layer may be provided on both sides of the copper foil. Further, the bonding may be performed by pressure bonding and bonding.

In another aspect, the surface-treated copper foil of the present invention comprises: a copper foil having roughened particles; and a release layer provided on the roughened surface of the copper foil, and pasting the copper foil from the side of the release layer The resin substrate at the time of the resin substrate can be peeled off. Further, the release layer may be provided on both sides of the copper foil.

The copper foil (also referred to as a green foil) may also be formed of any one of an electrolytic copper foil or a rolled copper foil. The thickness of the copper foil is not particularly limited and may be, for example, 5 to 105 μm. Further, the thickness of the surface-treated copper foil is preferably from 9 to 70 μm, more preferably from 12 to 35 μm, even more preferably from 18 to 35 μm, from the viewpoint that the peeling of the resin substrate is facilitated.

The method for producing the copper foil (raw foil) is not particularly limited. For example, in the case of producing a conventional electrolytic green foil, the electrolytic conditions can be set as follows.

Electrolytic conditions for ordinary electrolytic foil: Cu: 80~120g/L

H ₂ SO ₄ : 80~120g/L

Chloride ion (Cl): 30~100ppm

Leveling agent (glue): 0.1~10ppm

Electrolyte temperature: 50~65°C

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

Current density: 50~150A/dm ²

Electrolyte line speed: 1.5~5m/sec

Further, in the case of producing an electrolytic green foil having a flat surface on both sides, the electrolysis conditions can be set as follows.

Electrolytic conditions for flat electrolyzed foil on both sides

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

Homogenizer 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

Electrolyte temperature: 50~65°C

Electrolysis time: 0.5 to 10 minutes (adjusted according to the copper thickness and current density)

Current density: 70~100A/dm ²

Electrolyte line speed: 1.5~5m/sec

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group).

In the present invention, the "removal" of the resin substrate from the copper foil means that the resin substrate is physically peeled off from the copper foil by peeling or the like, and the copper foil is not removed from the resin substrate by chemical treatment such as etching. . When the resin substrate is bonded to the surface-treated copper foil of the present invention as described above and then peeled off, the resin substrate and the surface-treated copper foil are separated from the release layer. However, in this case, the release surface of the resin substrate may be peeled off. A layer, a roughened particle of the following copper foil, a heat-resistant layer, a rust preventive layer, a chromate-treated layer, a decane coupling treatment layer, or the like, but preferably no residue.

In the surface-treated copper foil of the present invention, when the resin substrate is bonded to the copper foil from the side of the release layer, the peel strength at the time of peeling off the resin substrate is preferably 200 gf/cm or less. By controlling in this way, physical peeling of the resin substrate becomes easy, and the contour of the surface of the copper 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.

Regarding the surface-treated copper foil of the present invention, in one aspect, the surface of the copper foil is set to have no roughened particles, and the Rz measured according to JIS B0601 (1994) is 0.1 to 5.0 μm. a surface having irregularities or a surface having roughened particles. According to this configuration, when the surface-treated copper foil is bonded to the resin substrate and the copper foil is peeled off, the surface of the copper foil is transferred onto the surface of the resin substrate, but the peeling can be easily performed with low peeling. Further, the contour of the surface of the copper foil is firmly transferred to the surface of the resin substrate, whereby the adhesion of the electroless ‧ electroplated copper in the semi-additive step can be sufficiently ensured.

The roughened particle layer formed on the surface of the copper foil can be formed by using an electrolytic bath composed of at least one of sulfuric acid and copper sulfate containing at least one selected from the group consisting of an alkyl sulfate salt, a tungsten ion, and an arsenic ion. It is composed of spherical particles or fine particles. The surface roughness of the roughened particle layer can be controlled by appropriately adjusting the electrolytic treatment conditions. Further, when the copper foil is made of an electrolytic copper foil, the matte side of the electrolytic copper foil may be a roughened surface of the copper foil. The surface roughness of the matte side of the electrolytic copper foil can be controlled by appropriately adjusting the electrolytic treatment conditions.

The roughened particle layer can be produced by using an electrolytic bath composed of at least one of sulfuric acid and copper sulfate containing at least one selected from the group consisting of an alkyl sulfate salt, a tungsten ion, and an arsenic ion. Specific processing conditions are as follows, for example.

(liquid composition 1)

CuSO ₄ ‧5H ₂ O 39.3~118g/L

Cu 10~30g/L

H ₂ SO ₄ 10~150g/L

Na ₂ WO ₄ ‧2H ₂ O 0~90mg/L

W 0~50mg/L

Sodium lauryl sulfate added 0~50pp

H ₃ AsO ₃ (60% aqueous solution) 0~6315mg/L

As 0~2000mg/L

(plating condition 1)

Temperature 30~70°C

(current condition 1)

Current density 25~110A/dm ²

Plating time 0.5~20 seconds

(liquid composition 2)

CuSO ₄ ‧5H ₂ O 78~314g/L

Cu 20~80g/L

H ₂ SO ₄ 50~200g/L

(plating condition 2)

Temperature 30~70°C

(current condition 2)

Current density 5~50A/dm ²

Plating time 1~60 seconds

Further, the roughened particle layer can also be formed in the following manner. First, a Cu-Co-Ni ternary alloy layer is formed. The Co and Ni contents are 1 to 4% by mass Co and 0.5 to 1.5% by mass of Ni. The processing conditions of the ternary alloy plating are shown below.

(liquid composition)

Cu 10~20g/L

Co 1~10g/L

Ni 1~10g/L

pH 1~4

(plating conditions)

Temperature 40~50°C

Current density 20~30A/dm ²

Processing time 1~5 seconds

After the above-described roughening treatment, plating is performed twice to form a cobalt plating layer or a plating layer composed of cobalt and nickel. The conditions for cobalt plating or cobalt and nickel plating are as follows.

‧Cobalt plating

(liquid composition)

Cobalt-coated Co 1~30g/L

pH 1.0~3.5

(plating conditions)

Temperature 30~80°C

Current density 1~10A/dm ²

Processing time 0.5~4 seconds

‧Cobalt-nickel plating

(liquid composition)

Co 1~30g/L, Ni 1~30g/L

pH 1.0~3.5

(plating conditions)

Temperature 30~80°C

Current density 1~10A/dm ²

Processing time 0.5~4 seconds

Further, the roughened particle layer may be formed by spherical roughening. An example of the processing conditions thereof is shown below.

(liquid composition)

Cu 20~30g/L (added as copper sulfate 5 hydrate, the same applies below)

H ₂ SO ₄ 80~120g/L

Arsenic 1.0~2.0g/L

(plating conditions)

Temperature 35~40°C

Current density 70A/dm ² (above the limit current density of the bath)

Processing time 0.5~20 seconds

The surface on which the roughening plating was carried out under the above conditions was plated by a copper electrolytic bath composed of sulfuric acid and copper sulfate in order to prevent the coarse particles from falling off. Examples of plating conditions are shown below.

(liquid composition)

Cu 40~50g/L

H ₂ SO ₄ 80~120g/L

(plating conditions)

Temperature 43~47°C

Current density 29A/dm ² [Unlimited bath current limit]

Processing time 0.5~20 seconds

The surface of the copper foil which does not have roughened particles and which has an unevenness with an Rz of 0.1 to 5.0 μm measured according to JIS B0601 (1994) or a surface having roughened particles preferably has a surface roughness Rz of 0.1~ 5.0 μm. When the surface roughness Rz is less than 0.1 μm, there is a problem in that the adhesion of the electroless copper plating in the semi-additive step cannot be sufficiently ensured, and the wiring is peeled off after the formation of the fine wiring, if the surface roughness is obtained. When Rz exceeds 5.0 μm, there is a problem that the fine wiring forming ability in the semi-addition step is lowered. The surface roughness Rz is more preferably 0.2 to 4.0 μm, still more preferably 0.3 to 3.5 μm, still more preferably 0.4 to 3.0 μm.

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

(1) decane compound

A decane compound having a structure represented by the following formula, or a hydrolyzate thereof, or a condensate of the hydrolyzate (hereinafter, simply referred to as a decane compound) may be used alone or in combination to form a release layer, thereby When the surface-treated copper foil is bonded to the resin substrate, the adhesion is appropriately lowered, and the peel strength 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 the above one or more hydrogen atoms are substituted with a halogen atom; Any of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are substituted Any of the above hydrocarbon groups of a halogen atom).

The decane compound must have at least one alkoxy group. In the absence of alkoxy groups In the case where only a hydrocarbon group selected from 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 constitutes a substituent, there are a resin substrate and copper. The adhesion of the foil tends to be too low. 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 above hydrocarbon 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 copper foil tends to increase. Further, the alkoxy group also includes an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

The decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (including one or more hydrogen atoms substituted with a halogen atom). If it is represented by the above formula, both of R ³ and R ⁴ are alkoxy groups.

The alkoxy group is not limited, and examples thereof include a methoxy group, an ethoxy group, and a positive or an equivalent. Linear or branched chain such as propoxy, n-, i- or ter-butoxy, n-, iso- or neopentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, and n-octyloxy Or ring carbon number 1 to 20, preferably carbon The number is 1 to 10, more preferably an alkoxy group having 1 to 5 carbon atoms.

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

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

The cycloalkyl group is not limited, and examples thereof include a ring having 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. alkyl.

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 6 14 aryl groups.

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

As an example of a preferable decane compound, methyl trimethoxy decane, ethyl trimethoxy decane, n- or isopropyl trimethoxy decane, n-, iso- or tri-butyl butyl trimethoxy decane, , iso- or neopentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, phenyltrimethoxydecane;alkyl-substituted phenyltrimethoxynonane (for example, P-(methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or isopropyltriethoxydecane, n-, iso- or tert-butyl butyl triethyl Oxy decane, pentyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane, alkyl substituted phenyl triethyl Oxydecane (for example, p-(methyl)phenyltriethoxydecane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluorooctyltriethoxydecane, A Trichloromethane, dimethyl dichlorodecane, trimethylchlorodecane, phenyl trichlorodecane, trimethylfluorodecane, dimethyl dibromodecane, diphenyl Bromodecane, such hydrolyzed A product, a condensate of the hydrolyzed product, and the like. Among these, from the viewpoint of easiness of availability, propyltrimethoxydecane, methyltriethoxydecane, hexyltrimethoxydecane, phenyltriethoxydecane, decyltrimethoxy is preferred. Base decane.

In the step of forming the release layer, the decane compound may be in the form of an aqueous solution. use. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is effective especially when a highly hydrophobic decane compound is used. The aqueous solution of the decane compound accelerates the 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 undergoes hydrolysis and condensation after a sufficient stirring time is used, the peel strength of the resin substrate and the copper foil tends to decrease. Therefore, the peel strength can be adjusted by the adjustment of the stirring time. Although not limited, the stirring time after dissolving the decane compound in water can be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there are also methods that are used without stirring.

When the concentration of the decane compound in the aqueous solution of the decane compound is high, there is a metal The peeling strength of the foil and the plate-shaped carrier tends to decrease, and the peel strength can be adjusted by adjusting the concentration of the decane compound. Although not limited, the concentration in the aqueous solution of the decane compound can be set to 0.01 to 10.0% by volume, and typically 0.1 to 5.0% by volume.

The pH of the aqueous solution of the decane compound is not particularly limited, regardless of the acidic side. It is also applicable on 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 particularly adjusting the pH value, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH value in the range of 7.0 to 9.0.

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

The release layer is formed by using a compound having two or more mercapto groups in the molecule, and the resin substrate and the copper foil are bonded together via the release layer, whereby the adhesion is appropriately lowered, and the peel strength can be adjusted.

In the case where a compound having three or more mercapto groups in the molecule or a salt thereof is bonded between the resin substrate and the copper foil, the purpose of lowering the peel strength is not satisfied. It can be considered that the reason is that if the thiol group in the molecule is excessively present, the sulfur bond, the disulfide bond or the polysulfide bond is excessively generated due to the chemical reaction of the sulfhydryl group with each other, or the sulfhydryl group and the plate-like carrier, or the sulfhydryl group and the metal foil, thereby A strong three-dimensional crosslinked structure is formed between the substrate and the copper foil, whereby the peel strength is increased. The above examples are disclosed in Japanese Laid-Open Patent Publication No. 2000-196207.

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

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

A dithiol is a compound having two mercapto groups in the molecule, for example, represented by R(SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may contain a hydroxyl group or an amine group. In addition, 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.

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

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

Sulfuric acid is a compound in which a hydroxyl group of an organic sulfonic acid is substituted with a mercapto 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 contain a hydroxyl group or an amine group. Further, sulfuric acid may be used in the form of a salt.

The disulfuric acid is a compound in which two hydroxyl groups of the organic disulfonic acid are substituted with a mercapto group, respectively, and is represented, for example, by R-((SO ₂ )-SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may contain a hydroxyl group or an amine group. In addition, 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, examples of the aliphatic hydrocarbon group which is suitable as R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain 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, an iso or a tertiary butyl group, a normal, an iso- or neopentyl group, a n-hexyl group, an n-octyl group, and a positive group. A linear or branched carbon number of 1 to 20 such as a mercapto group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 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 7 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Cycloalkyl.

Further, examples of the aromatic hydrocarbon group which is suitable as R 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. 20, preferably 6 to 14 aryl groups, these hydrocarbon groups may also contain any one of a hydroxyl group and an amine group or Both.

Further, examples of the heterocyclic group which is suitable as R include imidazole and triazole. Tetrazolium, benzimidazole, benzotriazole, thiazole, benzothiazole may also contain either or both of a hydroxyl group and an amine group.

Preferred examples of the compound having two or less mercapto 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-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol, Thiobenzoic acid, 4-amino-thiophenol, p-toluene mercaptan, 2,4-dimethylthiophenol, 3-mercapto-1,2,4 triazole, 2-mercapto-benzothiazole . 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 sulfhydryl groups in the molecule The substance 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 effective especially when a compound having two or less mercapto groups in a molecule having high hydrophobicity is used.

The concentration in the aqueous solution of the compound having 2 or less thiol groups in the molecule When the height is high, the peeling strength of the resin substrate and the copper foil tends to decrease, and the peel strength can be adjusted by adjusting the concentration of the compound having two or less sulfhydryl groups in the molecule. Although not limited, the concentration in the aqueous solution of the compound having two or less thiol groups in the molecule may be 0.01 to 10.0% by weight, and typically 0.1 to 5.0% by weight.

The pH of the aqueous solution of the compound having 2 or less thiol groups in the molecule is not It is particularly limited, and it can be applied on both the acidic side and the alkaline side. For example, it can range from 3.0 to 10.0. The pH is used. From the viewpoint of not particularly adjusting the pH value, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH value in the range of 7.0 to 9.0.

(3) Metal alkoxide

An aluminate compound, a titanate compound, a zirconate compound, or a hydrolyzate thereof, or a condensate of the hydrolyzate (hereinafter, simply referred to as a metal alkoxide) having a structure represented by the following formula may also be used. The release layer is formed by using it alone or in combination of a plurality of uses. By bonding the resin substrate and the copper foil through the release layer, the adhesion is appropriately lowered, and the peel strength can be adjusted.

(R ¹ ) _m -M-(R ² ) _n

In the formula, R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one or more hydrogen atoms are substituted with a halogen atom. The hydrocarbon group, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group. Further, m+n is a 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. In the case where the alkoxy group is not present and only the hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of the above-described hydrocarbon groups in which one or more hydrogen atoms is substituted with a halogen atom constitutes a substituent There is a tendency that the adhesion between the resin substrate and the copper foil is too low. Further, the metal alkoxide must have 0 to 2 hydrocarbon groups selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any one of the above hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. The reason is: there are more than 3 In the case of the hydrocarbon group, the adhesion between the resin substrate and the copper foil tends to be excessively lowered. Further, the alkoxy group also includes an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom. In adjusting the peeling strength of the resin substrate and the copper foil to the above range, the metal alkoxide preferably has two or more alkoxy groups, one or two of the above hydrocarbon groups (including one or more hydrogen atoms substituted with a halogen) Hydrocarbon group of an atom).

Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a positive or a different one. a linear or branched carbon number of 1 to 20, preferably a carbon number, such as a propyl group, a normal or an iso- or a tri-butyl group, a normal or an iso- or neopentyl group, a n-hexyl group, an n-octyl group or a n-decyl group. 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 cyclopropyl group, a cyclobutyl group, and a ring. The pentyl group, the cyclohexyl group, the cycloheptyl group, and the cyclooctyl group have a carbon number of 3 to 10, preferably a cycloalkyl group having 5 to 7 carbon atoms.

Further, examples of the aromatic hydrocarbon group which is suitable as 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. ～20, preferably 6 to 14 aryl groups, these hydrocarbon groups may also contain either or both of a hydroxyl group and an amine group. These hydrocarbon groups may have one or more hydrogen atoms substituted with a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

As an example of a preferred aluminate compound, trimethoxy aluminum and A are mentioned. Alkali dimethoxy aluminum, ethyl dimethoxy aluminum, n- or isopropyl dimethoxy aluminum, n-, iso- or tert-butyl butyl dimethoxy aluminum, n-, iso- or neopentyl dimethoxy Aluminium, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, phenyldimethoxyaluminum; alkyl-substituted phenyldimethoxyaluminum (for example, pair (A Phenyldimethoxyaluminum), dimethylmethoxyaluminum, triethoxyaluminum, methyldiethoxyaluminum,ethyldiethoxyaluminum, n- or isopropyldiethoxy Aluminum, n-, iso- or tert-butyl butyl diethoxy aluminum, pentyl diethoxy aluminum, hexyl diethoxy aluminum, octyl diethoxy aluminum, Mercapto-diethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (for example, p-(methyl)phenyldiethoxyaluminum), dimethylethoxyaluminum , aluminum triisopropoxide, aluminum aluminum diisopropoxide, aluminum aluminum diisopropoxide, normal or isopropyl diethoxy aluminum, n-, iso- or tert-butyl diisopropoxy Aluminum, pentyl aluminum diisopropoxide, aluminum hexyl diisopropoxide, aluminum octyl diisopropoxide, aluminum decyl diisopropoxide, aluminum phenyl diisopropoxide, alkyl substituted benzene Aluminium diisopropoxide (for example, p-(methyl)phenyl diisopropoxy aluminum), dimethyl isopropoxide aluminum, (3,3,3-trifluoropropyl)dimethoxy Aluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, Diphenyl bromide, a hydrolyzate, and a condensate of the hydrolyzate. Among these, from the viewpoint of easiness of acquisition, trimethoxy aluminum, triethoxy aluminum, and aluminum triisopropoxide are preferred.

As an example of a preferable titanate compound, titanium tetramethoxide and methyl group are mentioned. Trimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tri-tert-butyltrimethoxytitanium, n-, iso- or neopentyltrimethoxytitanium, hexyltrimethoxy Titanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (for example, p-(methyl)phenyltrimethoxytitanium), Methyl dimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, n- or isopropyltriethoxytitanium, n-, iso- or tert-butyl butyl Ethoxy titanium, pentyl triethoxy titanium, hexyl triethoxy titanium, octyl triethoxy titanium, decyl triethoxy titanium, phenyl triethoxy titanium, alkyl substituted phenyl three Titanium ethoxide (for example, p-(meth)phenyltriethoxytitanium), dimethyldiethoxytitanium, tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriiso Titanium propoxide, titanium or n-propyltriethoxytitanium, n-, iso- or tert-butyl butyl triisopropoxide, titanium pentyl triisopropoxide, titanium hexyl triisopropoxide, octyl Titanium triisopropoxide, titanium decyl triisopropoxide, phenyl triiso Titanium group, an alkyl-substituted phenyl titanium triisopropoxide (Example For example, p-(methyl)phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl)trimethoxytitanium, and tridecafluorooctyl Triethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromo Titanium, the hydrolyzed product, and a condensate of the hydrolyzed product. Among these, from the viewpoint of easiness of acquisition, titanium tetramethoxide, titanium tetraethoxide, and titanium tetraisopropoxide are preferable.

As an example of a preferable zirconate compound, tetramethoxy zirconium and a methyl group are mentioned. Trimethoxy zirconium, ethyltrimethoxy zirconium, n- or isopropyltrimethoxy zirconium, n-, iso- or tri-butyl butyl trimethoxy zirconium, n-, iso- or neopentyl trimethoxy zirconium, hexyl trimethoxy Zirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl substituted phenyltrimethoxyzirconium (for example, p-(methyl)phenyltrimethoxyzirconium), Methyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, n- or isopropyltriethoxyzirconium, n-, iso- or tert-butyl butyl Zirconium ethoxide, zirconium pentyl triethoxy zirconium, zirconium triethoxy zirconium, octyl triethoxy zirconium, decyl triethoxy zirconium, phenyl triethoxy zirconium, alkyl substituted phenyl tri Zirconium ethoxide (for example, p-(methyl)phenyltriethoxy zirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriiso Zirconium propoxide, zirconium n- or isopropyltriethoxylate, zirconium, n- or tri-butyl butyl triisopropoxide, zirconium pentyl triisopropoxide, zirconium hexyl triisopropoxide, octyl Zirconium triisopropoxide, zirconium decyl triisopropoxide, phenyl triiso Zirconyloxy, alkyl substituted phenyl triisopropoxy zirconium (for example, p-(methyl)phenyl triisopropoxytitanium), zirconium dimethyl diisopropoxide, (3,3,3- Trifluoropropyl)trimethoxyzirconium, and trifluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyl Difluorozirconium, zirconium dimethyldibromide, zirconium diphenyldibromide, a hydrolyzate, and a condensate of the hydrolyzate. 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 in the form of an aqueous solution. use. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is effective especially when a highly hydrophobic metal alkoxide is used.

When the concentration of the metal alkoxide in the aqueous solution is high, there is a resin substrate and a copper foil The tendency of the peel strength to decrease is adjusted by adjusting the concentration of the metal alkoxide. Although not limited, the concentration in the aqueous solution of the metal alkoxide may be 0.001 to 1.0 mol/L, and typically 0.005 to 0.2 mol/L.

The pH of the aqueous solution of the metal alkoxide is not particularly limited, and is acidic. The side or the alkaline side can be applied. For example, it can be used at a pH in the range of 3.0 to 10.0. From the viewpoint of not particularly adjusting the pH value, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH value in the range of 7.0 to 9.0.

The surface-treated copper foil of the present invention can also be disposed between the copper foil and the release layer. One or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer are selected. The chromate treatment layer herein 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 elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium (also may be metals, alloys, oxides, nitrides, sulfides). Any form of matter). Specific examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Processing layers, etc.

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, The layer of one or more elements in the group of cerium may also be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum. A metal layer or an alloy layer composed of one or more elements of a group of elements, iron, and lanthanum. In addition, the heat-resistant layer and/or the rust-preventing layer may also contain 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 in 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 rustproof layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may 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 adhesion amount of zinc and nickel in 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 amount of adhesion of zinc (=the amount of adhesion of nickel/the amount of adhesion of zinc) is preferably 1.5 to 10. Further, the amount of nickel contained in the layer containing the nickel-zinc alloy 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 having a deposition amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and attached thereto. The heat resistant layer and/or the rustproof layer of the tin layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² , the nickel alloy layer may also be nickel-molybdenum or nickel-zinc Any of nickel-molybdenum-cobalt. Further, the heat-resistant layer and/or the rust-preventive layer preferably have a total adhesion amount of nickel or a nickel alloy to tin of 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, the heat-resistant layer and/or the rust-preventive layer are preferably [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] = 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, the decane coupling agent may also be a vinyl trimethoxy decane, a vinyl phenyl trimethoxy decane, a γ-methyl propylene methoxy propyl trimethoxy decane, or a γ-glycidoxy propyl trimethoxy group. Baseline, 4-epoxypropylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N- β- (aminoethyl)-γ-aminopropyltrimethoxydecane, N-3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, triazine decane, γ-mercaptopropyltrimethoxydecane Wait.

The above decane coupling treatment layer may also be an epoxy decane, an amine decane, or a It is formed by a decane coupling agent such as a propylene oxy oxane or a decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, a decane coupling treatment layer formed using an amino decane coupling agent or an epoxy decane coupling agent is preferred.

The amino-based decane coupling agent herein may also be selected from N-(2-amino group). Ethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, aminopropyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-benzene Aminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane , (Aminoethylaminomethyl) phenethyltrimethoxydecane, N-(2-aminoethyl-3-aminopropyl)trimethoxynonane, N-(2-aminoethyl) 3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl)trimethoxynonane, aminophenyltrimethoxydecane, 3-(1- Aminopropyloxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyltris(methoxyethoxyethoxy)decane, 3-aminopropyl Triethoxy decane, 3-aminopropyltrimethoxydecane, ω-aminoundecyltrimethoxydecane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxynonane, double (2 -hydroxyethyl)-3-aminopropyltriethoxydecane, (N,N-diethyl-3-aminopropyl)trimethoxydecane, (N,N-dimethyl-3- Aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-amine Ethylethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-3 An amine-based decane coupling agent in the group consisting of -(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane.

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. Set within the range of /m ² . In the case of the above range, the adhesion between the resin substrate and the copper foil can be further improved.

In addition, the copper layer, the roughened particle layer, the heat resistant layer, the rustproof layer, and the decane coupling The surface of the treatment layer or the chromate treatment layer is disclosed in International Publication No. WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/ The surface treatment described in Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, and Japanese Patent Laid-Open No. 2013-19056.

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

The resin layer may be a bonding resin, that is, a bonding agent, a primer, or an insulating resin layer in a semi-hardened state (B-stage state) for bonding. Semi-hardened state (B The stage state includes a state in which there is no stickiness even when the surface is touched by a finger, and the insulating resin layer can be stacked for storage, and if subjected to heat treatment, a hardening reaction occurs.

Further, the above resin layer may contain a thermosetting resin or a thermoplastic tree. fat. Further, the above resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, and the like. In addition, as the above-mentioned resin layer, for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. No., International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003- No. 304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, and 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. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153 Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, and 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. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009 /008471, Japan Special Open 2011-14727, International Public Number WO2009/001850, International Public Number WO2009 /145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open Publication No. 2013-19056 (resin, resin curing agent, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, pre- It is formed by a method of forming a blister, a skeleton, or the like and/or a resin layer, and a forming apparatus.

A resin substrate can be provided on the release layer side of the surface-treated copper foil of the present invention. Used as a copper clad laminate. The copper clad laminate can also be a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, a glass cloth ‧ paper composite substrate epoxy resin, a glass cloth ‧ glass non-woven composite substrate The epoxy resin and the glass cloth substrate epoxy resin 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 a copper foil on the surface of the copper clad laminate. 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 as described above. In addition, an electronic device can be produced by using the printed wiring board described above, and an electronic device can be produced by using the printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured by 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 produced by using the above semiconductor package.

The copper foil of the present invention can be used to form a fine circuit by a semi-additive method. figure 1 A schematic example of a semi-additive method using a profile of a copper foil. A surface profile of the copper foil is used in the semi-additive process. Specifically, first, the surface-treated copper foil of the present invention is laminated on the resin substrate from the release layer side to prepare a copper foil laminate. Then, the copper foil (surface-treated copper foil) of the copper foil laminate was peeled off without etching. Then, the surface of the copper foil is transferred by using dilute sulfuric acid or the like. After the surface of the contoured resin substrate is cleaned, electroless copper plating is performed. Then, the surface of the resin substrate which is not formed with a circuit such as a dry film is coated with electric (electrolytic) copper plating on the surface of the electroless copper plating layer which is not covered with the dry film. 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. Since 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 copper foil of the present invention is transferred, the adhesion (peeling strength) is improved.

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

The semi-additive method is a method in which a thin electroless plating is performed on a resin substrate or a copper foil, and a pattern is formed, and a conductor pattern is formed by plating and etching. Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the semi-additive method, the method comprising the steps of: preparing the surface-treated copper foil of the present invention and a resin substrate; and treating the copper foil from the surface a step of laminating the resin substrate on the release layer side; a step of peeling off the surface-treated copper foil after laminating the surface-treated copper foil and the resin substrate; and peeling off the resin substrate by peeling off the surface-treated copper foil a step of providing a through hole or/and a blind hole; performing a desmear treatment step on the region including the through hole or/and the blind hole; and the resin substrate and the region including the through hole or/and the blind hole, a step of cleaning the surface of the resin substrate with dilute sulfuric acid or the like and providing an electroless plating layer (for example, an electroless copper plating layer); and providing a plating resist on the electroless plating layer; and exposing the anti-plating agent, a step of removing the plating resist for the region in which the circuit is formed; a step of providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the above-mentioned circuit is formed by removing the plating resist; a step of removing the plating resist; and a rapid etching or the like A step of removing electroless plating from a region other than the region in which the circuit is formed.

In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method comprises the steps of: preparing a surface-treated copper foil of the present invention and a resin substrate; and self-depositing the surface-treated copper foil a step of laminating the resin substrate on the mold layer side; a step of peeling off the surface-treated copper foil after laminating the surface-treated copper foil and the resin substrate; and a peeling surface of the resin substrate produced by peeling off the surface-treated copper foil a step of cleaning the surface of the resin substrate with dilute sulfuric acid or the like and providing an electroless plating layer (for example, an electroless copper plating layer); and providing a plating resist on the electroless plating layer; and exposing the anti-plating agent a step of removing the plating resist for the region in which the circuit is formed; a step of providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the above-mentioned circuit is formed by removing the plating resist; a step of removing the dressing; and a step of removing the electroless plating layer existing in the region other than the region for forming the circuit by rapid etching or the like.

Thus, the peeling surface of the resin substrate after the surface-treated copper foil is peeled off can form electricity. In the road, a printed circuit forming substrate and a circuit forming substrate for semiconductor packaging are produced. Further, a printed wiring board or a semiconductor package can be produced by forming a substrate using the above-described circuit. Further, an electronic device can be produced by using the above printed wiring board or semiconductor package.

On the other hand, in another embodiment of the method for producing a printed wiring board of the present invention using the full additive method, the method comprising the steps of: preparing the surface-treated copper foil of the present invention and a resin substrate; and performing the above surface treatment a step of laminating a resin substrate from the release layer side of the copper foil; a step of peeling off the surface-treated copper foil after laminating the surface-treated copper foil and the resin substrate; and a resin base generated by peeling off the surface-treated copper foil a peeling surface of the material, a step of washing the surface of the resin substrate with dilute sulfuric acid or the like; a step of providing a plating resist on the surface of the cleaned resin substrate; exposing the plating resist to the surface, and thereafter forming a step of removing the plating resist in the region of the circuit; and providing an electroless plating layer (for example, an electroless copper plating layer or a thick electroless plating layer) in a region where the above-mentioned circuit is formed by removing the plating resist a step; and a step of removing the above-mentioned anti-plating agent.

Further, in the semi-additive method and the full-addition method, there is a case where it is easy to provide an electroless plating layer by washing the surface of the resin substrate. In particular, when the release layer remains on the surface of the resin substrate, there is a case where a part or all of the release layer is removed from the surface of the resin substrate by the above cleaning, and thus The surface of the resin substrate is cleaned to make it easier to provide an electroless plating layer. This cleaning can be carried out by washing using a known cleaning 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 a part or all of the release layer of the present invention.

Thus, the resin substrate after the copper foil is peeled off by the full addition method The peeling surface forms a circuit to form a printed circuit forming substrate and a circuit forming substrate for semiconductor packaging. Further, a printed wiring board or a semiconductor package can be produced by forming a substrate using the above-described circuit. Further, an electronic device can be produced by using the above printed wiring board or semiconductor package.

In addition, the use of XPS (X-ray photoelectron spectroscopy device), EPMA (electric A device such as a sub-probe microanalyzer or an EDX (energy dispersive X-ray analysis) scanning electron microscope measures the surface of a copper foil or a surface-treated copper foil. If Si is detected, it is presumed that it is in copper foil or A decane compound is present on the surface of the surface treated copper foil. When the peel strength (peel strength) of the surface-treated copper foil and the resin substrate is 200 gf/cm or less, it is presumed that the above-described decane compound which can be used in the release layer of the present invention is used.

In addition, it is equipped with XPS (X-ray photoelectron spectroscopy device), EPMA (electricity) A device such as a sub-probe microanalyzer) or an EDX (energy dispersive X-ray analysis) scanning electron microscope measures the surface of a copper foil or a surface-treated copper foil, and simultaneously detects the surface of the copper foil and detects the S When the peeling strength (peeling strength) of the resin substrate is 200 gf/cm or less, it is presumed that the surface of the copper foil or the surface-treated copper foil has two or less sulfhydryl groups in the molecule which can be used in the release layer of the present invention. Compound.

In addition, a copper foil or a surface-treated copper foil is used in a device such as a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy device), an EPMA (electron probe micro analyzer), and an EDX (energy dispersive X-ray analysis). The surface is measured, and when Al, Ti, and Zr are detected, the surface is When the peel strength (peel strength) of the surface-treated copper foil and the resin substrate is 200 gf/cm or less, it is presumed that the metal alkoxide which can be used for the release layer of the present invention is present on the surface of the copper foil or the surface-treated copper foil. .

[Examples]

The following is a description of the embodiments of the present invention and the comparative examples, which are intended to provide a better understanding of the invention and its advantages, and are not intended to limit the invention.

‧Production of raw foil (copper foil before surface treatment)

Under the following respective electrolysis conditions, a common electrolytic green foil having a thickness described in Table 1 and a double-sided flat electrolytic green foil were produced.

(1) Ordinary electrolytic foil

Cu 120g/L

H ₂ SO ₄ 100g/L

Chloride ion (Cl ^- ) 70ppm

Leveling agent (glue) 3ppm

Electrolyte temperature 60 ° C

Current density 70A/dm ²

Electrolyte line speed 2m/sec

(2) Two-sided flat electrolytic foil

Electrolytic conditions for flat electrolyzed foil on both sides

Cu 120g/L

H ₂ SO ₄ 100g/L

Chloride ion (Cl ^- ) 70ppm

Leveling agent 1 (bis(3 sulfopropyl) disulfide) 20 ppm

Leveling agent 2 (amine compound) 20ppm

Electrolyte temperature 60 ° C

Current density 70A/dm ²

Electrolyte line speed 2m/sec

As the above amine compound, an amine compound of the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are a group selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group).

‧Surface treatment

Then, as the surface treatment, the M surface (matte surface) of the green foil can be subjected to roughening treatment, barrier processing (heat treatment), rust prevention treatment, decane coupling treatment, and resin layer formation under the respective conditions described below. Any one of the processes is processed, or each process is combined. Then, a release layer was formed on the surface of the above-mentioned processing side of the copper foil under the conditions shown below. In addition, there is no special In the case of not mentioning, each process is performed in the order described above.

(1) roughening treatment

[spherical roughening (usually)]

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

(liquid composition 1)

CuSO ₄ ‧5H ₂ O 98g/L

Cu 25g/L

H ₂ SO ₄ 100g/L

Arsenic 1.5g/L

(plating temperature 1) 38 ° C

(current condition 1) current density 70A/dm ² (above the limit current density of the bath)

Then, in order to prevent the peeling of the roughened particles and the peeling strength from being improved, plating was performed using a copper electrolytic bath composed of sulfuric acid and copper sulfate. The plating conditions are described below.

(liquid composition 2)

CuSO ₄ ‧5H ₂ O 176g/L

Cu 45g/L

H ₂ SO ₄ 100g/L

(plating temperature 2) 45 ° C

(Current condition 2) Current density: 29 A/dm ² (unlimited current density of the bath)

[Micro-roughening (Type1)]

First, the roughening treatment is performed under the following conditions. The relative limit current density ratio at the time of formation of the roughened particles was set to 2.50.

(liquid composition 1)

CuSO ₄ ‧5H ₂ O 58.9g/L

Cu 15g/L

H ₂ SO ₄ 100g/L

Na ₂ WO ₄ ‧2H ₂ O 5.4mg/L

Sodium lauryl sulfate added 10ppm

(plating temperature 1) 40 ° C

(current condition 1) current density 54A/dm ²

Then, normal plating was performed under the conditions shown below.

(liquid composition 2)

CuSO ₄ ‧5H ₂ O 176g/L

Cu 45g/L

H ₂ SO ₄ 100g/L

(plating temperature 2) 45 ° C

(current condition 2) current density 41A/dm ²

[Micro-roughening (Type2)]

First, after forming a Cu-Co-Ni ternary alloy layer by the following liquid composition 1 and plating condition 1, a cobalt plating layer is formed on the ternary alloy layer by the following liquid composition 2 and plating condition 2.

(liquid composition 1)

Cu 10~20g/L

Co 1~10g/L

Ni 1~10g/L

pH 1~4

(plating temperature 1) 40~50°C

(current condition 1) current density 25A/dm ²

(liquid composition 2)

Co 1~30g/L

Ni 1~30g/L

pH 1.0~3.5

(plating temperature 2) 30~80°C

(current condition 2) current density 5A/dm ²

(2) Barrier treatment (heat treatment)

With respect to Examples 9, 11, and 12, a barrier (heat-resistant) treatment was performed under the following conditions to form a brass-plated layer.

(liquid composition)

Cu 70g/L

Zn 5g/L

NaOH 70g/L

NaCN 20g/L

(plating conditions)

Temperature 70 ° C

Current density 8A/dm ² (multi-stage processing)

(3) Anti-rust treatment

With respect to Examples 10, 11, and 12, rust-preventing treatment (zinc chromate treatment) was carried out under the following conditions to form a rust-preventing treatment layer.

(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

With respect to Examples 11 and 12, a decane coupling agent coating treatment was carried out under the following conditions to form a decane coupling layer.

(liquid composition)

Alkoxydecane content 0.4%

pH 7.5

Coating method spray solution

(5) Formation of release layer

[Release layer A]

Using a spray coater, an aqueous solution of a decane compound (n-propyltrimethoxydecane: 4% by weight) was applied to the treated surface of the copper foil, and then the surface of the copper foil was dried in air at 100 ° C for 5 minutes to form a release layer A. After the decane compound was dissolved in water until the stirring time before coating was 30 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 3.8 to 4.2.

[release layer B]

Using sodium 1-dodecyl mercaptan sulfonate as a compound having 2 or less sulfhydryl groups in the molecule, an aqueous solution of sodium 1-dodecanethiol sulfonate (1-10) was coated on the treated surface of the copper foil using a spray coater. After the sodium dialkyl mercaptan sulfonate concentration: 3 wt%), it was dried in air at 100 ° C for 5 minutes to prepare a release layer B. The pH of the aqueous solution is set to 5-9.

[release layer C]

Using aluminum triisopropoxide as an aluminate compound as a metal alkoxide, an aqueous solution of aluminum triisopropoxide was applied to the treated surface of the copper foil using a spray coater (concentration of aluminum triisopropoxide: 0.04 mol/ After L), it was dried in air at 100 ° C for 5 minutes to prepare a release layer C. After the aluminate compound was dissolved in water until the stirring time before coating was 2 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5 to 9.

[release layer D]

Using n-decyl-triisopropoxytitanium as a titanate compound as a metal alkoxide, an aqueous solution of n-decyl-triisopropoxytitanium was coated on the treated surface of the copper foil using a spray coater (n-decyl group) After the concentration of titanium triisopropoxide: 0.01 mol/L, it was dried in air at 100 ° C for 5 minutes to prepare a release layer D. After the titanate compound was dissolved in water until the stirring time before the coating was 24 hours, the methanol concentration in the aqueous solution was 20 vol%, and the pH of the aqueous solution was 5 to 9.

[release layer E]

Using n-propyl-tri-n-butoxyzirconium as a zirconate compound as a metal alkoxide, an aqueous solution of n-propyl-tri-n-butoxyzirconium (n-propyl group) was applied to the treated surface of the copper foil using a spray coater. After the concentration of tri-n-butoxyzirconium: 0.04 mol/L, it was dried in air at 100 ° C for 5 minutes to produce a release layer E. After the titanate compound was dissolved in water until the stirring time before coating was 12 hours, the alcohol concentration in the aqueous solution was set to 0 vol%, and the pH of the aqueous solution was set to 5 to 9.

The release layers of Examples 19 to 54 and Comparative Examples 6 to 7 were subjected to decaneization. In the case of the compound, the release layer forming conditions not described in the following tables are the same as those of the release layer A. Further, in the case of using a mercapto compound, the release layer formation conditions not described in the following Table are the same as those of the release layer B. Further, in the case of using a metal alkoxide, the release layer forming conditions not described in the following table are the same as those of the release layer C.

(6) Resin layer formation treatment

Regarding Example 12, in the barrier treatment, the rustproof treatment, the decane coupling agent coating, and the release layer shape After the formation, the formation of the resin layer was further carried out under the following conditions.

(Resin Synthesis Example)

Add 3,4,3',4'- to a 2-liter three-necked flask equipped with a reflux condenser with a spherical condenser on a separator with a stainless steel anchor stir bar, nitrogen inlet pipe and end plug. Benzene tetracarboxylic dianhydride 117.68 g (400 mmol), 1,3-bis(3-aminophenoxy)benzene 87.7 g (300 mmol), γ-valerolactone 4.0 g (40 mmol), pyridine 4.8 g (60 mmol) ), 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were heated at 180 ° C for 1 hour, and then cooled to near room temperature, after which 3,4,3',4'-biphenyltetracarboxylate was added. Acid dianhydride 29.42 g (100 mmol), 2,2-bis{4-(4-aminophenoxy)phenyl}propane 82.12 g (200 mmol), NMP 200 g, toluene 40 g, mixed at room temperature for 1 hour After heating at 180 ° C for 3 hours, a block copolymerized polyimine of 38% of a solid content was obtained. The block copolymerized polyimine has the following general formula (1): general formula (2) = 3:2, number average molecular weight: 70,000, and weight average molecular weight: 150,000.

Further diluting the block copolymerized polyfluorene obtained in the synthesis example by using NMP The amine solution was made into a block copolymerized polyimine solution having a solid content of 10%. Solid matter A block copolymerized polyimine of bis(4-maleimidophenyl)methane (BMI-H, KI Chemical Industry) at a weight ratio of 35, and a solid component weight ratio of 65 (i.e., contained in a resin solution) Bis(4-maleimide phenyl)methane solids component weight: block copolymer copolymerized polyimine solid content component of resin solution = 35:65) dissolved at 60 ° C mixed in the block The resin solution was prepared by copolymerizing a polyimine solution. Thereafter, the resin solution was applied to the release layer forming surface of Example 12, dried in a nitrogen atmosphere at 120 ° C for 3 minutes, dried at 160 ° C for 3 minutes, and finally heated at 300 ° C for 2 minutes. The copper foil having a resin layer was produced by the treatment. Further, the thickness of the resin layer was set to 2 μm.

‧ Evaluation of surface roughness Rz of copper foil (raw foil) and surface treated copper foil

The ten-point average roughness Rz of the treated surface of the surface-treated copper foil was measured in accordance with JIS B0601 (1994) using a contact roughness meter SP-11 manufactured by Kosaka Research Institute Co., Ltd. The measurement position was changed 10 times, and the value in 10 measurements was obtained. Further, in the same manner, the surface roughness Rz of the copper foil (raw foil) before the surface treatment was also measured.

‧Manufacturing of copper clad laminates

One of the following resin base materials 1 to 3 is bonded to the surface of the treated side of each surface-treated copper foil.

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

Substrate 2: Hitachi Chemical Industry Co., Ltd. manufactures 679-FG

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

The temperature, pressure, and time of the build-up pressure are recommended by the manufacturer of each substrate.

‧ Evaluation of peel strength (peel strength)

The copper-clad laminate was measured by the tensile tester autostereograph 100 according to IPC-TM-650, and the normal peel strength when peeling the resin substrate from the copper foil was measured.

‧Evaluation of the rupture mode of the resin

The peeling surface of the resin substrate after peeling was observed with an electron microscope, and the cracking method (aggregation, interface, aggregation, and interfacial mixing) of the resin was observed. Regarding the cracking method of the resin, the "interface" indicates that peeling occurs at the interface between the copper foil and the resin, "aggregation" indicates that the peel strength is too strong, and the resin is broken, and "mixed presence" indicates that the "interface" and "aggregation" are mixed.

‧Wiring formation

With respect to the semi-additive method according to FIG. 1 , the resin substrate is subjected to electroless copper plating or electrolytic copper plating, and a copper plate having a copper layer thickness of 12 μm is laminated, and the copper plating layer is processed by etching. And form L (line) / S (space) = 30 μm / 30 μm circuit. At this time, the wiring formed on the resin substrate was observed with an optical microscope of 100 to 500 times, and the case where no circuit defect was present was set to OK (○), and the case where the circuit defect was present was set to NG (×).

The test conditions and evaluation results are shown in Tables 1 to 4.

As shown in Tables 1 to 4, in Examples 1 to 54, a specific release layer was provided, and the peel strength was suppressed, and the cracking mode of the resin was only the interface. Therefore, it can be said that physical peeling can be performed after bonding to a resin base material.

On the other hand, in Comparative Examples 1 to 7, the release layer was not provided, or the release layer was not formed because the compound to be used for forming the release layer was not suitable, and the peel strength was large, and the cracking mode of the resin was agglomeration. Any of a mixture of agglutination and interface. Therefore, it can be said that physical peeling cannot be performed after bonding to a resin base material.

Claims (30)

A surface-treated copper foil comprising: a copper foil which has no roughened particles and has a surface roughness of 0.1 to 5.0 μm according to JIS B0601 (1994); and a release layer, The release layer is provided on the surface of the copper foil having the surface unevenness, and the resin substrate when the resin substrate is bonded to the copper foil from the release layer side is peelable. The surface-treated copper foil according to the first aspect of the invention, wherein the resin substrate is bonded to the copper foil from the side of the release layer, and the peel strength at the time of peeling off the resin substrate is 200 gf/cm or less. The surface-treated copper foil according to the first aspect of the invention, wherein the mold release layer is obtained by using a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product, alone or in combination. (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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. Any of these hydrocarbon groups which are halogen atoms). The surface-treated copper foil according to the first aspect of the invention, wherein the release layer is a compound having two or less sulfhydryl groups in the molecule. The surface-treated copper foil according to the first aspect of the invention, wherein the release layer is an aluminate compound, a titanate compound, a zirconate compound, or a hydrolyzed product represented by the following formula, which is hydrolyzed. The condensate of the substance is used singly or in combination of two or more, (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 or a cycloalkane. a hydrocarbon group in the group consisting of a group and an aryl group, or any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom, and M is any one of Al, Ti, and Zr, and n is 0 or 1 or 2 m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group, and m+n is a valence of M, that is, 3 in the case of Al, and Ti. In the case of Zr, it is 4). A surface-treated copper foil comprising: a copper foil having roughened particles; and a release layer which is a release layer provided on a surface of the roughened particles of the copper foil, and is provided from the side of the release layer to the side The resin substrate described above when the copper foil is bonded to the resin substrate can be peeled off. The surface-treated copper foil according to the sixth aspect of the invention, wherein, when the resin substrate is bonded to the copper foil from the side of the release layer, the peel strength at the time of peeling off the resin substrate is 200 gf/cm or less. The surface-treated copper foil according to the sixth aspect of the invention, wherein the mold release layer is obtained by using a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product, alone or in combination. (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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. Any of these hydrocarbon groups which are halogen atoms). The surface-treated copper foil according to the second or seventh aspect of the invention, wherein the mold release layer is a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product, used alone or in combination. to make, (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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. Any of these hydrocarbon groups which are halogen atoms). The surface-treated copper foil according to claim 6, wherein the release layer is a compound having two or less sulfhydryl groups in the molecule. The surface treated copper foil of claim 2 or 7, wherein the release layer is A compound having two or less sulfhydryl groups in the molecule is used. The surface-treated copper foil according to the sixth aspect of the invention, wherein the release layer is an aluminate compound, a titanate compound, a zirconate compound, or a hydrolyzate produced by the following formula, and the hydrolysis is formed. The condensate of the substance is used singly or in combination of two or more, (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 or a cycloalkane. a hydrocarbon group in the group consisting of a group and an aryl group, or any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom, and M is any one of Al, Ti, and Zr, and n is 0 or 1 or 2 m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group, and m+n is a valence of M, that is, 3 in the case of Al, and Ti. In the case of Zr, it is 4). The surface-treated copper foil according to claim 2, wherein the release layer is an aluminate compound, a titanate compound, a zirconate compound, or the like, which is represented by the following formula, The condensate of the hydrolyzate is used singly or in combination of two or more, (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, a hydrocarbon group in a group consisting of a cycloalkyl group and an aryl group, or any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom, and M is any one of Al, Ti, and Zr, and n is 0 or 1 Or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ is an alkoxy group, and 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 copper foil according to any one of the preceding claims, wherein the copper foil and the release layer are provided with a heat-resistant layer, a rustproof layer, and a chromate. One or more layers of the group consisting of the treatment layer and the decane coupling treatment layer. The surface-treated copper foil according to any one of claims 1 to 8, 10, and 12, wherein a surface of the surface-treated copper foil is provided with a resin layer. The surface-treated copper foil according to claim 14, wherein a surface of the surface-treated copper foil is provided with a resin layer. The surface-treated copper foil according to claim 15, wherein the resin layer is a resin for bonding, a primer or a resin in a semi-hardened state. The surface-treated copper foil according to any one of claims 1 to 8, 10, and 12, wherein the surface-treated copper foil has a thickness of 9 to 70 μm. The surface-treated copper foil according to any one of claims 1 to 8, 10, and 12, which is applicable to a method for producing a printed wiring board, the method comprising the steps of: resin-based from the side of the release layer a step of bonding the material to the surface-treated copper foil; and peeling off the surface-treated copper foil from the resin substrate without etching, thereby obtaining a resin having a surface profile of the copper foil transferred on the peeling surface a step of forming a substrate; and a step of forming a circuit on the side of the peeling surface of the resin substrate to which the surface profile is transferred. A surface-treated copper foil comprising: a copper foil having a roughened particle and having a surface roughness of 0.1 to 5.0 μm according to JIS B0601 (1994); and a release layer The surface-treated copper foil which is provided on the surface of the copper foil having the surface unevenness and the release layer, and the resin substrate when the resin substrate is bonded to the copper foil from the release layer side is peelable; When the resin substrate is bonded to the copper foil from the mold release layer side to the above-mentioned (A) to (I), the peel strength at the time of peeling off the resin substrate is 200 gf. (B) The above-mentioned release layer is obtained by using a decane compound represented by the following formula, a hydrolyzate thereof, or a condensate of the hydrolyzate, either alone or in combination. (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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. (C) the above-mentioned release layer is a compound having two or less sulfhydryl groups in the molecule; (D) the above release layer is an aluminate represented by the following formula The compound, the titanate compound, the zirconate compound, the hydrolyzate, and the condensate of the hydrolyzate are used singly or in combination of two or more, (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 any one of which one or more hydrogen atoms are substituted with a halogen atom. a hydrocarbon group, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, and m is an integer of 1 or more and a valence of M or less, R ¹ is at least one alkoxy group, in addition, m + n is the valence of M, i.e., in the case of Al is 3, in the case of Ti, Zr is is 4); (E) In the above copper foil One or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer are disposed between the release layer; (F) a surface of the surface-treated copper foil (G) In the above (F), the resin layer is a resin for bonding, a primer or a resin in a semi-cured state; (H) the surface-treated copper foil has a thickness of 9 to 70 μm; (I) A method for producing a printed wiring board, the method comprising the steps of: bonding a resin substrate to the surface-treated copper foil from the side of the release layer; and etching the surface-treated copper foil without etching In the case of peeling off from the resin substrate, a step of transferring a resin substrate having a surface profile of the copper foil on the peeling surface; and forming a circuit on the peeling surface side of the resin substrate to which the surface profile is transferred is obtained A step of. A surface-treated copper foil comprising: a copper foil having roughened particles; and a release layer provided on a release layer of the roughened particle surface of the copper foil, and laterally from the release layer When the copper foil is bonded to the resin substrate, the resin substrate is peelable; the surface-treated copper foil satisfies any one of the following (A) to (I), and (A) laterally from the release layer When the copper foil is bonded to the resin substrate, the peeling strength when the resin substrate is peeled off is 200 gf/cm or less; and (B) the release layer is a decane compound represented by the following formula, and a hydrolyzed product thereof. The condensate of the hydrolysis product is used singly or in combination of two or more. (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; And any one of the hydrocarbon groups, wherein R ³ and R ⁴ are each independently a halogen atom or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are substituted. (C) the above-mentioned release layer is a compound having two or less sulfhydryl groups in the molecule; (D) the above release layer is an aluminate compound represented by the following formula And a titanate compound, a zirconate compound, the hydrolyzate, and a condensate of the hydrolyzate are used singly or in combination of two or more, (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 any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, and m is an integer of 1 or more and a valence of M or less, R ¹ is at least one alkoxy group, in addition, m + n is the valence of M, i.e., in the case of Al is 3, in the case of Ti, Zr is is 4); (E) In the above copper foil Between the above-mentioned release layer, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer; (F) a surface of the surface-treated copper foil (G) In the above (F), the resin layer is a resin for bonding, a primer or a resin in a semi-cured state; (H) the surface-treated copper foil has a thickness of 9 to 70 μm; (I) A method for producing a printed wiring board, the method comprising the steps of: bonding a resin substrate to the surface-treated copper foil from the side of the release layer; and etching the surface-treated copper foil without etching In the case of peeling from the resin substrate, a step of transferring a resin substrate having a surface profile of the copper foil on the release surface; and forming a circuit on the peeling surface side of the resin substrate having the surface profile transferred thereto A step of. A copper-clad laminate comprising: a surface-treated copper foil according to any one of claims 1 to 21; and a resin substrate provided on a side of the release layer of the surface-treated copper foil. The copper clad laminate according to claim 22, wherein the resin substrate is a prepreg or a thermosetting resin. A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 21. A printed wiring board manufactured by using the surface-treated copper foil according to any one of claims 1 to 21. A semiconductor package comprising the printed wiring board of claim 24 or 25. An electronic machine using the printed wiring board of claim 24 or the semiconductor package of claim 26 of the patent application. A method of producing a printed wiring board, comprising the steps of: bonding a resin substrate to the surface-treated copper foil according to any one of claims 1 to 21 from the side of the release layer; a step of peeling the surface-treated copper foil from the resin substrate without etching to obtain a resin substrate having a surface profile of the copper foil transferred on the peeling surface; and a resin having the surface profile transferred thereon The step of forming a circuit on the peeling surface side of the substrate. A printed wiring board manufactured by the method of claim 28 of the patent application. A resin substrate obtained by laminating a resin substrate from the side of the release layer to the surface-treated copper foil according to any one of claims 1 to 21, by not subjecting the surface-treated copper foil to In the case of etching, the resin substrate is peeled off from the resin substrate, and the surface profile of the copper foil is transferred onto the release surface.