TWI639515B - A metal foil with a carrier - Google Patents

Abstract

The present invention provides a resin-made plate-shaped carrier and an attached sub-metal foil whose peel strength is adjusted.

An attached sub-metal foil characterized by a plate-shaped carrier made of a resin and an attached sub-metal foil formed of a metal foil which is peelable and adhered to at least one surface of the carrier; and a plate shape The carrier and the metal foil are an aluminate compound, a titanate compound or a zirconate compound having a predetermined structure, a hydrolyzed product thereof, a condensate of the hydrolyzed product, and a combination of them alone or in combination. Put it together.

Description

Attached metal foil

The present invention relates to an attached sub-metal foil. More specifically, it relates to a single-layer or two-layer multilayer laminate used on a printed wiring board, or an attached sub-metal foil used for the manufacture of an extremely thin coreless substrate.

In general, a printed circuit board is a basic material called a "prepreg" obtained by immersing a base material such as a synthetic resin plate, a glass plate, a glass nonwoven fabric, or paper. On the opposite side of the prepreg, a sheet such as a copper or copper alloy foil having current conductivity is bonded. The laminate thus combined is generally referred to as a CCL (Copper Clad Laminate) material. Usually, in order to enhance the joint strength, the copper foil surface bonded to the prepreg is used as a mat surface. As a substitute for copper or copper alloy foil, aluminum foil, nickel foil or zinc foil may be used. The thickness of these metal foils is usually about 5 to 200 μm. Such a commonly used CCL (Copper Clad Laminate) material is shown in FIG.

Patent Document 1 provides an attached sub-metal foil characterized in that it is a plate-shaped carrier made of synthetic resin, and a metal foil which can be mechanically peeled off and adhered to at least one surface of the carrier. The sub-metal foil is attached, and the attached sub-metal foil is a combination of printed wiring boards. This patent also discloses that the peeling strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. By using the attached sub-metal foil, the synthetic resin is supported entirely across the copper foil, and the occurrence of wrinkles of the copper foil in the laminate can be prevented. And such a carrier metal foil, Since the metal foil and the synthetic resin are seamlessly adhered to each other, when the surface of the metal foil is plated with gold or etched, it can be put into a gold plating or etching liquid. Further, since the coefficient of linear expansion of the synthetic resin is equivalent to the copper foil of the constituent material of the substrate and the prepreg after the superposition of the substrate, the positional deviation of the circuit is not caused, and the occurrence of defective products is lowered, and the occurrence of defective products can be made. Excellent effect of increasing yield.

[Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-196207

The attached sub-metal foil described in Patent Document 1 is an epoch-making invention that simplifies the manufacturing process of a printed circuit board and contributes to cost reduction due to an increase in yield, but relates to a plate-shaped carrier and a metal foil. The optimization of the peel strength and its means still leave room for review. In particular, a problem that is significant to the inventors is that the peel strength of the plate-shaped carrier and the metal foil is excessively increased with the material of the plate-shaped carrier, and an ideal system can provide an easy adjustment of the peeling. The means of strength. Therefore, in the present invention, an object of the present invention is to provide a carrier-supported metal foil having a peeling strength of a plate-shaped carrier and a metal foil.

The inventors focused on adjusting the peel strength between the resin sheet and the metal foil As a result of the research, it was found that the resin plate and the metal foil were coated on at least one surface with an aluminate compound, a titanate compound or a chromate compound having a specific structure. The present invention has been completed in accordance with the peel strength of the intended use.

That is, the present invention is as follows.

(1) An attached sub-metal foil characterized by a plate-shaped carrier made of a resin and an attached sub-metal foil formed of a metal foil which is peelable and adhered to at least one surface of the carrier; And the plate-shaped carrier and the metal foil are of the following formula: [Chemical Formula 1] (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is an alkoxy group or a halogen atom; R ² is selected a hydrocarbon group grouped from an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; any one of M systems of Al, Ti or Zr; 0 or 1 or 2, m is an integer below 1 valence of M, 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, Ti, Zr The aluminate compound, the titanate compound or the zirconate compound shown in 4), the hydrolyzed product thereof, and the condensate of the hydrolyzed product are used alone or in combination. By.

(2) The sub-metal foil according to (1), wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less.

(3) The sub-metal foil according to (1) or (2), wherein the resin-made plate-shaped carrier comprises Thermosetting resin.

(4) The attached sub-metal foil according to any one of (1) to (3), wherein the resin-made plate-shaped carrier is a prepreg.

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

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

(7) The attached sub-metal foil according to any one of (1) to (6), wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0. Below μ m.

(8) The attached sub-metal foil according to any one of (1) to (7), wherein the thickness of the metal foil is 1 μm or more and 400 μm or less.

(9) The attached sub-metal foil according to any one of (1) to (8), wherein the stripping of the metal foil and the plate-shaped carrier after at least one of heating processes at 220 ° C for 3 hours, 6 hours or 9 hours The strength is 10 gf/cm or more and 200 gf/cm or less.

(10) The attached sub-metal foil according to any one of (1) to (9), wherein the metal foil is a copper foil.

(11) A metal foil for a printed wiring board, wherein the surface of the metal foils thereon, the system having the formula: [Chemical Formula 2] _{^{(R 1) m -M- (R}} 2) n ( formula, R ¹ is Alkoxy or a halogen atom; R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; Any of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, the price of m+n is M The number, that is, the aluminum salt in the case of Al, the aluminum compound, the titanate compound or the zirconate compound represented by 4) in the case of Ti and Zr, and the hydrolyzed product thereof and the condensate of the hydrolyzed product. , in separate or plural combinations.

(12) The metal foil for a printed wiring board according to (11), wherein the hydrous product is hydrolyzed by an aluminate compound, a titanate compound or a zirconate compound of the metal foil, and the like. The condensate is subjected to a chromate treatment before the action of the compound with respect to the surface on the side on which the combination is applied singly or in combination.

(13) The metal foil for a printed wiring board according to (11) or (12), wherein a surface having a side joined to a carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(14) The metal foil for a printed wiring board according to any one of (11) to (13), wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm. Above 10.0 μ m.

(15) A metal foil for a printed wiring board according to any one of (11) to (14), wherein the metal foil is a copper foil.

(16) A metal foil characterized by being at least one side having the following formula: [Chemical Formula 3] (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 or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system is Al, Ti or Any one of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m + n is a valence of M, that is, In the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), a hydrolyzed product thereof, and the condensate of the hydrolyzed product, either alone or A metal foil of a plurality of combinations; and it can be used for a user who peels and seals a resin-made plate-shaped carrier on the surface.

(17) The metal foil according to (16), wherein the metallohydrate compound, the titanate compound or the zirconate compound of the metal foil, the hydrolyzed product thereof, and the condensate of the hydrolyzed product are The surface treated with the chromate is applied to the surface of the active side in combination with it alone or in combination.

(18) The metal foil according to (16) or (17), wherein the surface on the side joined to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(19) A resin-made plate-shaped carrier characterized by having at least one surface having the following formula: [Chemical Formula 4] (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 or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; Is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m+n is M The number of valences, that is, an aluminate compound, a titanate compound, or a zirconate compound represented by 4) in the case of Al and Ti in the case of Al, and a hydrolyzed product, etc., and condensation of the hydrolyzed product Body, in separate or plural combinations.

(20) A plate-shaped carrier characterized by being on at least one surface having a formula: [Chem. 5] (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 or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; Is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m+n is M The number of valences, that is, an aluminate compound, a titanate compound, or a zirconate compound represented by 4) in the case of Al and Ti in the case of Al, and a hydrolyzed product, etc., and condensation of the hydrolyzed product The body is a plate-shaped carrier made of resin alone or in combination; and it can be used for a user who peels off and adheres the metal foil on the surface.

(21) A method of producing a multilayer metal laminated laminate, characterized in that it comprises: a resin foil side with respect to at least one side of an attached sub-metal foil of any one of (1) to (10) The layers are laminated, and then the resin or metal foil is repeated one or more times for lamination.

(22) A method for producing a multilayer metal laminated laminate, comprising: laminating a resin on a side of a metal foil of any one of (1) to (10); and then The resin, the single-sided or double-sided metal laminate, or the attached sub-metal foil or any of the metal foils (1) to (10) may be laminated one or more times.

(23) A method for producing a multilayer metal laminate, characterized in that in the method for producing a multilayer metal laminate of (21) or (22), the plate-shaped carrier of the attached metal foil is further included The step of peeling and separating the metal foil.

(24) A method of producing a multilayered metal laminate, characterized in that the method of (23) comprises the step of removing one or all of the metal foil which has been peeled off and separated by etching.

(25) A multilayer metal laminate, which is characterized by being produced by any one of (21) to (24).

(26) A method of producing a composite substrate, comprising the step of forming one or more combined wiring layers on the metal foil side of the attached sub-metal foil of any one of (1) to (10).

(27) A method of producing a composite substrate according to (26), characterized in that the combined wiring layer is formed by using at least one of a subtractive method, a full additive method, or a semi-additive method.

(28) A method for producing a composite substrate, comprising: laminating a resin on at least one side of a metal foil of any one of (1) to (10); and then The resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal laminate, and the attached sub-metal foil or metal foil of any of (1) to (10) are laminated one or more times.

(29) A method of producing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate according to (28), a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminated laminate, and an attached The metal foil of the sub-metal foil, the plate-shaped carrier on which the sub-metal foil is attached, the metal foil or the resin is drilled, and the step of conducting electroplating is performed on the side surface or the bottom surface of the hole.

(30) A method of producing a composite substrate, characterized by further comprising: in the method for producing a composite substrate of (28) or (29), forming a metal foil of a single-sided or double-sided wiring substrate, forming a single side The step of forming one or more wirings on at least one of the metal foil of the double-sided metal laminate, the metal foil constituting the attached sub-metal foil, and the metal foil.

(31) The method for producing a composite substrate according to any one of (28) to (30), further comprising: (1) to (10) in which a metal foil is adhered to one surface on a surface formed by the wiring The side of the resin sheet on which the sub-metal foil is attached, in contact with it, and the step of laminating.

(32) The method for producing a composite substrate according to any one of (28) to (30), further comprising laminating the resin on the surface formed by the wiring, and using the metal foil on both sides of the resin One of the metal foils attached to the sub-metal foil of any one of (1) to (10) is brought into contact and laminated.

(33) A method of producing a composite substrate according to any one of (28) to (32), wherein at least one of the resins is a prepreg.

(34) A method for producing a composite wiring board, characterized in that, in the method for producing a composite substrate according to any one of (26) to (33), further comprising: carrying a plate-shaped carrier carrying a sub-metal foil and a metal foil The step of stripping and separating.

(35) A method of manufacturing a composite wiring board, characterized in that in the method of manufacturing a combined wiring board of (34), one or all of the metal foil adhered to the plate-shaped carrier is etched To remove the steps.

(36) A composite wiring board characterized by the production method of (34) or (35).

(37) A method of producing a printed circuit board, comprising the step of manufacturing a composite substrate by the method of any one of (26) to (33).

(38) A method of manufacturing a printed circuit board, comprising the step of manufacturing a combined wiring board by the manufacturing method of (34) or (35).

According to the present invention, the peel strength of the plate-shaped carrier and the metal foil can be easily adjusted. Therefore, for example, the attached sub-metal foil which has been conventionally exhibiting an excessively high peel strength can be adjusted to a preferable peel strength, whereby a printed wiring board using an attached sub-metal foil can be obtained, and the productivity is improved.

10‧‧‧Laminating mould

11‧‧‧With sub-metal foil

11a‧‧‧metal foil

11b‧‧‧Metal alkoxide

11c‧‧‧ plate-shaped carrier

12‧‧‧Prepreg

13‧‧‧ Inner core board

Page 14‧‧‧

15‧‧‧ben

16‧‧‧ combination layer

[Fig. 1] A diagram showing a configuration example of CCL

Fig. 2 is a view showing a configuration example of the attached sub-metal foil of the present invention.

Fig. 3 is a view showing an example of a combination of multilayer CCLs which are related to the sub-metal foil of the present invention (in the form of single-sided bonding of a resin sheet).

Fig. 4 is a view showing an example of a combination of multilayer CCLs which are related to the sub-metal foil of the present invention (in the form of double-sided bonding of a resin sheet).

In an embodiment of the attached sub-metal of the present invention, the resin-made plate-shaped carrier and one or both sides of the carrier are preferably formed on both sides to be peelable and adhered to the metal foil. Attached to the metal foil. A configuration example relating to the attached sub-metal foil of the present invention is shown in Figs. 2 and 3. In particular, at the beginning of Fig. 3, the attached sub-metal foil 11 is illustrated, in which the peelable metal foil 11a is adhered to both sides of the resin-made plate-shaped carrier 11c. Between the plate-shaped carrier 11c and the metal foil 11a, an aluminate compound having a specific structure described later, a zirconate compound, a zirconate compound, or the like, and a hydrolyzed product are used, and the condensation product is hydrolyzed. The body (hereinafter abbreviated as "metal alkoxide") 11b is attached.

Although the structure is similar to the CCL shown in Fig. 1, the attached sub-metal foil of the present invention has a structure which is easily peeled off because the metal foil and the resin are finally separated. At this point, because CCL is not a product to be stripped, it is completely different in structure and function.

The attached sub-metal foil used in the present invention must be peeled off at the end, and is not suitable for excessively improving the adhesion, and in the plate-shaped carrier and the metal foil, the metal plating performed in the process of manufacturing the printed circuit board, etc. In the chemical treatment project, it must be not peeled off, but it has a certain degree of adhesion.

In order to achieve the peel strength with such adhesion, a metal alkoxy group (aluminate compound, a titanate compound, a zirconate compound or such a hydrolyzed product) having the following specific configuration is used. Or the condensate of the hydrolyzed product substance) alone or in combination. Such a metal alkoxide is bonded between the plate-shaped carrier and the metal foil, and the adhesion is appropriately lowered, and the peel strength can be adjusted to the above range.

[6] (R ¹ ) _m -M-(R ² ) _n

Wherein R ¹ is an alkoxy group or a halogen atom; and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; The valence of +n is M, which is 3 for Al and 4 for Ti and Zr.

The metal alkoxide must have at least one alkoxy group. In the absence of an alkoxy group, a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a case where one or more hydrogen atoms thereof are substituted with a halogen atom and only one of these hydrocarbon groups constitutes a substituent The adhesion of the plate-shaped carrier to the surface of the metal foil tends to be excessively low. Further, the metal alkoxide must be one of 0 to 2, 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 thereof may be substituted with a halogen atom. Hydrocarbyl group. When the hydrocarbon group has three or more such hydrocarbon groups, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to be excessively lowered. Further, the alkoxy group related to the present invention also contains a case where one or more alkoxy groups in which a hydrogen atom is substituted with a halogen atom. When the peeling strength of the plate-shaped carrier and the metal foil is adjusted to the above range, the metal alkoxide has two or more alkoxy groups and has one or two of the above hydrocarbon groups (including one or more hydrogen atoms substituted with a halogen atom) The hydrocarbon group is preferred.

Further, the alkyl group is not limited, but may, for example, be a methyl group, an ethyl group, an n- or iso-propyl group, an n-, iso- or tert-butyl group, an n-, iso- or neo-pentane group. a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, preferably an n-hexyl group, an n-octyl group or an n-fluorenyl group. Carbon number 1~5 Alkyl.

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

Further, examples of the aromatic hydrocarbon group suitable for R ² include a phenyl group, a phenyl group substituted with an alkyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, a fluorenyl group or the like. The aryl group of 6 to 20 is preferably an aryl group having 6 to 14 carbon atoms, and the hydrocarbon group may be either or both of a hydrocarbon group and an amine group.

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

Preferred aluminate compounds are, for example, trimethyl aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or iso-propyl dimethoxy aluminum, n-, iso- Or tert-butyldimethoxyaluminum, n-, iso- or neo-pentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, Phenyldimethoxyaluminum; alkyl-substituted phenyldimethoxyaluminum (eg, p-(methyl)phenyldimethoxyaluminum), dimethylmethoxyaluminum, triethoxyaluminum, Methyldiethoxyaluminum, ethyldiethoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxylate Base aluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg: p-( Methyl)phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso- Propyldiethoxyaluminum, n-, iso- or tert-butylbisisopropoxyaluminum, pentyldiisopropoxyaluminum, hexyldiisopropoxyaluminum, octyldiiso Aluminum propoxide, aluminum decyl diisopropoxide, aluminum phenyl diisopropoxide, aluminum substituted alkyl phenyl diisopropoxide (eg p-(methyl)phenyl diisopropoxy) Aluminum), dimethyl isopropoxide aluminum, (3,3,3-trifluoropropyl)dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methylaluminum dichloride, two Methyl aluminum chloride, dimethyl aluminum chloride, phenyl aluminum dichloride, dimethyl aluminum fluoride, dimethyl aluminum bromide, diphenyl aluminum bromide, such hydrolyzed products, and The condensate of the hydrolyzed product and the like are exemplified, and among them, trimethoxy aluminum, triethoxy aluminum, and aluminum triisopropoxide are more preferable from the viewpoint of availability.

Preferred titanate compounds include, for example, tetramethoxytitanium and methyltrimethoxy. Titanium, ethyltrimethoxytitanium, n- or iso-propyltrimethoxytitanium, n-, iso- or tert-butyltrimethoxytitanium, n-, iso- or neo-pentyltrimethoxytitanium , hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium, alkyl-substituted phenyltrimethoxytitanium (eg, p-(methyl)phenyltrimethoxy) Titanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, n- or iso-propyltriethoxytitanium, n- , iso- or tert-butyl triethoxy titanium, pentyl triethoxy titanium, hexyl triethoxy titanium, octyl triethoxy titanium, decyl triethoxy titanium, phenyl triethoxy Titanium, alkyl substituted phenyl triethoxy titanium (such as: p-(methyl)phenyl triethoxy titanium), dimethyldiethoxy titanium, tetraisopropoxy titanium, methyl three Titanium isopropoxide, titanium triisopropoxide, titanium n- or iso-propyltriethoxy, n-, iso- or tert-butyl triisopropoxide, pentyl triisopropyl Titanium oxide, titanium hexyl triisopropoxide, titanium octyl triisopropoxide, titanium decyl triisopropoxide, titanium phenyl triisopropoxide, alkyl Phenyl phenyl triisopropoxide (eg p-(methyl)phenyl triisopropoxy titanium), dimethyl diisopropoxy titanium, (3,3,3-trifluoropropyl) Trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, A Base of titanium trichloride, dimethyl titanium dichloride, trimethyl titanium chloride, phenyl titanium trichloride, titanium dimethyl difluoride, titanium dimethyl dibromide, diphenyl dibromination Examples of titanium, such a hydrolyzed product, and a condensate of such a hydrolyzed product; among them, tetramethoxytitanium, tetraethoxytitanium, and tetraiso are preferable from the viewpoint of availability. Titanium propoxide is preferred.

Preferred zirconate compounds are exemplified by tetramethoxy zirconium and methyl trimethoxy group. Zirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium, n-, iso- or neo-pentyltrimethoxyzirconium , hexyltrimethoxy zirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl-substituted phenyltrimethoxyzirconium (eg, p-(methyl)phenyltrimethoxy) Chromium), dimethyl dimethoxy zirconium, tetraethoxy zirconium, methyl triethoxy zirconium, ethyl triethoxy zirconium, n- or iso-propyl triethoxy zirconium, n- , iso- or tert-butyltriethoxy zirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium,phenyltriethoxy Zirconium, alkyl substituted phenyl triethoxy zirconium (eg p-(methyl)phenyltriethoxy zirconium), dimethyldiethoxy zirconium, tetraisopropoxy zirconium, methyl three Zirconium isopropoxide, zirconium ethyl triisopropoxide, zirconium n- or iso-propyltriethoxylate, zirconium n-, iso- or tert-butyl triisopropoxy, pentyl triisopropyl Oxy zirconium, zirconium triisopropoxy zirconium, octyl triisopropoxy zirconium, decyl triisopropoxy zirconium, phenyl triisopropoxy zirconium, alkyl Phenyl phenyl triisopropoxy zirconium (eg p-(methyl)phenyl triisopropoxy zirconium), zirconium dimethyl diisopropoxide, (3,3,3-trifluoropropyl) Trimethoxy zirconium, and trifluorooctyloctyltriethoxy zirconium, methyltrichlorozirconium dichloride, dimethyl zirconium dichloride, trimethyl zirconium chloride, phenyl zirconium trichloride, dimethyl di Examples of zirconium fluoride, zirconium dimethyl zirconium dichloride, zirconium diphenyl zirconium dichloride, hydrolyzed products of these, and condensates of such hydrolyzed products are exemplified; Point of view It is preferable to use tetramethoxy zirconium, tetraethoxy zirconium or tetraisopropoxy zirconium.

It is possible to mount a sub-metal foil with a hot press to adhere a plate-shaped carrier and a metal foil.

For example, the bonding surface of the metal foil and/or the plate-shaped carrier is coated with the aforementioned metal alkoxide.

After that, the surface to which the metal foil is bonded is laminated by a hot press using a B-stage resin-shaped plate-shaped carrier, which is a possible manufacturing method.

The metal alkoxide can be used in the form of an aqueous solution. An alcohol solvent such as methanol or ethanol may be added to increase the solubility in water. The addition of an alcohol solvent is particularly effective when a highly hydrophobic metal alkoxide is used.

When the concentration of the metal alkoxide in the aqueous solution is high, the peel strength of the metal foil and the plate-shaped carrier tends to decrease, and the peel strength can be adjusted by adjusting the concentration of the metal alkoxide. Although not limited, the concentration of the metal alkoxide in the aqueous solution can be adjusted to 0.001 to 1.0 mol/L, which can be conventionally adjusted to 0.005 to 0.2 mol/L.

The pH of the aqueous solution of the metal alkoxide is not particularly limited, and both acidic and basic can be utilized. For example, a pH range of 3.0 to 10.0 can also be used. The pH value in the range of 5.0 to 9.0 near neutral is preferable, and the pH falling in the range of 7.0 to 9.0 is more preferable from the viewpoint of not particularly adjusting the pH range.

From the viewpoint of easy adjustment of the peel strength by the metal alkoxide, the peeling strength of the metal foil and the plate-shaped carrier is preferably 10 gf/cm or more, more preferably 30 gf/cm or more, and 50 gf/cm is optimal. On the other hand, it is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, and most preferably 80 gf/cm or less. By controlling the peel strength of the metal foil and the plate-shaped carrier within this range, it is not peeled off during handling or processing. It is also easy to peel off manually, that is, the peel strength that can be mechanically peeled off, and the adjustment will be easier.

In addition, in the manufacturing process of the multilayer printed wiring board, in the lamination step or degumming There are many heat treatment steps in the steps. Therefore, the heat history of the attached sub-metal foil will become more severe as the number of laminations increases. For this reason, in particular, in the application consideration of the multilayer printed wiring board, after the required heat treatment process, the peeling strength of the metal foil and the plate-shaped carrier is still within the above range.

To this end, in a more preferred embodiment of the invention, the multi-layer printing is preset. The heating condition in the manufacturing process of the wiring board, for example, after at least one heating process of 3 hours, 6 hours or 9 hours at 220 ° C, the peeling strength of the metal foil and the plate-shaped carrier is preferably 30 gf/cm or more. More preferably, 50 gf/cm or more. Further, the peel strength is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, and most preferably 80 gf/cm or less.

About the peel strength after heating at 220 ° C, from the ability to correspond to various types of lamination From the point of view of the number, after 3 hours and 6 hours, or after 6 hours and 9 hours, the peel strength is preferably in the range of 3 hours, 6 hours, and The peeling range of the entire procedure after 9 hours is better than the above range.

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

Hereinafter, specific constitutional requirements for each material for achieving the peel strength will be explained.

The resin used as the plate-shaped carrier is not particularly limited, but a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a rosin or the like can be used, but a thermosetting resin is preferred. In addition, prepreg sheets can also be used. The prepreg before bonding with the metal foil can be in the B-stage state. The coefficient of linear expansion of the prepreg (C stage) is 12 to 18 (×10 ^-6 /°C), 16.5 (×10 ^-6 /°C) of the copper foil as the constituent material of the substrate, or 17.3 of the SUS platen. ×10 ^-6 /°C) is almost equal, so the offset between the substrate size before and after pressurization and the position difference of the design (scale change) is difficult to occur. Furthermore, with the additive effect of these advantages, the production of a multi-layered ultra-thin coreless substrate is also possible. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board. Conventionally, a metal plate is used as a plate-shaped carrier for attaching a sub-metal foil; in this case, the plate-shaped carrier and the metal foil are adhered by fusion or subsequent bonding. In the case of using an adhesive, from the viewpoint of heat resistance, it is generally unsuitable for use in a combination, and in the case where it is adhered by welding, if the peeling strength is excessively high by using a full-welding method, In the latter stage, the step of easy manual peeling will become difficult. If partial welding is used, it will make it difficult to prevent the penetration of the liquid between the plate-shaped carrier and the metal foil. No matter in any direction, the combination step is not one. The right way. Then, by using a plate-shaped carrier made of a resin, it is possible to exhibit an appropriate peeling strength with the metal foil, and it is possible to sufficiently withstand the heat history at the time of the combination step by using the heat-resistant resin.

Therefore, if the plate-shaped carrier has a high glass transition temperature Tg, it is preferable to maintain the peel strength after heating in an optimum range, for example, 120 to 320 ° C, preferably Glass transition temperature Tg of 170~240 °C. Further, the glass transition temperature Tg is measured by DSC (differential scanning calorimetry).

Further, the coefficient of thermal expansion of the resin is preferably +10% or less than -30% of the thermal expansion coefficient of the metal foil. Thereby, the circuit caused by the difference in thermal expansion between the metal foil and the resin The positional shift can prevent the occurrence of defective products and increase the yield.

The thickness of the plate-shaped carrier is not particularly limited, and may be either hard or flexible. However, if the thickness is too thick, the heat distribution during hot pressing may have an adverse effect. On the other hand, if the thickness is too thin, the bending may cause the printed wiring board. Since the manufacturing process cannot be performed, it is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

As the material of the metal foil, it is represented by copper or a copper alloy foil, but materials such as aluminum foil, nickel foil, and zinc foil may also be used. In the case of using a copper or copper alloy foil, an electrolytic foil or a rolled foil can be used. The metal foil is not limited, and the wiring used as the printed circuit board is generally 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less. In the case where the metal foil is bonded to both sides of the plate-shaped carrier, a metal foil having the same thickness may be used, or a metal foil having a different thickness may be used.

Various surface treatments can be carried out on the metal foil used. Can be listed as: Metal plating for the purpose of heat resistance (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni alloy plating, etc.) Chromate treatment (including one or more alloying elements containing Zn, P, Ni, Mo, Zr, Ti, etc. in the chromate treatment liquid) to impart rust prevention or discoloration resistance, to roughen the surface roughness Treatment (Example: copper electro-graining or Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu-As alloy plating, The roughening effect obtained by copper alloy plating such as Cu-As-W alloy plating). Of course, the roughening treatment will have an effect on the peel strength of the metal foil and the plate-shaped carrier, and the chromate treatment also has a significant influence. Although chromate treatment to prevent rust and discoloration From the viewpoint of the nature, it is an important factor. However, since it is observed that the peel strength is remarkably increased significantly, it is also useful as a means for adjusting the peel strength.

Traditionally, CCL, the higher the peel strength of resin and copper foil, the more ideal, for example For example, the surface of the electrodeposited copper foil (M surface) is used as a bonding surface with the resin, and the surface treatment such as roughening treatment is performed to transmit the adhesion force by physical and chemical anchoring effects. achieve. Further, in terms of the resin side, in order to improve the adhesion to the metal foil, various adhesives are added in the same manner. As described above, in the present invention, the CCL is a dissimilar product, and the metal foil and the resin are necessary to be peeled off at the end, and the peel strength is excessively increased.

Here, in a preferred embodiment of the attached sub-metal foil of the present invention, in order to adjust the peeling strength of the metal foil and the plate-shaped carrier to the above-mentioned preferred range, the surface roughness of the bonding surface is determined. When JIS B 0601:2001 is used to measure the ten-point average roughness (Rz jis) of the surface of the metal foil, it is preferably 3.5 μm or less, and further preferably 3.0 μm or less. However, the reduction of the surface roughness-consuming process without limitation will be the reason for the increase in cost, so it is preferably 0.1 μm or more, more preferably 0.3 μm or more. When an electrolytic copper foil is used as the metal foil, any surface of the glossy surface (shiny surface, S surface) and rough surface (mat surface, M surface) can be used if these surface roughness adjustments are used, but use It is easier to adjust to the above surface roughness when the S surface is used. On the other hand, the average ten-point roughness (Rz jis) of the surface on the side where the carrier does not contact the metal foil is preferably 0.4 μm or more and 10.0 μm or less.

Further, another preferred embodiment of the attached sub-metal foil associated with the present invention The surface to which the resin of the metal foil is bonded is not subjected to a surface treatment for improving the peel strength, such as a roughening treatment. Further, in another preferred embodiment of the attached sub-metal foil related to the present invention, It is contained in the resin, and is not added as an adhesive for improving the adhesion to the metal foil.

As a condition for producing hot pressing of the attached sub-metal foil, as in the case of using a prepreg as a plate-shaped carrier, it is a pressure of 30 to 40 kg/cm ² and a temperature higher than a glass transition temperature of the prepreg. It is preferred to carry out the hot pressing process.

From the above point of view, the present invention provides a metal foil for making a resin The plate-shaped carrier may be peeled off and adhered, and the close contact surface is a metal foil treated with the above metal alkoxide coating on the surface of at least one of the metal foils. Further, the surface of the metal foil may be subjected to a step such as chromate treatment as described above before the metal alkoxide coating.

From another point of view, the present invention provides a plate-like carrier as a metal The surface of at least one of the plate-shaped carriers on which the foil is adhered has the above-mentioned metal alkoxide. This plate-shaped carrier can be suitably used for the purpose of peeling off the metal foil as described above.

From another point of view, the present invention provides a coreless multilayer printed wiring board A metal foil is used which is coated on the surface of the above metal foil with the above metal alkoxide. Further, the surface of the metal foil may be subjected to a step such as chromate treatment as described above before being covered with a metal alkoxide.

Moreover, the surface of the metal foil or resin is provided with XPS (X-ray photoelectron spectroscopy) Instrument, EPMA (Electronic Micro-Detector), EDX (X-ray Energy Dispersion Analyzer) electronic scanning microscope instrument to measure, if Al, Ti, Zr can be detected, it can be inferred that there is such a surface on the metal foil or resin The above metal alkoxide.

Furthermore, from another point of view, the present invention provides a carrier metal as described above. The use of foil.

First, a method for manufacturing a multilayer metal laminate is provided, comprising The side of the metal foil on which the carrier metal foil is attached is laminated with a resin, and then laminated with a resin or a metal foil once or more, for example, 1 to 10 times of reverse lamination.

Secondly, a method for manufacturing a multilayer metal laminate layer is provided, which is included in the above The metal foil side of the attached sub-metal foil is laminated with a resin, and then the resin, the single-sided or double-sided metal laminate, or the attached sub-metal foil or the metal foil of the present invention is laminated one or more times, for example 1~10 times of repeated lamination steps. Further, the lamination after the initial deposition of the sub-metal foil with the resin is carried out only in the desired number of laminations, and the resin, the single-sided or double-sided metal laminate, and the first attached sub-metal foil are used in each number of lamination times. It is arbitrarily selected and used in combination with other attached sub-metal foils of the present invention and metal foils.

In the above method for manufacturing a multilayer metal laminate, the above may further comprise The step of peeling and separating the plate-shaped carrier and the metal foil of the sub-metal foil are attached.

Furthermore, the method further comprises separating and separating the plate-shaped carrier from the metal foil, and then The step of removing one or all of the metal foil by etching.

Thirdly, a method for manufacturing a combined substrate is provided, which is included in the above-mentioned attached gold The metal foil side of the foil is laminated with a resin, and then the resin, the single-sided or double-sided wiring substrate, the single-sided or double-sided metal laminated layer, or the attached sub-metal foil or the metal foil of the present invention is used once or more. For example, 1 to 10 times of overlapping laminate steps. Further, the lamination after the initial lamination of the sub-metal foil with the resin is performed only in the number of times of lamination desired, and the resin, the single-sided or double-sided wiring substrate, the one-sided or double-sided metal laminated layer, with each number of lamination times The plate, the initial attached sub-metal foil, and other groups of the attached sub-metal foil of the present invention, and the metal foil are arbitrarily selected and used.

Fourthly, there is provided a method for producing a composite substrate comprising the step of laminating one or more laminated wiring layers on the side of the metal foil of the attached sub-metal foil. At this time, the combined wiring layer can It is formed by at least one of a subtractive method or a full additive method or a semi-additive method.

Regarding the subtractive method, it refers to a metal laminate or a wiring board (including printing) A method of forming a conductor pattern by selectively removing an unnecessary portion of a metal foil on a wiring board, a printed circuit board, or the like by etching or the like. Regarding the full addition method, which is a method of forming a conductor pattern by electroless plating or/and electrolytic plating without using a metal foil on a conductor layer, a semi-additive method such as a seed layer formed of a metal foil After the electroless metal precipitation, electrolytic plating, etching, or both, the conductor pattern is formed, the unnecessary inoculation layer is removed by etching, thereby obtaining a conductor pattern.

In the above method for manufacturing a combined substrate, it may be included in one or both sides. Wire substrate, single-sided or double-sided metal laminate, metal foil with sub-metal foil, plate-shaped carrier with metal foil, metal foil, or resin drilled, conductive plating step on the side and bottom of the hole . Or the metal foil constituting the single-sided or double-sided wiring substrate may be formed on at least one of a metal foil constituting a single-sided or double-sided metal laminate layer and a metal foil constituting the attached sub-metal foil. Steps are performed more than once.

In the above method of manufacturing a combined substrate, the wiring layer may be further included therein. On the surface, the metal foil is adhered to one side, and the carrier side of the attached metal foil of the present invention is laminated. Further, the method further includes the step of laminating the resin on the surface of the wiring, laminating the resin, and laminating the resin with the attached sub-metal foil of the present invention which is adhered to the metal foil on both sides.

Moreover, the term "surface formed by wiring" means that when the combination step is performed, Each time it appears on the surface to form a portion of the wiring, which also includes the combined substrate as the final product, which is in the middle of being formed.

In the above method for manufacturing a combined substrate, the aforementioned auxiliary gold may be further included The step of peeling off and separating the plate-shaped carrier of the foil from the metal foil.

Furthermore, the plate-shaped carrier and the metal foil described above may be further stripped and separated. Thereafter, the step of removing one or all of the metal foil by etching is performed.

Moreover, the method for manufacturing the above-mentioned multilayer metal laminated layer and the system for fabricating the combined substrate In the production method, the layers can be laminated by thermocompression bonding to each other. The thermocompression bonding can be carried out after laminating one layer at a time, or after laminating to a certain extent, or laminating to the end and then uniformly.

In particular, the present invention provides a method of manufacturing a combined substrate, wherein In the method for manufacturing a composite substrate, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminate, a metal foil or a resin is drilled, and conductive plating is performed on the side surface and the bottom surface of the hole, and then The metal foil and the circuit portion constituting the single-sided or double-sided wiring substrate, the metal foil constituting the single-sided or double-sided metal laminate, and the metal foil are subjected to at least one circuit formation.

Hereinafter, as a specific example of the above use, the use and the attachment of the present invention will be described. A method of preparing a 4-layer CCL of a sub-metal foil. The attached sub-metal foil used here is an auxiliary sub-metal foil 11 which is adhered to the metal foil 11a on one side of the plate-shaped carrier 11c. The sub-metal foil 11 is attached thereto with a desired number of prepregs 12, followed by a 2-layer printed circuit board or a 2-layer metal laminate which is referred to as an inner core sheet 13, followed by a prepreg 12 Then, in the order in which the sub-metal foils 11 are attached, the combined units of one set of four-layer CCLs are completed. Next, this unit 14 (generally referred to as "page") is repeated ten times to form a pressurized composition 15 (generally referred to as "this") (Fig. 3). Thereafter, the present 15 is placed in a hot press by the laminating mold 10, and is press-formed at a predetermined temperature and pressure, whereby a plurality of four layers of CCL can be simultaneously produced. As the laminated mold 10, a flat plate made of stainless steel can be used. As for the tablet, although there is no limit, Thick plates such as 1~10mm can be used. With regard to CCL of 4 or more layers, generally, the number of layers of the inner core sheets is increased, that is, it can be produced in the same procedure.

Hereinafter, as a specific example of the above use, the resin board of the present invention is used. The method of manufacturing the coreless composite substrate will be described by way of example on the both sides of the carrier 11c with the metal foil 11 attached to the metal foil. In this method, after the necessary number of layers are laminated on both sides of the attached sub-metal foil 11 by the combined layer 16, the metal foil of both sides is peeled off by the attached sub-metal foil 11 (refer FIG. 4).

For example, on the metal foil side of the attached sub-metal foil of the present invention, as an insulating layer The resin, the two-layer circuit board, and the resin as the insulating layer are sequentially superposed on each other, and the metal foil side is brought into contact with the resin sheet thereon, and then the metal foil of the attached sub-metal foil of the present invention is sequentially superposed to be produced. Combine the substrate.

Further, another method is a double-sided or single sheet of a resin-made plate-shaped carrier 11c. The metal foil side of at least one of the metal foil-attached metal foil is adhered to the resin as the insulating layer, and then laminated as the metal foil of the conductor layer. Then, depending on the requirements, a step of adjusting the thickness of the metal foil by a half etching process may be included. Then, the predetermined position of the metal foil after lamination is processed by laser, the metal foil and the resin are formed through the hole, and the glue removal process is performed to remove the colloid in the hole, and then pass through the bottom of the hole, the side surface and the metal foil. The whole or one part of the electroless plating layer is indirectly continued, and electrolytic plating is performed according to the needs thereof. It is also possible to form a plating resist layer in advance on the metal foil without electroless plating or electrolytic plating before the respective plating steps are performed. Further, in the case of electroless plating, electrolytic plating, and insufficient adhesion between the plating resist and the metal foil, the surface of the metal foil may be chemically roughened in advance. When the plating resist is used, the plating resist is removed after electrolysis. Next, the metal foil and the electroless plating part and the electroplating part are not required. Part of it is removed by etching to form a circuit. Thereby, a combined substrate can be obtained. It is also possible to produce a plurality of laminated substrates by repeating the steps from the lamination of the resin and the copper foil to the formation of the circuit.

Furthermore, the outer surface of the substrate can also be combined with the single-sided adhesion metal of the present invention. The foil side of the metal foil of the metal foil attached to the foil may be brought into contact for lamination, or the resin sheet may be laminated first, and then one side of the metal foil attached to the double-sided adhesive metal foil of the present invention may be The contacts are laminated.

Here, a resin sheet for forming a composite substrate may be selected from a prepreg containing a thermosetting resin.

Still another method is a single-sided or double-sided metal foil of the plate-shaped carrier of the present invention, for example, a laminate obtained by bonding a copper foil, and a resin which is used as an insulating layer, for example, pre-impregnated on the exposed surface of the metal foil. Sheet or photosensitive resin. Thereafter, a through hole is formed at a predetermined position of the resin. When a prepreg is used, the resin used can be processed by laser through a hole. After the laser processing, a gel removal step can be performed to remove the colloid in the hole. Alternatively, in the case where a photosensitive resin is used as the resin, the resin passing through the hole forming portion can be removed by photolithography. Then, the layer is indirectly formed by electroless plating through the bottom of the hole, the side surface, and the whole or a part of the resin, and electroplating is performed in accordance with the necessity. It is also possible to form a plating resist in advance before the respective plating steps are performed on portions of the resin which are not required for electroless plating or electrolytic plating. Further, in the case of electroless plating, electrolytic plating, and insufficient adhesion between the plating resist and the resin, the surface of the resin may be chemically roughened in advance. When the plating resist is used, the plating resist is removed after electrolysis. Then, the electroless plating portion or the electrolytic plating portion is not partially removed by etching to form a circuit. Thereby, a combined substrate can be obtained. It is also possible to carry out the steps from the lamination of the resin to the formation of the circuit in a plurality of times to obtain a composite substrate of more layers.

Furthermore, the outer surface of the substrate can also be combined with the single-sided adhesion metal of the present invention. The resin side of the foil laminate or the resin side of the metal foil with the metal foil attached to the metal foil is brought into contact for lamination, and the double-sided adhesive metal of the present invention may be further laminated after the resin is laminated. One side of the laminate of the foil or a metal foil having one side of the metal foil attached to the metal foil is contacted and laminated.

For the coreless composite substrate fabricated in such a manner, undergoing a plating step and/or etching The engraving step causes the wiring to be formed, and then the carrier resin and the metal foil are peeled off and separated to complete a combined wiring board. For the peeling surface of the peeled and separated metal foil, wiring may be formed, or the metal foil may be completely removed by etching as a combined wiring board. Further, a printed circuit board is completed by mounting electronic components on the combination wiring board. Further, a printed circuit board can be obtained by directly mounting an electronic component on the coreless composite substrate before resin peeling.

[Examples]

The embodiments of the present invention and the experimental examples of the comparative examples are disclosed below, but the examples are provided to further understand the present invention and its advantages, and are not intended to limit the invention.

(with sub-metal foil) <Experimental Examples 1 to 15>

Prepare a plurality of electrolytic copper foils (thickness 12 μm , rough surface roughness Rz jis 3.7 μm ), and perform nickel-zinc (Ni-Zn) on the bright (glossy) side of each electrolytic copper foil. Alloy plating treatment and chromate (Cr-Zn chromate) treatment, the ten point average roughness (measured according to Rz jis: JIS B 0601:2001) on the bonding surface (herein referred to as S surface) is treated as After 1.5 μm , the prepreg (FR-4 resin: glass transition temperature Tg=140°C; thickness 200 μm ) of South Asia Plastics Co., Ltd. was used as the resin to adhere to the S surface of the electrolytic foil, and 100 minutes at 170 ° C. Hot press processing to produce a carrier copper foil.

(nickel-zinc alloy plating)

Ni concentration 17g / L (added by NiSO ₄ method)

Zn concentration 4g / L (added by ZnSO ₄ method)

pH 3.1

Liquid temperature 40 ° C

Current density 0.1~10A/dm ²

Plating time 0.1~10 seconds

(chromate treatment)

Cr concentration 1.4g / L (added as CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01~1.0g/L (added by ZnSO ₄ method)

Na ₂ SO ₄ concentration 10g / L

pH 4.8

Liquid temperature 55 ° C

Current density 0.1~10A/dm ²

Plating time 0.1~10 seconds

Further, after the glossy surface was coated with an aqueous solution of a metal alkoxide shown in Table 1, it was coated with a spray coater. After drying in air at 100 ° C, the prepreg and the copper foil were bonded. The conditions for use of the metal alkoxide are disclosed in Table 1.

Further, among the copper foils to be attached, there are several cases in which the copper foil is subjected to further heat treatment such as circuit formation, and the heat history is carried out, and the conditions described in Table 1 are performed (here, 220). Heat treatment at °C for 3 hours, 6 hours, and 9 hours).

The copper foil and the plate-shaped carrier (heated resin) were measured by the copper foil attached to the hot pressing step and the copper foil after the heat treatment for 3 hours, 6 hours, and 9 hours thereafter. Peel strength. The respective results are shown in Table 1.

Further, in order to evaluate the peeling workability, the manual work time (time/number) was evaluated by the number of individual units. The results are shown in Table 2.

<Experimental Example 16>

In Experimental Example 1, when the copper foil was bonded to the prepreg, the prepreg was treated with the same conditions as in Experimental Example 1 except that the prepreg was not subjected to any metal alkoxide treatment, and the carrier copper foil was prepared. Evaluate the peel strength and working time at each stage. The respective results are shown in Tables 1 and 2.

Although not recorded in the table, the metal alkoxide, whether it is treated on the surface of the copper foil or on the surface of the prepreg, is treated under the same conditions of the same compound, and the peel strength of the laminate after the heating is heated. It is known that the peeling strength and the workability of peeling are equivalent.

【Table 1】

(combined wiring board)

FR-4 prepreg (made by Nanya Plastics Co., Ltd.) and copper foil (JTC Nisshin Nippon Metal Co., Ltd., JTC12 μm (product name) on both sides of the copper plated in this way The order of the layers is overlapped, and then a hot pressing step is performed under the heating conditions of the respective labels in the table at a pressure of 3 MPa to prepare a 4-layer copper laminate.

Next, the copper foil on the surface of the four-layer copper laminate layer and the insulating layer (pre-impregnated prepreg) on the lower surface were passed through, and a hole having a diameter of 100 μm was cut by a laser processing machine. In the pre-continuation step, the surface of the copper foil on the copper foil attached to the bottom of the hole and the side surface of the hole and the copper foil on the surface of the four-layer copper laminate are subjected to electroless copper plating and electrolytic copper plating. The copper plating, the copper foil with the carrier copper foil and the copper foil on the surface of the four-layer copper laminate layer form a current connection. In the pre-continuation step, one of the copper foils on the surface of the four-layer copper laminate is etched with an iron chloride-based etching solution to form an electric circuit. These steps operate to obtain a 4-layer composite substrate.

In the pre-continuation step, in the four-layer composite substrate, the plate-shaped carrier of the carrier copper foil and the copper foil were peeled off and separated to obtain two sets of two-layer composite wiring boards.

In the pre-continuation step, wiring is formed on the two-layer combination wiring board of the two groups described above, and the copper foil adhered to the plate-shaped carrier is etched to obtain two sets of two-layer composite wiring boards.

Each of the experimental examples was prepared by using a plurality of composite substrates of a plurality of layers, and in the combined substrate production step, the prepreg and the copper foil of the carrier copper foil were adhered to each other in a combined substrate, and visually confirmed. The peeling strength of Tables 1 and 3 and the peeling strength after heating are evaluated as "G" conditions, which means that when the copper foil to be produced is used as a composite wiring board, the resin of the copper foil is attached at the combination step ( The plate-shaped carrier was unbroken and successfully peeled off.

On the other hand, the condition of evaluation of "N" refers to the peeling operation of the copper foil of the carrier copper foil in the combination step, the resin is broken, or the resin is left on the surface of the unpeeled copper foil.

On the other hand, the condition of evaluation of "-" refers to the peeling operation of the copper foil of the copper foil attached to the carrier, and the resin is not broken and peeled off, but the copper foil is peeled off without performing the peeling operation.

Claims (41)

An attached sub-metal foil which is a plate-shaped carrier made of resin and an attached sub-metal foil which is made of a metal foil which is peelable and adhered to at least one side of the carrier; and the plate-shaped carrier and The metal foil is selected from the following formula: [Chemical Formula 1] (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is an alkoxy group or a halogen atom; and R ² is selected from an alkyl group and a ring. a hydrocarbon group in which an alkyl group or an aryl group is grouped, or a hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, the valence of m + n is M, that is, 3 for Al and 4 for Ti and Zr; An aluminate compound, a titanate compound or a zirconate compound, a hydrolyzed product of the aluminate compound, a hydrolyzed product of the titanate compound, a hydrolyzed product of the zirconate compound, a condensate of a hydrolyzed product of the aluminate compound, a condensate of a hydrolyzed product of the titanate compound, and a water addition of the zirconate compound In the group of the condensed products of the product, the attached metal foil is used by being used in combination or in combination, and the metal foil is characterized in that the metal foil satisfies any one of the following (1) and (2) or (1) The tenth point average roughness (Rz jis) of the surface of the metal foil not contacting the carrier side is 0.4 μm or more; (2) the metal foil is not in contact with the carrier The tenth point average roughness (Rz jis) of the surface of the sub-side is 10.0 μm or less; and the attached sub-metal foil satisfies the following sub-metal foil of either or both of (A) and (B) (A) the peeling strength of the plate-shaped carrier and the metal foil is 200 gf/cm or less; (B) after the heating process at 220 ° C for 3 hours, 6 hours or 9 hours, the metal foil and the foregoing The peeling strength of the plate-shaped carrier is 200 gf/cm or less. The sub-metal foil according to the first aspect of the invention, wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less. The sub-metal foil according to claim 1, wherein the resin-made plate-shaped carrier comprises a thermosetting resin. The sub-metal foil according to the first aspect of the patent application, wherein the resin-made plate-shaped carrier is a prepreg. The sub-metal foil of claim 3, wherein the resin-made plate-shaped carrier has a glass transition temperature Tg of 120 to 320 °C. The sub-metal foil attached to the first aspect of the patent application, wherein the surface on the side joined to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less. The sub-metal foil according to the first aspect of the patent application, wherein the thickness of the metal foil is 1 μm or more and 400 μm or less. The sub-metal foil according to Item 1 of the patent application, wherein the peeling strength of the metal foil and the plate-shaped carrier is 10 gf/cm or more and 200 gf after at least one heating process of 3 hours, 6 hours or 9 hours at 220 ° C. /cm below. The attached sub-metal foil according to any one of claims 1 to 8, wherein the metal foil is a copper foil. A metal foil for a printed wiring board having a surface selected from the group consisting of the following formula: [Chem. 2] (R ¹ ) _m -M-(R ² ) _n (wherein the R ¹ alkoxy group) Or a halogen atom; R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system is Al, Ti or Any one of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m + n is a valence of M, that is, In the case of Al, it is 3, and in the case of Ti and Zr, the aluminate compound, the titanate compound, the zirconate compound, the hydrolyzate of the aluminate compound, and the hydrolyzed product of the titanate compound are formed. a hydrolyzed product of the zirconate compound, a condensate of the hydrolyzed product of the aluminate compound, a condensate of the hydrolyzed product of the titanate compound, and hydrolyzed formation of the zirconate compound A metal foil for a printed wiring board which is a combination of a condensed body of a substance, which is characterized by the above-mentioned metal foil a metal foil for a printed wiring board that satisfies any one or both of the following (3) and (4); (3) an aluminate compound, a titanate compound, a zirconate compound, and the like selected from the metal foil a hydrolyzed product of the aluminate compound, a hydrolyzed product of the titanate compound, a hydrolyzed product of the zirconate compound, a condensate of the hydrolyzate of the aluminate compound, and the titanic acid In the group of the condensate of the hydrolyzed product of the salt compound and the condensate of the hydrolyzed product of the zirconate compound, the surface which is not in contact with the carrier alone or in combination with the surface on the opposite side The point average roughness (Rz jis) is 0.4 μm or more; (4) the hydrolyzate product having the aluminate compound, the titanate compound, the zirconate compound, and the aluminate compound described above selected from the metal foil described above. And a hydrolyzed product of the titanate compound, a hydrolyzed product of the zirconate compound, a condensate of a hydrolyzed product of the aluminate compound, and the titanate compound In the group of the condensate of the hydrolyzed product and the condensate of the hydrolyzed product of the zirconate compound, the side of the surface which is not in contact with the carrier alone or in combination with the surface on the opposite side The thickness (Rz jis) is 10.0 μm or less; and the metal foil of the printed wiring board which satisfies any one or both of the following (C) and (D); (C) the metal foil In the case where the metal foil is peeled off from the resin, the peeling strength of the metal foil and the resin is 200 gf/cm or less; (D) after laminating the resin on the metal foil, the metal foil and the foregoing The peeling strength of the metal foil and the plate-shaped carrier is 200 gf/cm in the case where the resin is peeled off from the resin after the resin is peeled off at 220 ° C for at least one of 3 hours, 6 hours or 9 hours. The following. The metal foil for a printed wiring board according to claim 10, wherein the metallohydrate compound, the titanate compound or the zirconate compound of the metal foil is hydrolyzed, and the hydrolyzed product is hydrolyzed. The condensate is subjected to a chromate treatment before the action of the compound with respect to the surface on the side on which the combination is applied singly or in combination. The metal foil for a printed wiring board according to claim 10, wherein the metal foil has an aluminate compound, a titanate compound, a zirconate compound, a hydrolyzed product thereof, and the hydrolyzed product. The condensed body, the surface on the side of the combination of singly or plural, has a ten-point average roughness (Rz jis) of 3.5 μm or less. The metal foil for a printed wiring board according to claim 10, wherein the metal foil is a copper foil. A metal foil having at least one side selected from the group consisting of: (Chemical Formula 3) (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 or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; and M is any one of Al, Ti or Zr n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, the valence of m + n is M, that is, 3 when Al is In the case of Ti and Zr, the aluminate compound, the titanate compound or the zirconate compound shown in 4), the hydrolyzed product of the above aluminate compound, the hydrolyzed product of the titanate compound, and the aforementioned zirconate a hydrated product of a salt compound, a condensate of a hydrolyzed product of the above aluminate compound, a condensate of a hydrolyzed product of the titanate compound, and a condensate of a hydrolyzed product of the zirconate compound a metal foil in a group, either alone or in combination, and which can be used to: peel a resin-made plate-shaped carrier on the surface A metal foil for use in a close contact with the metal foil of any one of the following (5) and (6); (5) a plate-shaped carrier made of the resin of the metal foil is predetermined The ten-point average roughness (Rz jis) of the surface on the non-contact side is 0.4 μm or more; (6) the ten-point average roughness of the surface on the side of the predetermined non-contact side of the above-mentioned resin-made plate-shaped carrier of the metal foil ( Rz jis) is 10.0 μm or less; and the metal foil of the following (E) and (F) is satisfied by the metal foil; (E) after the resin is laminated on the metal foil, the foregoing In the case where the metal foil is peeled off from the resin, the peel strength of the metal foil and the resin is 200 gf/cm or less; (F) after the resin is laminated on the metal foil, the metal foil and the resin are passed at 220 ° C for 3 hours. In the case where the metal foil is peeled off from the resin after at least one of the heating process for 6 hours or 9 hours, the peeling strength of the metal foil and the plate-shaped carrier is 200 gf/cm or less. The metal foil of claim 14, wherein the metal foil is an aluminate compound, a titanate compound or a zirconate compound, and the like, a hydrolyzed product, the condensate of the hydrolyzed product, The surface treated with the chromate is applied to the surface of the active side in combination with it alone or in combination. The metal foil of claim 14, wherein the surface of the metal foil on the side where the carrier is bonded has a ten point average roughness (Rz jis) of 3.5 μm or less. A plate-shaped carrier made of resin, which is at least on one surface, has a formula selected from the group consisting of: (Chemical Formula 4) (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is a kind Alkoxy or a halogen atom; R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M-based Al Any of Ti, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m + n is a valence of M , that is, 3 when Al is 3, an aluminate compound, a titanate compound or a zirconate compound represented by 4) in the case of Ti and Zr, a hydrolyzed product of the above aluminate compound, and the aforementioned titanate compound. a hydrolyzed product, a hydrolyzed product of the zirconate compound, a condensate of the hydrolyzate of the aluminate compound, a condensate of the hydrolyzate of the titanate compound, and the zirconate compound In the group in which the condensate of the hydrolyzed product is added, the plate-shaped carrier made of a resin which is combined singly or in plural is characterized in that it satisfies the following a plate-shaped carrier made of a resin of either or both of (G) and (H); (G) a layered carrier made of the resin after laminating a metal foil on the plate-shaped carrier made of the resin In the case where the metal foil is peeled off, the peel strength of the resin-made plate-shaped carrier and the metal foil is 200 gf/cm or less; (H) after the metal foil is laminated on the resin-made plate-shaped carrier, In the case where the resin-made plate-shaped carrier and the metal foil are subjected to at least one heating process at 220 ° C for 3 hours, 6 hours or 9 hours, the resin-made plate-shaped carrier is peeled off from the metal foil, the aforementioned The peel strength of the resin-made plate-shaped carrier and the metal foil plate is 200 gf/cm or less. A plate-shaped carrier having at least one surface having a formula selected from the group consisting of: (5) (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 or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system is Al, Ti or Any one of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R ¹ is an alkoxy group; further, m + n is a valence of M, that is, In the case of Al, it is 3, and in the case of Ti and Zr, the aluminate compound, the titanate compound or the zirconate compound shown in 4), the hydrolyzed product of the aluminate compound, and the hydrolyzed product of the titanate compound are formed. a hydrolyzed product of the zirconate compound, a condensate of the hydrolyzed product of the aluminate compound, a condensate of the hydrolyzed product of the titanate compound, and hydrolyzed formation of the zirconate compound a plate-shaped carrier made of a resin which is singly or in combination of a plurality of condensed bodies; and the system can be used for: gold on the surface A plate-shaped carrier made of a resin which is used for peeling and sealing the foil, and is characterized by a plate-shaped carrier made of a resin which satisfies either or both of the following (I) and (J); After the metal foil is laminated on the resin-made plate-shaped carrier, and the resin-made plate-shaped carrier is peeled off from the metal foil, the peel strength of the resin-made plate-shaped carrier and the metal foil is 200 gf/cm or less; (J) After laminating a metal foil on the resin-made plate-shaped carrier, the resin-made plate-shaped carrier and the metal foil are allowed to pass at 220 ° C for 3 hours, 6 hours or 9 hours. In the case where the resin-made plate-shaped carrier is peeled off from the metal foil after at least one heating process, the peeling strength of the resin-made plate-shaped carrier and the metal foil plate is 200 gf/cm or less. A method for producing a multilayer metal laminated laminate, characterized in that it comprises: laminating a resin with respect to a metal foil side of at least one side of the attached sub-metal foil according to any one of claims 1 to 9; The resin or metal foil is repeated one or more times for lamination. A method for producing a multilayer metal laminated laminate, characterized in that it comprises: laminating a resin on a side of a metal foil attached to a sub-metal foil according to any one of claims 1 to 9, and then A resin, a single-sided or double-sided metal laminate, or an attached sub-metal foil or a metal foil repeat according to any one of claims 1 to 9. Laminating more than once. The invention relates to a method for manufacturing a multi-layer metal laminate, which is characterized in that the method for manufacturing a multilayer metal laminate of the 19th or 20th patent of the patent application further comprises a plate-shaped carrier and a metal with a metal foil attached thereto. The step of peeling and separating the foil. A method for producing a multilayer metal laminated laminate, characterized in that in the manufacturing method of claim 21, a step of removing one or all of the metal foil which has been peeled off and separated by etching is included. A multilayer metal laminated laminate characterized by the method of manufacturing according to any one of claims 19 to 22. A method for producing a composite substrate, which comprises the step of forming one or more layers of the wiring layer on the side of the metal foil to which the sub-metal foil is attached, according to any one of claims 1 to 9. The method for producing a composite substrate according to claim 24, wherein the combined wiring layer is formed by using at least one of a subtractive method or a full additive method or a semi-additive method. A method for producing a composite substrate, comprising: laminating a resin on at least one side of a metal foil attached to at least one side of a sub-metal foil according to any one of claims 1 to 9, and then resinating the resin A single-sided or double-sided wiring board, a single-sided or double-sided metal laminate, and a sub-metal foil or a metal foil attached to any one of the above claims 1 to 9 may be laminated one or more times. A method for manufacturing a composite substrate, characterized by further comprising: in the method for manufacturing a composite substrate of claim 26, on a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminate, and an attached The metal foil of the sub-metal foil, the plate-shaped carrier on which the sub-metal foil is attached, the metal foil or the resin is drilled, and the step of conducting electroplating is performed on the side surface or the bottom surface of the hole. A method of manufacturing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate of claim 26, in forming a metal foil of a single-sided or double-sided wiring substrate, forming a single-sided or double-sided metal One time on at least one of the metal foil of the laminate, the metal foil constituting the attached metal foil, and the metal foil The above steps of wiring formation. A method of manufacturing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate of claim 27, forming a metal foil of a single-sided or double-sided wiring substrate, forming a single-sided or double-sided metal The step of forming one or more wirings on at least one of the metal foil of the laminate, the metal foil constituting the attached sub-metal foil, and the metal foil. The method for manufacturing a composite substrate according to claim 28, further comprising: attaching any one of the first to ninth claims of the patented surface on the surface formed by the wiring on the surface of the wiring The resin sheet side of the sub-metal foil is in contact with it and is subjected to a lamination step. The method for manufacturing a composite substrate according to claim 29, further comprising: attaching any one of the first to the ninth to the application of the metal foil on the surface formed on the wiring The resin sheet side of the sub-metal foil is in contact with it and is subjected to a lamination step. The method for manufacturing a composite substrate according to claim 28, further comprising a method of laminating a resin on a surface formed by the wiring, and applying the patent to the resin on both sides of the resin. Any one of the metal foils of the sub-metal foil attached to any one of items 1 to 9 is brought into contact and laminated. The method for manufacturing a composite substrate according to claim 29, further comprising: laminating the resin on the surface formed by the wiring, and applying the patent to the resin on both sides of the resin. Any one of the metal foils of the sub-metal foil attached to any one of items 1 to 9 is brought into contact and laminated. The method for producing a composite substrate according to any one of claims 26 to 33, wherein at least one of the resins is a prepreg. A method of manufacturing a composite wiring board according to any one of claims 24 to 33, further comprising: stripping the plate-shaped carrier carrying the metal foil with the metal foil And the steps of separation. A manufacturing method of a combined wiring board, characterized in that in the method for manufacturing a combined substrate of claim 34, a plate-shaped carrier to which a sub-metal foil is attached is further included The step of peeling off and separating from the metal foil. A method of manufacturing a composite wiring board, characterized in that in the method of manufacturing a composite wiring board according to claim 35, one or all of the metal foil adhered to the plate-shaped carrier are removed by etching. step. A combination wiring board characterized by being produced by the manufacturing method of any one of claims 35 to 37. A method of manufacturing a printed circuit board, comprising the step of manufacturing a composite substrate by the manufacturing method according to any one of claims 24 to 33. A method of manufacturing a printed circuit board, comprising the steps of: manufacturing a combined wiring board by the manufacturing method of claim 35. A method of manufacturing a printed circuit board, characterized by comprising the step of manufacturing a combined wiring board by the manufacturing method of claim 36.