JP2015107598A - Laminate with resin substrates in close contact with each other in peelable manner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which can be suitably used in the production of a multilayer wiring board such as a multilayer metal-clad laminate plate and a build-up substrate.SOLUTION: This invention provides a laminate in which a release agent is interposed between two resin substrates, with the resin substrates in close contact with each other in a peelable manner.

Description

  The present invention relates to a laminate in which resin substrates are brought into close contact with each other in a peelable manner. More specifically, the present invention relates to a laminate used in the production of a single-sided or two- or more-layer laminated board used for a printed wiring board or an ultra-thin coreless substrate.

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

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

JP 2009-272589 A JP 2000-196207 A

  The metal foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to the reduction of the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield, but the multilayer metal-clad laminate having various configurations In order to deal with the production of multilayer wiring boards such as build-up boards and the like, there is still room for study on laminated bodies having various configurations replacing the metal foil with carrier.

  As a result of intensive studies on a laminate that replaces a metal foil with a carrier composed of a resin plate and a metal foil, the present inventors have also found that a laminate in which resin substrates are brought into close contact with each other in a peelable manner is also a multilayer metal-clad laminate. The present invention has been completed by finding that it can be suitably used for the production of multilayer wiring boards such as slabs and build-up boards.

That is, the present invention is as follows.
(1) A laminate in which a release agent is interposed between two resin substrates, and these resin substrates are detachably adhered to each other.
(2) The laminate according to (1), wherein the peel strength between the resin substrates is 10 gf / cm or more and 200 gf / cm or less.
(3) The said resin substrate is a laminated body as described in (1) or (2) which has the glass transition temperature Tg of 120-320 degreeC.
(4) The peel strength between the resin substrates after heating at 220 ° C. for at least one of 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less (1) to ( The laminated body in any one of 3).
(5) The laminate according to any one of (1) to (4), wherein the release agent is at least one selected from the group consisting of the following (a) to (d):
(A) Silane compound

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
A silane compound, a hydrolysis product thereof, or a condensate of the hydrolysis product, alone or in combination;
(B) a compound having two or less mercapto groups in the molecule;
(C) Metal alkoxide

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
An aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, a condensate of the hydrolysis product, alone or in combination, and (d) a silicone, an epoxy resin, a melamine resin, and A composition comprising any one or more resins selected from fluororesins.
(6) The laminate according to any one of (1) to (5), wherein the thickness of the resin substrate is 5 μm or more and 1000 μm or less.
(7) A laminate obtained by laminating at least one other resin substrate on an exposed surface of at least one resin substrate of the laminate according to any one of (1) to (6).
(8) The laminate according to any one of (1) to (7), wherein the resin substrate is obtained by curing a thermosetting resin.
(9) The laminate according to any one of (1) to (8), wherein the resin substrate is a prepreg.
(10) A laminate obtained by laminating a metal foil on an exposed surface of at least one resin substrate present on the resurface of the laminate according to any one of (1) to (9).
(11) The laminate according to (10), wherein the metal foil is a copper foil.
(12) Multilayer metal tension comprising laminating a resin on at least one metal foil side of the laminate according to (10) or (11) and then repeatedly laminating the resin or metal foil one or more times A manufacturing method of a laminated board.
(13) A resin is laminated on the metal foil side of the laminate according to (10) or (11), and then the resin, the laminate according to any one of claims 1 to 9, single-sided or double-sided metal-clad A method for producing a multilayer metal-clad laminate comprising laminating a laminate, the laminate according to claim 10 or 11, or a metal foil repeatedly at least once.
(14) In the method for producing a multilayer metal-clad laminate according to (12) or (13), the multilayer metal-clad further comprising a step of separating and separating the resin substrates that are in close contact with each other in a peelable manner. A manufacturing method of a laminated board.
(15) The method for producing a multilayer metal-clad laminate comprising the step of removing a part or all of the separated and separated resin substrate by etching in the production method according to (14).
(16) A multilayer metal-clad laminate obtained by the production method according to any one of (12) to (15).
(17) A method for producing a buildup substrate, comprising a step of forming one or more buildup wiring layers on at least one metal foil side of the laminate according to (10) or (11).
(18) The buildup wiring layer manufacturing method according to (17), wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semi-additive method.
(19) A resin is laminated on at least one metal foil side of the laminate according to (10) or (11), and then the resin, the laminate according to any one of (1) to (9), one side Or the manufacturing method of the buildup board | substrate including repeatedly laminating | stacking a double-sided wiring board, a single-sided or double-sided metal-clad laminated board, the laminated body as described in (10) or (11), or metal foil once or more.
(20) In the method for manufacturing a build-up board according to (19), a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a laminate metal foil, a laminate resin substrate, a metal foil, or a hole in the resin The manufacturing method of the buildup board | substrate which further includes the process of carrying out conductive plating on the side surface and bottom face of the said hole.
(21) In the method for manufacturing a buildup board according to (19) or (20), a metal foil constituting the single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a laminate A build-up substrate manufacturing method further comprising performing at least one step of forming a wiring on at least one of the metal foil and the metal foil to be configured.
(22) The method further includes a step of laminating one resin substrate side of the laminate according to any one of (1) to (9) in which a metal foil is adhered to one surface on the surface on which the wiring is formed (19 )-(21) The manufacturing method of the buildup board | substrate as described in any one of.
(23) The method further includes the step of laminating the laminate according to any one of (1) to (9) in which a resin is laminated on the surface on which the wiring is formed, and a metal foil is adhered to both sides of the resin. (19) The manufacturing method of the buildup board | substrate in any one of (21).
(24) The method for manufacturing a buildup substrate according to any one of (19) to (23), wherein at least one of the resin substrates is a prepreg.
(25) In the method for manufacturing a buildup substrate according to any one of (17) to (24), the buildup further includes a step of separating and separating the resin substrates that are in close contact with each other in a peelable manner. A method for manufacturing a wiring board.
(26) The method for manufacturing a buildup wiring board according to (25), including a step of removing a part or all of the separated and separated resin substrate by etching.
(27) A build-up wiring board obtained by the manufacturing method according to (25) or (26).
(28) A method for producing a printed circuit board, comprising a step of producing a build-up substrate by the method according to any one of (17) to (24).
(29) A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to (25) or (26).

  The present invention provides a laminate that can be suitably used for the production of multilayer wiring boards such as multilayer metal-clad laminates and build-up boards, and has the advantage of improving the productivity of printed wiring boards using this.

An example of the configuration of CCL is shown. One structural example of the laminated body which concerns on this invention is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined to the single side | surface of the resin board) is shown. The assembly example of the multilayer CCL using the laminated body which concerns on this invention is shown.

  In one embodiment of the laminated body according to the present invention, a laminated body in which two resin substrates are brought into close contact with each other is prepared. One structural example of the laminated body which concerns on this invention is shown in FIG. 2 and FIG. In FIG. 2, two resin substrates are bonded together using a layer made of a release agent or a release material (release agent / release material) described later. In particular, at the beginning of FIG. 4, there is described a laminate 11 obtained by bonding two resin substrate 11a using a layer made of a release agent or a release material 11b described later.

  Since the resin substrate used in the present invention must be peeled off eventually, it is inconvenient that the adhesiveness is excessively high, but both the resin substrates are not peeled off in the chemical treatment process such as plating performed in the printed circuit board manufacturing process. The adhesion of is necessary. From such a viewpoint, the peel strength between the resin substrates is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and even more preferably 50 gf / cm or more, / Cm or less, more preferably 150 gf / cm or less, and still more preferably 80 gf / cm or less. By setting the peel strengths of the resin substrates to such a range, the resin substrates can be easily and mechanically peeled off without being peeled off during transport or processing.

  The adjustment of the peel strength for realizing such adhesion can be easily realized by using a layer made of a specific release agent or a release material. This is because, by using a layer or a release material made of such a release agent, the two resin substrates are bonded to each other, whereby the adhesiveness is appropriately lowered and the peel strength can be adjusted to the above-described range.

  Next, a release agent or a release material that can be preferably used when two resin substrates are bonded together in order to achieve adhesion required for the use of the laminate described later will be described.

(1) Silane compound A silane compound having a structure represented by the following formula, a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a silane compound) is used alone or in combination. Then, by adhering the two resin substrates, the adhesion is moderately lowered, and the peel strength can be adjusted to a range as described later.

formula:

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

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

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

Examples of the alkoxy group include, but are not limited to, methoxy group, ethoxy group, n- or iso-propoxy group, n-, iso- or tert-butoxy group, n-, iso- or neo-pentoxy group, n-hexoxy. Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group, etc., linear, branched, or cyclic carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 5 alkoxy groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, and n-hexyl. A linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as a group, an n-octyl group, and an n-decyl group.

  Examples of the cycloalkyl group include, but are not limited to, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, and the like. An alkyl group is mentioned.

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

  In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

  Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo-pentyl. Trimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl-substituted phenyltrimethoxysilane (eg, p- (methyl) phenyltrimethoxysilane), methyltriethoxysilane, ethyl Triethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxy Lan, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane (eg, p- (methyl) phenyltriethoxysilane), (3,3,3-trifluoropropyl) trimethoxysilane, and trideca Fluorooctyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, their hydrolysis products, and condensates of these hydrolysis products Etc. Among these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of availability.

  The laminate can be manufactured by coating the silane compound on the bonding surface of at least one resin substrate, and hot-pressing a B-stage resin substrate on the bonding surface.

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

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

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

(2) Compound having two or less mercapto groups in the molecule Adhesion is also lowered moderately by bonding two resin substrates using a compound having two or more mercapto groups in the molecule. The peel strength can be adjusted to a range as described later.
However, when a compound having three or more mercapto groups in the molecule or a salt thereof is bonded between two resin substrates, it is considered that the compound is not suitable for the purpose of reducing the peel strength described in the present application. This is because, if there is an excessive amount of mercapto groups in the molecule, excessive chemical bonds between the mercapto groups or the mercapto group and the resin substrate generate excessive sulfide bonds, disulfide bonds, or polysulfide bonds. This is because it is considered that the peel strength may be increased by forming a crosslinked structure. Such an example is disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2000-196207) as an embodiment used as an inclusion of a copper foil-resin base material.

  Examples of the compound having two or less mercapto groups in the molecule include thiol, dithiol, thiocarboxylic acid or a salt thereof, dithiocarboxylic acid or a salt thereof, thiosulfonic acid or a salt thereof, and dithiosulfonic acid or a salt thereof. At least one selected from these can be used.

  The thiol has one mercapto group in the molecule and is represented by R-SH, for example. Here, R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.

Dithiol has two mercapto groups in the molecule and is represented by, for example, R (SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Two mercapto groups may be bonded to the same carbon, or may be bonded to different carbons or nitrogens.

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

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

The thiosulfonic acid is obtained by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, and is represented by, for example, R (SO ₂ ) —SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Further, thiosulfonic acid can be used in the form of a salt.

Dithiosulfonic acid is one in which two hydroxyl groups of an organic disulfonic acid are each substituted with a mercapto group, and is represented by, for example, R-((SO ₂ ) -SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Two thiosulfonic acid groups may be bonded to the same carbon, or may be bonded to different carbons. Dithiosulfonic acid can also be used in the form of a salt.

  Here, examples of the aliphatic hydrocarbon group 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 amino group.

  Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n -A linear or branched alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as a hexyl group, an n-octyl group, and an n-decyl group. .

  Moreover, as a cycloalkyl group, although it is not limited, C3-C10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Preferably it is C5-C7 Of the cycloalkyl group.

  Further, examples of the aromatic hydrocarbon group suitable as R include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group and the like. -20, preferably 6-14 aryl groups are included, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

  Moreover, examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, which may contain one or both of a hydroxyl group and an amino group.

  Preferred examples of the compound having 2 or less mercapto groups in the molecule include 3-mercapto-1,2propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1-hexanol, 1- Octanethiol, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol, thiobenzoic acid, Examples include 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, and 2-mercapto-benzothiazole. Among these, 3-mercapto-1,2 propanediol is preferable from the viewpoint of water solubility and waste disposal.

  The laminated body is obtained by coating at least one resin substrate with a compound having two or less mercapto groups in the molecule, and hot-pressing the B-stage resin substrate on the bonded surface. It can be manufactured by laminating.

  A compound having two or less mercapto groups in the molecule can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a compound having two or less mercapto groups in a highly hydrophobic molecule is used.

  The higher the concentration in the aqueous solution of the compound having 2 or less mercapto groups in the molecule, the lower the peel strength between the resin substrates. By adjusting the concentration of the compound having 2 or less mercapto groups in the molecule The peel strength can be adjusted. Although it is not limited, the concentration of the compound having 2 or less mercapto groups in the molecule in the aqueous solution can be 0.01 to 10.0% by weight, typically 0.1 to 5.0%. % By weight.

  The pH of the aqueous solution of the compound having two or less mercapto groups in the molecule is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

(3) Metal alkoxide An aluminate compound, titanate compound, zirconate compound having a structure represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a metal alkoxide) alone Or by mixing and using two resin substrates, the adhesiveness is moderately lowered, and the peel strength can be adjusted to a range as described later.

In the formula, R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms. Any one of these substituted hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, m is an integer from 1 to M, and R1 At least one of these is an alkoxy group. M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.

The metal alkoxide needs to have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much. The metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have 0 to 2 pieces. This is because when three or more hydrocarbon groups are present, the adhesion between the plate-like carrier and the metal foil surface tends to be excessively lowered. The alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.
In adjusting the peel strength between the resin substrates to the above-described range, the metal alkoxide includes two or more alkoxy groups and the hydrocarbon group (including a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom). ) Are preferably included.

  Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n -A linear or branched alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as a hexyl group, an n-octyl group, and an n-decyl group. .

  Moreover, as a cycloalkyl group, although it is not limited, C3-C10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Preferably it is C5-C7 Of the cycloalkyl group.

In addition, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples thereof include 6 to 20, preferably 6 to 14, aryl groups, and these hydrocarbon groups may contain one or both of a hydroxyl group and an amino group.
In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

  Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or iso-propyldimethoxyaluminum, n-, iso- or tert-butyldimethoxyaluminum, n-, iso- or neo- Pentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; alkyl-substituted phenyl dimethoxy aluminum (for example, p- (methyl) phenyl dimethoxy aluminum), dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethoxy Luminium, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diiso Ropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3- Trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, and their hydrolysis products And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

  Examples of preferred titanate compounds include tetramethoxy titanium, methyl trimethoxy titanium, ethyl trimethoxy titanium, n- or iso-propyl trimethoxy titanium, n-, iso- or tert-butyl trimethoxy titanium, n-, iso- Or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (eg, p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxy Titanium, tetraethoxy titanium, methyl triethoxy titanium, ethyl triethoxy titanium, n- or iso-propyl triethoxy titanium, n-, iso- or tert-butyl triethoxy titanium, Tiltlyethoxytitanium, Hexyltriethoxytitanium, Octyltriethoxytitanium, Decyltriethoxytitanium, Phenyltriethoxytitanium, Alkyl-substituted phenyltriethoxytitanium (eg, p- (methyl) phenyltriethoxytitanium), Dimethyldiethoxytitanium, Tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltriiso Propoxy titanium, octyltriisopropoxy titanium, decyl triisopropoxy titanium, phenyl triisopropoxy titanium, alkyl substituted phenyl triisopropoxy titanium (example P- (methyl) phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichloro Examples include titanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, hydrolysis products thereof, and condensates of these hydrolysis products. Among these, tetramethoxy titanium, tetraethoxy titanium, and tetraisopropoxy titanium are preferable from the viewpoint of availability.

  Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium, n-, iso- Or neo-pentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl-substituted phenyltrimethoxyzirconium (eg, p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxy Zirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, n Or iso-propyltriethoxyzirconium, n-, iso- or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyltri Ethoxyzirconium (eg, p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, n- , Iso- or tert-butyltriisopropoxyzirconium, pentyltriisopropoxydi Konium, hexyltriisopropoxyzirconium, octyltriisopropoxyzirconium, decyltriisopropoxyzirconium, phenyltriisopropoxyzirconium, alkyl-substituted phenyltriisopropoxyzirconium (eg, p- (methyl) phenyltriisopropoxytitanium), dimethyldi Isopropoxyzirconium, (3,3,3-trifluoropropyl) trimethoxyzirconium, and tridecafluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldibromo Zirconium, diphenyldibromozirconium and their hydrolyzed products Examples thereof include condensates of these products and hydrolysis products thereof. Among these, tetramethoxyzirconium, tetraethoxyzirconium, and tetraisopropoxyzirconium are preferable from the viewpoint of availability.

  The laminate is manufactured by applying the metal alkoxide in the molecule to the bonding surface of at least one resin substrate and hot-pressing a B-stage resin substrate on the bonding surface. Is possible.

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

  The higher the concentration of the metal alkoxide in the aqueous solution, the lower the peel strength between the resin substrates, and the peel strength can be adjusted by adjusting the metal alkoxide concentration. Although not limited, the concentration of the metal alkoxide in the aqueous solution can 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 can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

(4) Release material composed of resin coating film Two resin substrates are formed of a resin coating film composed of silicone and any one or more resins selected from epoxy resins, melamine resins and fluororesins. By using and sticking together, the adhesiveness is moderately lowered, and the peel strength can be adjusted to a range as described later.

  As described later, the adjustment of the peel strength for realizing such adhesion is composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin. This is done by using a resin coating. Such a resin coating film is subjected to a baking process under predetermined conditions as will be described later, and is hot-pressed and bonded between the resin substrates, so that the adhesiveness is appropriately reduced and the peel strength is within the above-described range. This is because it can be adjusted.

  Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, Examples thereof include brominated phenoxy resin.

  Examples of the melamine-based resin include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol-modified melamine resin. The melamine resin may be a mixed resin of the resin and a butylated urea resin, a butylated benzoguanamine resin, or the like.

  The number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000. By having such a number average molecular weight, the resin can be made into a paint and the adhesive strength of the resin coating film can be easily adjusted to a predetermined range.

  Examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

  Examples of silicone include methylphenylpolysiloxane, methylhydropolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures thereof. Here, the modification is, for example, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification. And acyloxyalkyl modification, halogenated alkylacyloxyalkyl modification, halogenated alkyl modification, aminoglycol modification, mercapto modification, hydroxyl group-containing polyester modification, and the like.

  In the resin coating film, when the film thickness is too small, the resin coating film is too thin and difficult to form, so that productivity is easily lowered. Moreover, even if a film thickness exceeds a fixed magnitude | size, the further improvement of the peelability of a resin coating film is not seen, but the manufacturing cost of a resin coating film tends to become high. From such a viewpoint, the resin coating film preferably has a thickness of 0.1 to 10 μm, and more preferably 0.5 to 5 μm. Moreover, the film thickness of a resin coating film is achieved by apply | coating a resin coating material by the predetermined application amount in the procedure mentioned later.

  In the resin coating film, silicone functions as a release agent for the resin coating film. Therefore, if the total amount of epoxy resin and melamine resin is too much compared to silicone, the peel strength imparted by the resin coating between the resin substrates will increase, and the peelability of the resin coating will be reduced. It may not be easily peeled off. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-described peel strength is reduced, and thus the laminate may be peeled during transport or processing. From this viewpoint, it is preferable that the total of the epoxy resin and the melamine resin is included in an amount of 10 to 1500 parts by mass, and more preferably 20 to 800 parts by mass with respect to 100 parts by mass of silicone. Is preferred.

  Further, like silicone, the fluororesin functions as a release agent and has the effect of improving the heat resistance of the resin coating film. If the amount of fluororesin is too much compared to silicone, the aforementioned peel strength will be reduced, which may cause peeling when the laminate is transported or processed, and it will be uneconomical because the temperature required for the baking process described later will increase. . From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of silicone.

The resin coating film is selected from SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg (OH) ₂ in addition to silicone and epoxy resin and / or melamine resin and, if necessary, fluororesin 1 You may further contain the surface roughening particle | grains of a seed | species or more. When the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the resin substrate to which the resin coating film is applied becomes uneven and becomes a matte surface. Although content of the surface roughening particle | grains will not be specifically limited if a resin coating film is uneven | corrugated, 1-10 mass parts is preferable with respect to 100 mass parts of silicone.

  The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm. Here, the particle diameter means an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph or the like. When the particle diameter of the surface roughened particles is within the above range, the unevenness on the surface of the resin coating film can be easily adjusted, and as a result, the unevenness on the surface of the plate-like carrier or metal foil can be easily adjusted. Specifically, the unevenness on the surface of the resin substrate is about 4.0 μm in terms of the maximum height roughness Ry defined by JIS.

Here, the manufacturing method of a laminated body is demonstrated.
This laminate is obtained through a procedure that includes a step of applying the above-described resin coating to the surface of at least one resin substrate and a baking step of curing the applied resin coating. Hereinafter, each step will be described.

(Coating process)
In the coating process, a resin coating is applied to the surface of the resin substrate by applying a resin coating composed of silicone as the main agent, epoxy resin or melamine resin as the curing agent, and fluororesin as the release agent as necessary. This is a step of forming a film. The resin paint is obtained by dissolving an epoxy resin, a melamine resin, a fluororesin, and silicone in an organic solvent such as alcohol. Moreover, it is preferable that the compounding quantity (addition quantity) in a resin coating material is 10-1500 mass parts with respect to 100 mass parts of ricone, and a total of an epoxy resin and a melamine resin. Moreover, it is preferable that a fluororesin is 0-50 mass parts with respect to 100 mass parts of silicone.

The coating method in the coating process is not particularly limited as long as a resin coating film can be formed, but a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, a method using an electrostatic coating machine, etc. are used. In view of the uniformity of the resin coating film and the ease of work, the gravure coating method is preferred. Moreover, as an application quantity, 1.0-2.0 g / m < ² > is preferable as a resin quantity so that the resin coating film 3 may become preferable film thickness: 0.5-5 micrometers.

  The gravure coating method is a method in which a resin coating film is formed on the surface of a resin substrate by transferring a resin coating filled in a recess (cell) provided on the roll surface to a plate-like carrier. Specifically, the lower part of the lower roll having cells provided on the surface is immersed in the resin paint, and the resin paint is pumped into the cell by the rotation of the lower roll. Then, the plate-like carrier is arranged between the lower roll and the upper roll arranged on the upper side of the lower roll, and the lower roll and the upper roll are held while pressing the plate-like carrier against the lower roll with the upper roll. By rotating, the plate-like carrier is conveyed, and the resin paint pumped into the cell is transferred (applied) to one side of the plate-like carrier.

  Also, by placing a doctor blade on the resin substrate carry-in side so as to contact the surface of the lower roll, excess resin paint pumped up to the roll surface other than the cell is removed, and the resin substrate surface is placed. A fixed amount of resin paint is applied. In addition, when the count (size and depth) of a cell is large, or when the viscosity of a resin coating material is high, the resin coating film formed on one side of a resin substrate becomes difficult to become smooth. Therefore, a smoothing roll may be arranged on the carry-out side of the resin substrate to maintain the smoothness of the resin coating film.

  When forming a resin coating on both sides of the laminate, after forming the resin coating on one side of the laminate, turn the laminate over and place it again between the lower roll and the upper roll. To do. Then, in the same manner as described above, the resin paint in the cell of the lower roll is transferred (applied) to the back surface of the laminate.

(Baking process)
A baking process is a process of performing the baking process for 0.5 to 60 second (baking time) at 125-320 degreeC (baking temperature) to the resin coating film formed at the application | coating process. As described above, by subjecting the resin coating film formed of the predetermined amount of resin coating to a baking process under predetermined conditions, the peel strength between the resin substrates applied by the resin coating film is controlled within a predetermined range. In the present invention, the baking temperature is the ultimate temperature of the resin substrate. Moreover, a conventionally well-known apparatus is used as a heating means used for a baking process.

  When the baking is insufficient, for example, when the baking temperature is less than 125 ° C. or when the baking time is less than 0.5 seconds, the resin coating becomes insufficiently cured, and the peel strength exceeds 200 gf / cm, The peelability is reduced. Moreover, when baking is an excessive condition, for example, when baking temperature exceeds 320 degreeC, a resin coating film deteriorates, the said peeling strength exceeds 200 gf / cm, and the workability | operativity at the time of peeling deteriorates. Or a plate-shaped carrier may change in quality by high temperature. Further, when the baking time exceeds 60 seconds, the productivity is deteriorated.

In the method for producing a laminate, the resin coating in the application step includes silicone as a main agent, epoxy resin as a curing agent, melamine resin, fluororesin as a release agent, SiO ₂ , MgO, Al ₂ O. ₃ or one or more kinds of surface roughened particles selected from BaSO ₄ and Mg (OH) ₂ .

  Specifically, the resin coating is obtained by further adding surface roughening particles to the above-described silicone-added resin solution. By further adding such surface-roughened particles to the resin coating, the surface of the resin coating becomes uneven, and the resin substrate becomes uneven due to the unevenness, resulting in a matte surface. And in order to obtain the resin substrate which has such a matt surface, the compounding quantity (addition amount) of the surface roughening particle | grains in a resin coating is 1-10 mass parts with respect to 100 mass parts of silicone. Is preferred. Moreover, it is more preferable that the particle diameter of the surface roughened particles is 15 nm to 4 μm.

  The production method according to the present invention is as described above. However, in carrying out the present invention, other steps may be included between or before and after each step within a range that does not adversely affect each step. . For example, you may perform the washing | cleaning process which wash | cleans the surface of a plate-shaped carrier before an application | coating process.

  In the production process of a multilayer printed wiring board, heat treatment is often performed in a lamination press process or a desmear process. Therefore, the thermal history received by the laminate becomes more severe as the number of layers increases. Therefore, when considering application to a multilayer printed wiring board in particular, it is desirable that the peel strength between the resin substrates is in the above-described range even after passing through a required thermal history.

  Accordingly, in a further preferred embodiment of the present invention, the resin after heating at least one of 3 hours, 6 hours, or 9 hours, for example, at 220 ° C., assuming heating conditions in the production process of the multilayer printed wiring board. The peel strength between the substrates is preferably 30 gf / cm or more, and more preferably 50 gf / cm or more. The peel strength is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and even more preferably 80 gf / cm or less.

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

  In this invention, peel strength is measured based on the 90 degree peel strength measuring method prescribed | regulated to JISC6481.

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

Although there is no restriction | limiting in particular as a resin substrate, Although a phenol resin, a polyimide resin, an epoxy resin, natural rubber, pine resin, etc. can be used, it is preferable that it is a thermosetting resin. A prepreg can also be used. The prepreg before bonding is preferably in the B stage state. The linear expansion coefficient of the prepreg (C stage) is 12 to 18 (× 10 ⁻⁶ / ° C.), 16.5 (× 10 ⁻⁶ / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 (× 10 ⁻⁶ / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultra-thin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

  This thermosetting resin or prepreg preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimum range. For example, the glass transition temperature is 120 to 320 ° C, preferably 170 to 240 ° C. Tg. The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

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

  The thickness of the resin substrate is not particularly limited, and it may be rigid or flexible, but if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin it will bend and will not flow through the printed wiring board manufacturing process. Usually, it is 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.

  In the laminate of the present invention, at least one other resin substrate may be laminated on the exposed surface of at least one resin substrate. As other resin substrates, those described above can be used. Further, when “another resin substrate” is laminated, it may be in a state where it can be peeled off by the above-described method, or may be in a state where it cannot be peeled off by being bonded by a conventional method.

In the laminate of the present invention, a metal foil may be laminated on the exposed surface of at least one of the resin substrates present on the resurface.
As the metal foil, copper or copper alloy foil is typical, but foils of aluminum, nickel, zinc and the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used. Although not limited, the metal foil generally has a thickness of 1 [mu] m or more, preferably 5 [mu] m or more, and 400 [mu] m or less, preferably 120 [mu] m or less, considering use as a wiring of a printed circuit board. When metal foil is affixed on both surfaces of the plate-like carrier, metal foils having the same thickness may be used, or metal foils having different thicknesses may be used.

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

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

  Therefore, in a preferred embodiment of the laminate according to the present invention, in order to adjust the peel strength between the resin substrates to the preferred range described above, the surface roughness of the bonded surface is based on JIS B 0601: 2001. Expressed by the measured 10-point average roughness (Rz jis), it is preferably 3.5 μm or less, more preferably 3.0 μm or less. However, reducing the surface roughness indefinitely takes time and increases costs, so it is preferably 0.1 μm or more, and more preferably 0.3 μm or more.

  Moreover, in preferable one Embodiment of the laminated body which concerns on this invention, surface treatment for peeling strength improvement, such as a roughening process, is not performed with respect to the bonding surface of a resin substrate. Moreover, in one preferable embodiment of the laminate according to the present invention, a binder for increasing the adhesive strength is not added to the resin substrate.

As conditions for hot pressing for producing a laminate, when using a prepreg as a resin substrate, it is preferable to hot press at a pressure of 30 to 40 kg / cm ² and a temperature higher than the glass transition temperature of the prepreg.

  From the above viewpoints, the present invention provides the above-mentioned release agent on at least one surface of the resin base material as described above, which serves as the adhesion surface, in order to allow the resin-made plate carrier to be adhered in a peelable manner. A resin base material coated with a layer or a release material is provided. The surface of the resin substrate may be subjected to the chromate treatment as described above before coating with a compound having two or less mercapto groups in the molecule.

  From another viewpoint, the present invention provides a plate-like carrier having a layer made of the above-mentioned release agent or a release material on at least one surface of the plate-like carrier that serves as an adhesive surface of a resin substrate. This plate-like carrier can be suitably used for applications in which the above-described resin base material is detachably adhered.

  From still another aspect, the present invention provides a resin base material for a coreless multilayer printed wiring board in which the surface of the resin base material as described above is coated with a layer or a release material made of the above release agent. The surface of the resin substrate may be subjected to the chromate treatment as described above before being coated with a compound having two or less mercapto groups in the molecule.

  The surface of the resin substrate was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), and Si was detected. Then, it can be inferred that a silane compound is present on the surface of the resin substrate, and if S is detected, it is inferred that a compound having two or less mercapto groups in the molecule is present on the surface of the resin substrate. If Al, Ti, and Zr are detected, it can be assumed that the metal alkoxide is present on the surface of the resin substrate.

Furthermore, from another viewpoint, the present invention is the above-described laminate in which metal foil is laminated (hereinafter simply referred to as “laminate”. The laminate before the metal foil is laminated is also referred to as “lamination of metal foil”. Application of the "predetermined laminate".
First, a multilayer metal-clad laminate comprising laminating a resin on at least one metal foil side of the laminate described above, and then laminating the resin or metal foil one or more times, for example 1 to 10 times. A method of manufacturing a board is provided.

  Second, the resin is laminated on the metal foil side of the laminate described above, and then the resin, the laminate before laminating the metal foil of the present invention, the single-sided or double-sided metal-clad laminate, the laminate of the present invention, or the metal There is provided a method for producing a multilayer metal-clad laminate comprising laminating a foil one or more times, for example 1 to 10 times. In addition, the lamination after the resin first laminated on the laminate of the present invention is performed as many times as desired, and in each lamination, the laminate before laminating the resin and the metal foil of the present invention, single-sided or double-sided metal-clad It can be arbitrarily selected from the group consisting of a laminate, a laminate of the present invention different from the initial laminate, and a metal foil.

  In the manufacturing method of said multilayer metal-clad laminated board, the process of peeling and isolate | separating the resin substrates of the said laminated body can be further included.

  Furthermore, after peeling and separating the resin substrates, a step of removing a part or all of the resin substrates by etching can be further included.

  Third, a resin is laminated on at least one metal foil side of the laminate described above, and then the resin, the laminate before laminating the metal foil of the present invention, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate There is provided a method for producing a build-up substrate, which includes laminating a plate, a laminate of the present invention, or a metal foil repeatedly at least once, for example, 1 to 10 times. In addition, the lamination after the resin first laminated on the laminate of the present invention is performed as many times as desired, and in each lamination, the laminate before laminating the resin and the metal foil of the present invention, single-sided or double-sided metal-clad It can be arbitrarily selected from the group consisting of a laminate, a laminate of the present invention different from the initial laminate, and a metal foil.

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

  The subtractive method is a method of forming a conductor pattern by selectively removing unnecessary portions of metal foil on a metal-clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like. Point to. The full additive method is a method of forming a conductor pattern by electroless plating and / or electrolytic plating without using a metal foil for the conductor layer. The semi-additive method is a method of forming a conductive pattern on a seed layer made of metal foil, for example. In this method, a conductive pattern is formed by using electrolytic metal deposition and electrolytic plating, etching, or a combination thereof, and then the unnecessary seed layer is removed by etching.

  In the build-up board manufacturing method, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a laminated metal foil, a laminated resin substrate, a metal foil, or a resin The method may further include conducting a conductive plating on the side surface and the bottom surface. A step of forming wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, the metal foil constituting the laminate, or the metal foil; It may further include performing one or more times.

In the manufacturing method of said buildup board | substrate, the process of laminating | stacking the resin substrate side of the laminated body which concerns on this invention which made metal foil closely_contact | adhere on one side can also be further included on the surface in which wiring was formed. Moreover, the process of laminating | stacking resin on the surface in which wiring was formed, and laminating | stacking the laminated body based on this invention which made metal foil adhere | attach both surfaces on the said resin can also be further included.
The “surface on which the wiring is formed” means a portion where wiring is formed on the surface that appears every time a buildup is performed, and the buildup substrate includes both a final product and an intermediate product.

  In the manufacturing method of said buildup board | substrate, the process of peeling and isolate | separating the resin substrates of the said laminated body can further be included.

  Furthermore, after peeling and separating the resin substrates, a step of removing a part or all of the resin substrates by etching can be further included.

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

  In particular, the present invention provides a method for manufacturing a build-up board as described above, wherein a hole is made in a single-sided or double-sided wiring board, a single-sided or double-sided copper-clad laminate, a metal foil or a resin, and conductive plating is performed on the side and bottom surfaces of the hole. Further, the metal foil and circuit portion constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided copper-clad laminate, and the method for producing a build-up board at least including the step of forming a circuit on the metal foil I will provide a.

  Hereinafter, as a specific example of the above-described application, a method for producing a four-layer metal-clad laminate using the laminate according to the present invention will be described. The laminate used here is the laminate 11 in which the resin substrate 11c and the resin substrate 11a are in close contact. On this laminate 11, a desired number of prepregs 12, then a two-layer printed circuit board or two-layer metal-clad laminate called an inner core 13, and then a prepreg 12 and then a laminate 11 are sequentially stacked to form a set. A four-layer metal-clad laminate assembly unit is completed. Next, the unit 14 (commonly called “page”) is repeated about 10 times to form a press assembly 15 (commonly called “book”) (FIG. 3). Thereafter, a large number of four-layer metal-clad laminates can be produced simultaneously by sandwiching the book 15 between the laminated molds 10 and setting the book 15 in a hot press machine, followed by pressure molding at a predetermined temperature and pressure. As the laminated mold 10, for example, a stainless plate can be used. Although a plate is not limited, For example, a thick board about 1-10 mm can be used. A metal-clad laminate having four or more layers can generally be produced in the same process by increasing the number of inner core layers.

  Hereinafter, as a specific example of the above-described application, a method for producing a coreless build-up substrate using the laminate before laminating the metal foil according to the present invention will be exemplarily described. In this method, after a required number of buildup layers 16 are laminated on both sides of a laminate 11 formed by bonding two resin substrates 11a using a layer made of a release agent or a release material 11b, the resin substrate of the laminate 11 is obtained. 11a is separated (see FIG. 4).

  For example, on the metal foil side of the laminate in which the metal foil of the present invention is laminated, a resin as an insulating layer, a two-layer circuit board, and a resin as an insulating layer are sequentially stacked so that the metal foil side is in contact with the resin. A build-up substrate can be manufactured by stacking the metal foils of the laminated body in which the metal foils of the present invention are laminated in order.

As another method, as an insulating layer, at least one metal foil side of the laminate in which the metal foil is adhered to both surfaces or one surface of the laminate in which two resin substrates are detachably bonded to each other is used. A resin and a metal foil as a conductor layer are sequentially laminated. Next, if necessary, a step of half-etching the entire surface of the metal foil to adjust the thickness may be included. Next, laser processing is performed at a predetermined position of the laminated metal foil to form a via hole penetrating the metal foil and the resin, and after applying a desmear process for removing smear in the via hole, the bottom of the via hole, the side surface and the metal foil Electroless plating is performed on the entire surface or a part of the substrate to form an interlayer connection, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the metal foil where electroless plating or electrolytic plating is unnecessary before performing each plating. In addition, when the electroless plating, the electrolytic plating, or the adhesion between the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. When a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the metal foil and the electroless plating portion and the electrolytic plating portion by etching. In this way, a build-up substrate can be manufactured. The steps from the lamination of the resin and the copper foil to the circuit formation may be repeated a plurality of times to form a multilayer build-up substrate.
Furthermore, on the outermost surface of this build-up substrate, the resin side of the metal foil of the laminate in which the metal foil is adhered to one surface of the present invention may be contacted and laminated, or after the resin is once laminated, You may laminate | stack by contacting one metal foil of the laminated body which made metal foil contact | adhere to both surfaces of invention.

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

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

  For the coreless build-up board manufactured in this way, the wiring is formed on the surface through the plating process and / or the etching process, and the build-up wiring board is separated by separating the two resin boards. Complete. After peeling and separating, the metal foil may be laminated on the peeling surface of the resin substrate, and then wiring may be formed, or the entire surface of the metal foil may be removed by etching to form a build-up wiring board. Furthermore, a printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, a printed circuit board can be obtained even if an electronic component is mounted directly on a coreless buildup substrate before resin peeling.

  Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

<Experimental example 1>
Prepare two prepregs (FR-4 resin) made by Nanya Plastic Co. as a resin substrate, apply the release agent listed in Table 1 on the surface of one prepreg, and bond the other prepreg together The laminate was manufactured by hot pressing at 170 ° C. for 100 minutes.

Regarding the release agent treatment, an aqueous solution of the release agent is applied using a spray coater, and then the surface of the prepreg coated with the release agent in air at 100 ° C. is dried, and then the other prepreg is used. Bonding was performed. Regarding the use conditions of the release agent, the type of release agent, the stirring time from when the release agent is dissolved in water to before application, the concentration of the release agent in the aqueous solution, the alcohol concentration in the aqueous solution, the pH of the aqueous solution Is shown in Table 1.
Moreover, after forming the release agent resin coating film on the surface of one prepreg by the gravure coating method, the thickness of the resin coating film having the composition shown in Table 1 is set to 2 to 2 by using a doctor blade. Adjusted to 4 μm. Moreover, the applied resin coating film was baked by heating at 150 ° C. for 30 seconds. The epoxy resin shown in Table 1 is a bisphenol A type epoxy resin, the melamine resin is a methyl etherified melamine resin, the fluororesin is polytetrafluoroethylene, and the dimethyl silicone resin is dimethyl Polysiloxane was used.

  In addition, assuming that the laminated body has a thermal history during the further heat treatment such as circuit formation for the laminated body, heat treatment under the conditions described in Table 1 (here, 220 ° C. for 3 hours) Went.

  The peel strength between prepregs in the laminate obtained by hot pressing and in the laminate after further heat treatment was measured. The results are shown in Table 1.

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

<Experimental Examples 2 to 11>
Using a resin substrate (prepreg) and a release agent shown in Table 1, a laminate was produced in the same procedure as in Experimental Example 1. In Experimental Examples 3, 7, and 10, the release agent was applied on the resin substrate. Moreover, the heat processing of the conditions shown in Table 1 was performed. Each was evaluated in the same way as in Experimental Example 1. The results are shown in Tables 1 and 2.

  The types of the resin substrate, surface treatment conditions and surface roughness Rz jis, use conditions of the release agent, and lamination conditions are as shown in Table 1.

(Build-up wiring board)
Copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., JTC 12 μm (product name)), FR-4 prepreg (manufactured by Nanya Plastic Co.) and copper foil (JX Nippon Mining) Nisseki Metal Co., Ltd., JTC 12 μm (product name)) was stacked in order, and hot pressing was performed under the heating conditions shown in each table at a pressure of 3 MPa to prepare a four-layer copper-clad laminate.

  Next, a 100 μm diameter hole penetrating the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine. Subsequently, copper plating is performed by electroless copper plating and electrolytic copper plating on the copper foil surface on the laminate exposed at the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper-clad laminate. An electrical connection was formed between the copper foil on the laminate and the copper foil on the surface of the four-layer copper clad laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. In this way, a four-layer buildup substrate was obtained.

  Subsequently, in the four-layer buildup substrate, two sets of two-layer buildup wiring boards were obtained by peeling and separating the resin substrates of the laminate.

  Subsequently, a 100 μm diameter hole penetrating the resin substrate on the two sets of two-layer build-up wiring boards that had formed the laminate was drilled using a laser processing machine. Then, after performing the desmear process to the said resin substrate, the plating resist was formed in locations other than the location which forms wiring on the said resin substrate. Subsequently, the copper foil surface exposed at the bottom of a through hole having a diameter of 100 μm formed on the resin substrate constituting the laminated body, the side surface of the hole, and the resin substrate constituting the laminated body are not present. After performing copper plating by electrolytic copper plating and electrolytic copper plating, the plating resist is removed to form a circuit on the surface of the resin substrate constituting the laminate, and the resin substrate constituting the laminate An electrical connection is formed between the copper foil exposed at the bottom of the through-hole having a diameter of 100 μm and the circuit on the surface of the resin substrate constituting the laminate, and two sets of three-layer build-up wiring boards Got.

In each experimental example, a plurality of four-layer buildup substrates were produced, and for each, the degree of adhesion between the prepregs constituting the laminate in the buildup substrate manufacturing process was visually confirmed. In the build-up wiring board using the laminate manufactured under the condition that the peel strength of the laminate was evaluated as “G”, the resin substrate of the laminate could be peeled without being destroyed during the build-up.
In addition, regarding the condition evaluated as “N”, the resin substrate was destroyed at the time of the build-up operation of the resin substrate in the laminated body, or one of the other resin substrates was not removed on the surface of one resin substrate. Department remained.
In addition, regarding the conditions evaluated as “-”, the resin was peeled off without being destroyed during the peeling operation of the resin substrate in the laminate during build-up, but the resin substrate was peeled off without the peeling operation. was there.

DESCRIPTION OF SYMBOLS 10 Laminated metal mold 11 Laminated body 11a Resin substrate 11b Release layer or release material 11c Resin substrate 12 Prepreg 13 Inner core 14 Page 15 Book 16 Build-up layer

Claims (29)

  A laminate in which a release agent is interposed between two resin substrates, and these resin substrates are detachably adhered to each other.   The laminate according to claim 1, wherein the peel strength between the resin substrates is 10 gf / cm or more and 200 gf / cm or less.   The laminate according to claim 1 or 2, wherein the resin substrate has a glass transition temperature Tg of 120 to 320 ° C.   The peel strength between the resin substrates after heating at least one of 3 hours, 6 hours, or 9 hours at 220 ° C is 10 gf / cm or more and 200 gf / cm or less. The laminate according to one item. The laminate according to any one of claims 1 to 4, wherein the release agent is at least one selected from the group consisting of the following (1) to (4).
(1) Silane compounds

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
A silane compound, a hydrolysis product thereof, or a condensate of the hydrolysis product, alone or in combination;
(2) a compound having two or less mercapto groups in the molecule;
(3) Metal alkoxide

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
An aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, a condensate of the hydrolysis product alone or in combination, and (4) silicone, an epoxy resin, a melamine resin, and A composition comprising any one or more resins selected from fluororesins.   The laminate according to claim 1, wherein the resin substrate has a thickness of 5 μm or more and 1000 μm or less.   The laminated body formed by laminating | stacking at least 1 other resin substrate on the exposed surface of at least one resin substrate of the laminated body as described in any one of Claims 1-6.   The laminate according to any one of claims 1 to 7, wherein the resin substrate is obtained by curing a thermosetting resin.   The laminate according to any one of claims 1 to 8, wherein the resin substrate is a prepreg.   The laminated body formed by laminating | stacking metal foil on the exposed surface of at least one resin substrate which exists in the resurface of the laminated body as described in any one of Claims 1-9.   The laminate according to claim 10, wherein the metal foil is a copper foil.   A method for producing a multilayer metal-clad laminate comprising laminating a resin on at least one metal foil side of the laminate according to claim 10 or 11 and then laminating the resin or metal foil one or more times. .   A resin is laminated on the metal foil side of the laminate according to claim 10 or 11, and then the resin, the laminate according to any one of claims 1 to 9, a single-sided or double-sided metal-clad laminate, A method for producing a multilayer metal-clad laminate comprising laminating a laminate according to 10 or 11 or a metal foil repeatedly at least once.   The method for producing a multilayer metal-clad laminate according to claim 12 or 13, further comprising a step of separating and separating the resin substrates in the laminate to be peelably adhered to each other. .   The method for producing a multilayer metal-clad laminate according to claim 14, comprising a step of removing a part or all of the separated and separated resin substrate by etching.   The multilayer metal-clad laminate obtained by the manufacturing method as described in any one of Claims 12-15.   The manufacturing method of the buildup board | substrate including the process of forming one or more buildup wiring layers in the at least 1 metal foil side of the laminated body of Claim 10 or 11.   The buildup wiring layer according to claim 17, wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semiadditive method.   A resin is laminated on at least one metal foil side of the laminate according to claim 10 or 11, and then the resin, the laminate according to any one of claims 1 to 9, a single-sided or double-sided wiring board, a single-sided or The manufacturing method of the buildup board | substrate including repeatedly laminating | stacking a double-sided metal-clad laminate, the laminated body of Claim 10 or 11, or metal foil once or more.   In the manufacturing method of the buildup board according to claim 19, a hole is made in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a laminated metal foil, a laminated resin substrate, a metal foil, or a resin, A method for manufacturing a build-up substrate, further comprising a step of conducting plating on the side surface and bottom surface of the hole.   The build-up board manufacturing method according to claim 19 or 20, wherein the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil constituting the laminate, And the manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil once or more.   The process of laminating | stacking one resin board | substrate side of the laminated body as described in any one of Claims 1-9 which made metal foil closely_contact | adhere on the surface in which wiring was formed. The manufacturing method of the buildup board | substrate as described in any one of these.   The method further comprising the step of laminating the laminate according to any one of claims 1 to 9, wherein a resin is laminated on the surface on which the wiring is formed, and a metal foil is adhered to both sides of the resin. The manufacturing method of the buildup board | substrate as described in any one of -21.   The method for manufacturing a buildup substrate according to any one of claims 19 to 23, wherein at least one of the resin substrates is a prepreg.   25. The buildup wiring board manufacturing method according to any one of claims 17 to 24, further comprising a step of separating and separating the resin substrates that are detachably adhered to each other in the laminate. Production method.   26. The method for manufacturing a buildup wiring board according to claim 25, further comprising a step of removing a part or all of the separated and separated resin substrate by etching.   A build-up wiring board obtained by the manufacturing method according to claim 25 or 26.   The manufacturing method of a printed circuit board including the process of manufacturing a buildup board | substrate by the method as described in any one of Claims 17-24.   A method for manufacturing a printed circuit board, comprising a step of manufacturing a build-up wiring board by the manufacturing method according to claim 25 or 26.

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