JP2013058724A - Manufacturing method of printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a printed wiring board excellent in initial adhesiveness and temporal stability of adhesiveness of an insulating resin layer.SOLUTION: A manufacturing method of a printed wiring board comprises: a first coating step of coating a surface of an insulating substrate 12 and a surface of a metal wiring 14 of an insulating substrate 10 with a metal wiring with a thiol compound having a prescribed functional group; a first cleaning step of removing a thiol compound 16 on the surface of the insulating substrate 10 by cleaning the insulating substrate 10 with a metal wiring with a solvent; a second coating step of coating the surface of the metal wiring 14 coated by the thiol compound 16 and the surface of the insulating substrate 10 with a polymer 20 having a prescribed functional group; a second cleaning step of removing the polymer 20 from the surface of the insulating substrate 12 by cleaning the insulating substrate 10 with a metal wiring with a solvent; and an insulating resin layer formation step of forming an insulating resin layer 24 on a surface of the metal wiring 14 side of the insulating substrate 10 with a metal wiring.

Description

  The present invention relates to a method for manufacturing a printed wiring board.

  2. Description of the Related Art In recent years, with the demand for higher functionality of electronic devices and the like, electronic components have been integrated at high density, and printed wiring boards and the like used for these have been downsized and increased in density. Under such circumstances, the metal wiring width in the printed wiring board is also narrowed.

Usually, a printed wiring board is obtained by laminating one or more metal wirings and insulating resin layers. At that time, if the adhesion between the metal wiring and the insulating resin layer is insufficient, a gap will be formed between the metal wiring and the insulating resin layer. Cause short circuit.
Conventionally, as a technique for improving the adhesion between the metal wiring and the insulating resin layer, a technique for roughening the surface of the metal wiring and generating an anchor effect has been used. However, under the current situation where the width of the metal wiring is narrowing, there is a problem that it is difficult to roughen the surface of the metal wiring and the high frequency characteristics are deteriorated due to the formed unevenness. .

  Therefore, as a method of improving the adhesion between the metal wiring and the insulating resin layer without roughening the surface of the metal wiring, a method of treating the metal wiring surface with a triazine thiol derivative (Patent Document 1), or a mercapto group A method (Patent Document 2) for treating a metal wiring surface with a silane coupling agent is proposed.

JP 2000-156563 A Japanese Patent Laid-Open No. 11-354922

  The present inventors use a triazine thiol compound (thiocyanuric acid) specifically disclosed in Patent Document 1 or a mercaptopropyltrimethoxysilane specifically disclosed in Patent Document 2 to form an insulating resin layer. As a result of studies on the adhesion, it has been found that the strength of the adhesion greatly decreases with time, and further improvement is necessary.

  In view of the above circumstances, an object of the present invention is to provide a method for manufacturing a printed wiring board excellent in initial adhesion of an insulating resin layer and stability over time of the adhesion of the insulating resin layer.

As a result of intensive studies, the present inventors have processed a metal wiring by using a thiol compound having a predetermined functional group, and then further processing the metal wiring with a polymer having a predetermined functional group. It has been found that the stability over time of the adhesion between the resin and the insulating resin layer is improved.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) It has two or more reactive functional groups X (excluding silanol groups and silicon atom-bonded hydrolyzable groups), and at least one of the reactive functional groups X is represented by the formula (1) described later. A first covering step of covering the insulating substrate surface and the metal wiring surface of the insulating substrate with the metal wiring having the insulating substrate and the metal wiring disposed on the insulating substrate using a thiol compound having a functional group;
A first cleaning step of cleaning the insulating substrate with metal wiring using a solvent to remove a thiol compound on the surface of the insulating substrate;
A second coating step of covering the insulating substrate surface and the metal wiring surface covered with the thiol compound using a polymer having at least three reactive functional groups Y that react with the reactive functional group X;
A second cleaning step of cleaning the insulating substrate with metal wiring using a solvent to remove the polymer on the surface of the insulating substrate;
A method for manufacturing a printed wiring board, comprising: an insulating resin layer forming step of forming an insulating resin layer on a surface of a metal wiring side of an insulating substrate with metal wiring, wherein the insulating resin layer is provided on the insulating substrate with metal wiring.

(2) The method for producing a printed wiring board according to (1), wherein the polymer has a number average molecular weight of 10,000 or more.
(3) The reactive functional group X is a group selected from the group consisting of a functional group represented by the following formula (1), a primary amino group, a secondary amino group, and an isocyanate group, (1 ) Or the method for producing a printed wiring board according to (2).
(4) The method for producing a printed wiring board according to any one of (1) to (3), wherein the reactive functional group Y is a group selected from the group consisting of an epoxy group, an acrylate group, and a methacrylate group. .

(5) The second coating step is a step of covering the insulating substrate surface and the metal wiring surface covered with the thiol compound using a polymer composition containing a polymer and substantially free of an inorganic filler. The manufacturing method of the printed wiring board in any one of (1)-(4).
(6) The manufacturing method of the printed wiring board as described in (5) whose content of the polymer in the said polymer composition is 0.01-80 mass% with respect to the polymer composition whole quantity.
(7) The manufacturing method of the printed wiring board in any one of (1)-(6) whose number of the said reactive functional groups X is four or more.
(8) An IC package substrate having a printed wiring board obtained by the manufacturing method according to any one of (1) to (7).

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the printed wiring board excellent in the initial time adhesiveness of an insulating resin layer and the temporal stability of the adhesiveness of an insulating resin layer can be provided.

It is typical sectional drawing from the board | substrate which shows each process in the manufacturing method of the printed wiring board of this invention in order to a printed wiring board. It is typical sectional drawing showing another aspect of the insulated substrate with metal wiring. It is typical sectional drawing showing the aspect which implemented various processes using the silane coupling agent which has a silicon atom bond hydrolysable group.

Below, the suitable embodiment of the manufacturing method of the printed wiring board of this invention is demonstrated.
First, the feature point compared with the prior art of this invention is explained in full detail.
A feature of the present invention is that the thiol compound has two or more reactive functional groups X, and at least one of the reactive functional groups X has a functional group represented by the formula (1) described later (hereinafter, simply After the metal wiring is treated with a thiol compound), the metal wiring is further treated with a polymer having three or more reactive functional groups Y that react with the reactive functional group X in the molecule (hereinafter also simply referred to as a polymer). A point is mentioned. That is, the surface of the metal wiring is covered with a thiol compound layer, and the thiol compound layer is further covered with a polymer layer. The thiol compound and the polymer serve to assist the adhesion between the metal wiring and the insulating resin layer (the role of the adhesion auxiliary layer).
The thiol compound is bonded to the metal wiring via the reactive functional group X (particularly, the group represented by the formula (1)). Furthermore, a polymer couple | bonds with a thiol compound via the reactive functional group Y, and the network structure (network structure) of a thiol compound and a polymer is formed on a metal wiring.

As described above, when a network structure of thiol compound and polymer is formed between the metal wiring and the insulating resin layer, it becomes difficult for moisture and the like to approach the metal wiring, and oxidation and corrosion of the metal wiring are suppressed. As a result, the temporal stability of the adhesiveness of the insulating resin layer is improved.
Moreover, when a polymer intervenes between a metal wiring and an insulating resin layer, it plays a role of alleviating the difference in thermal expansion between the two. In other words, the polymer plays a role of so-called stress relaxation, and as a result, the temporal stability of the adhesiveness of the insulating resin layer is improved.

  Another feature of the production method of the present invention is that after the thiol compound or polymer is brought into contact with the insulating substrate with metal wiring, cleaning is further performed using a solvent (cleaning solvent). If the unreacted physisorbed thiol compound or polymer remains on the insulating substrate, the present inventors may cause poor adhesion between the insulating resin layer and the insulating substrate, causing a short circuit. Is heading. As a result of examination based on the above knowledge, it is possible to secure the adhesion between the metal wiring and the insulating resin layer while removing the thiol compound and polymer on the insulating substrate by performing the treatment as in the present invention. Heading.

For example, a silane coupling agent having a silicon atom-bonded hydrolyzable group (specifically, alkoxysilane group) such as mercaptopropyltrimethoxysilane used in the prior art was used instead of the thiol compound. In this case, the silane coupling agent forms a chemical reaction not only with the metal wiring but also with the insulating substrate. Therefore, even if a cleaning process using a solvent is performed, it is difficult to remove the silane coupling agent from the insulating substrate. Specifically, as shown in FIG. 3A, not only the metal wiring 14 but also the insulating substrate 12 is covered with the silane coupling agent 60.
Furthermore, when a polymer is deposited on the insulating substrate, the silane coupling agent and the polymer are chemically bonded, and the polymer on the insulating substrate cannot be removed by the solvent. Specifically, as shown in FIG. 3B, a polymer 62 is deposited on the silane coupling agent 60.
When such a silane coupling agent or polymer is deposited on the surface of the insulating substrate, poor adhesion between the insulating resin layer and the insulating substrate occurs as described above, causing a short circuit.

First, the manufacturing method of the printed wiring board of this invention is explained in full detail, and the aspect of the printed wiring board manufactured after that is explained in full detail.
The method for manufacturing a printed wiring board of the present invention includes a first covering step, a first cleaning step, a second covering step, a second cleaning step, and an insulating resin layer forming step.
Below, with reference to drawings, the material used at each process and the procedure of a process are explained in full detail.

[First coating step]
The first coating step has two or more reactive functional groups X (excluding silanol groups and silicon atom-bonded hydrolyzable groups), and at least one of the reactive functional groups is represented by the formula (1) described later. This is a step of covering the insulating substrate surface and the metal wiring surface of the insulating substrate with the metal wiring having the insulating substrate and the metal wiring arranged on the insulating substrate using a thiol compound having a functional group represented by In other words, it is a step of covering the surface of the insulating substrate with metal wiring (particularly the surface on the metal wiring side) with a thiol compound. Through this step, a thiol compound layer (thiol compound layer) 16 is formed on the surface of the insulating substrate 12 and the surface of the metal wiring 14 of the insulating substrate with metal wiring 10 shown in FIG. B)). In particular, the thiol compound on the metal wiring 14 is bonded to the surface of the metal wiring 14 mainly through a group represented by the formula (1).
First, the materials (insulating substrate with metal wiring, thiol compound) used in this step will be described, and then the procedure of the step will be described.

(Insulated substrate with metal wiring)
The insulating substrate with metal wiring (inner layer substrate) used in this step has an insulating substrate and metal wiring arranged on the insulating substrate. In other words, the insulating substrate with metal wiring may have a laminated structure having at least an insulating substrate and metal wiring, and the metal wiring may be disposed in the outermost layer. FIG. 1A shows an embodiment of an insulating substrate with metal wiring. The insulating substrate 10 with metal wiring includes an insulating substrate 12 and a metal wiring 14 disposed on the insulating substrate 12. In FIG. 1A, the metal wiring 14 is provided only on one side of the substrate, but may be provided on both sides. That is, the insulating substrate 10 with metal wiring may be a single-sided substrate or a double-sided substrate.
In addition, when the metal wiring 14 is on both surfaces of the insulating substrate 10, the first covering step, the first cleaning step, the second covering step, the second cleaning step, and the insulating resin layer forming step are performed on both surfaces of the substrate. To be implemented.

The insulating substrate is not particularly limited as long as it is insulative and can support metal wiring. For example, an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.
Resin is mentioned as a material of an organic substrate, For example, it is preferable to use a thermosetting resin, a thermoplastic resin, or resin which mixed them. Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, furan resin, ketone resin, xylene resin, benzocyclo Examples include butene resin. Examples of the thermoplastic resin include polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer.
In addition, as a material of the organic substrate, a glass woven fabric, a glass nonwoven fabric, an aramid woven fabric, an aramid nonwoven fabric, an aromatic polyamide woven fabric, a material impregnated with the above resin, or the like can be used.

The metal wiring is mainly composed of metal. The type of metal is not particularly limited, and examples thereof include copper or copper alloy, silver or silver alloy, tin, palladium, gold, nickel, chromium, platinum, iron, gallium, indium, and combinations thereof.
The method for forming the metal wiring on the insulating substrate is not particularly limited, and a known method can be adopted. Typically, a subtractive method using an etching process and a semi-additive method using electrolytic plating can be given.
The metal wiring may contain an organic substance such as a binder resin as long as the effects of the present invention are not impaired.

The width of the metal wiring is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.1 to 25 μm, and still more preferably 0.1 to 10 μm from the viewpoint of high integration of the printed wiring board.
The distance between the metal wirings is not particularly limited, but is preferably 0.1 to 1000 μm, more preferably 0.1 to 25 μm, and still more preferably 0.1 to 10 μm from the viewpoint of high integration of the printed wiring board.
Further, the pattern shape of the metal wiring is not particularly limited, and may be an arbitrary pattern. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, and the like can be given.
The thickness of the metal wiring is not particularly limited, but is preferably 1 to 1000 μm, more preferably 3 to 25 μm, and still more preferably 10 to 20 μm from the viewpoint of high integration of the printed wiring board.

In the present invention, initial adhesion of an insulating resin layer to be described later can be ensured without roughening the surface of the metal wiring. Therefore, the surface roughness Rz of the metal wiring is not particularly limited, but is preferably 10 μm or less, more preferably 0.001 to 2.0 μm, and more preferably 0.01 to 0. 9 μm is more preferable, and 0.02 to 0.5 μm is particularly preferable.
Rz is measured according to JIS B 0601 (1994).

  Another aspect of the insulating substrate with metal wiring used in this step is a multilayer wiring substrate having two or more insulating substrates and two or more metal wirings alternately. For example, the multilayer wiring board may include another metal wiring 50 (metal wiring layer) and another insulating board 40 in this order between the insulating substrate 12 and the metal wiring 14 (see FIG. 2). The other metal wiring 50 and the other insulating substrate 40 may be alternately included in two layers or more in this order between the insulating substrate 12 and the metal wiring 14.

  The insulating substrate with metal wiring may be a so-called rigid substrate, flexible substrate, or rigid flexible substrate.

  In addition, a through hole may be formed in the insulating substrate. When metal wiring is provided on both surfaces of the insulating substrate, the metal wiring on both surfaces may be made conductive by filling the through hole with metal (for example, copper or copper alloy).

(Thiol compound)
The thiol compound used in this step has two or more reactive functional groups X (excluding silanol groups and silicon-bonded hydrolyzable groups), and at least one of the reactive functional groups X will be described later. It has a functional group represented by the formula (1). By surface-treating the metal wiring using the compound, the initial adhesiveness of the insulating resin layer laminated thereon and the temporal stability of the adhesiveness of the insulating resin layer can be improved.

The reactive functional group X which a thiol compound has should just be a functional group which reacts with the reactive functional group Y which the polymer mentioned later has. Examples thereof include a functional group represented by the formula (1), a primary amino group, a secondary amino group, an isocyanate group, a carboxylic acid, or a hydroxyl group.
Among them, the functional group, the primary amino group, the secondary amino group, and the isocyanate group represented by the formula (1) are more excellent in reactivity and more stable over time in the adhesiveness of the insulating resin layer. A group selected from the group consisting of In particular, the group represented by the formula (1) is more preferable.

However, the reactive functional group X does not include a silanol group or a silicon atom-bonded hydrolyzable group. The silanol group means a group (—Si—OH) in which a hydroxyl group is directly bonded to a silicon atom. The silicon atom-bonded hydrolyzable group means a hydrolyzable group bonded to a silicon atom (for example, an alkoxysilane group (—Si—OR (R: alkyl group) in which an alkoxy group is directly bonded to a silicon atom). Examples of hydrolyzable groups include alkoxy groups; hydrocarbon oxy groups; acyloxy groups; halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms; isocyanate groups; cyano groups; amino groups; Etc. can be illustrated.
If these groups are contained in the thiol compound, a hydrophilic silica network structure is formed on the surface of the metal wiring. When such a network is present, water easily comes into contact with the surface of the metal wiring, and as a result, the surface of the metal wiring is corroded, and the temporal stability of the adhesion with the insulating resin layer is impaired. In addition, a silica network structure is formed on the insulating substrate, and the insulation reliability is significantly reduced.

The thiol compound contains two or more reactive functional groups X. By including two or more reactive functional groups X, one of the reactive functional groups X can form a bond with the surface of the metal wiring, and the other reactive functional group X can bond to the polymer described later. it can.
Among them, the number of reactive functional groups X is preferably 3 or more, more preferably 3 to 20 in terms of further improving the initial adhesion of the insulating resin layer and the temporal stability of the adhesion of the insulating resin layer. 4 to 10 are more preferable, and 4 to 6 are particularly preferable.
When the number of the reactive functional groups X is 1, the initial adhesiveness of the insulating resin layer is extremely inferior.

  As the reactive functional group X of the thiol compound, at least one functional group represented by the following formula (1) is included. When the thiol compound has at least one of the functional groups, the initial adhesion of the insulating resin layer is improved.

L ¹ in the formula (1) represents a divalent aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Especially, C1-C20 is preferable, C2-C10 is more preferable, and C4-C8 is especially preferable at the point which the temporal stability of the adhesiveness of an insulating resin layer improves more.
More specific examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, a propylene group, an isopropylene group, and a butylene group.
In particular, the HS group in the formula (1) is preferably a primary thiol in terms of further improving the temporal stability of the adhesiveness of the insulating resin layer (that is, in L ¹ directly bonded to the HS group). The partial structure is preferably —CH ₂ —.

  On the other hand, in the case of a disulfide group such as —S—SH, or a group in which an HS group is bonded to a triazine ring or a benzene ring, the activity of the HS group is low. Therefore, when a compound having these groups is used, the initial adhesiveness of the insulating resin layer is extremely inferior.

The reactive functional group X equivalent (g / eq) of the thiol compound is not particularly limited, but is preferably 2100 or less from the viewpoint that the initial adhesion of the insulating resin layer or the temporal stability of the adhesion of the insulating resin layer is more excellent. 400 or less is more preferable, and 250 or less is more preferable. In addition, although it does not restrict | limit in particular regarding a minimum, Usually, it is often over 40 from the point on the synthesis | combination of a thiol compound.
In addition, reactive functional group X equivalent represents the magnitude | size of the molecule | numerator per unit quantity of the reactive functional group X contained in a thiol compound.

  Although the molecular weight of the thiol compound is not particularly limited, it is preferably 8400 or less, more preferably 3000 or less, and particularly preferably 2000 or less, from the viewpoint that the initial adhesiveness of the insulating resin layer is more excellent and the solubility in a solvent is excellent. In addition, although it does not restrict | limit in particular regarding a minimum, Usually, it is often over 80 from the point on the synthesis | combination of a thiol compound.

The sulfur atom content (sulfur atom content ratio) in the thiol compound is not particularly limited, but is preferably 20 wt% or more, more preferably 24 to 70 wt%, in that the stability over time of the adhesiveness of the insulating resin layer is more excellent. . Especially, it is preferable that it is 35 wt% or more at the point which the temporal stability of the adhesiveness of an insulating resin layer is excellent, and 35-64 wt% is more preferable.
In addition, this sulfur atom content represents content (mass%) of the sulfur atom in the total molecular weight of a thiol compound.

(Preferred embodiment of thiol compound)
As a suitable aspect of a thiol compound, the thiol compound represented by the following formula | equation (2) is mentioned. If it is this compound, the initial adhesiveness of an insulating resin layer or the temporal stability of the adhesiveness of an insulating resin layer is more excellent.

In formula (2), L ¹ has the same meaning as L ¹ in formula (1) described above, and the preferred range is also the same as above.
In formula (2), L ² and L ³ each independently represent a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms), -O-, -S —, —SO ₂ —, —N (R) — (R: alkyl group), —CO—, —NH—, —COO—, —CONH—, or a combination thereof (eg, alkyleneoxy group, alkylene Oxycarbonyl group, alkylenecarbonyloxy group, etc.).
Examples of the divalent aliphatic hydrocarbon group (for example, an alkylene group) include a methylene group, an ethylene group, a propylene group, or a butylene group.
Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthylene group.

Among these, L ² and L ³ are divalent aliphatic hydrocarbon groups, —CO—, —O—, —S—, or a combination thereof, in that the initial adhesion of the insulating resin layer is more excellent. It is preferable that

In the formula (2), R ¹ represents a group selected from the group consisting of the functional group represented by the above formula (1), a primary amino group, a secondary amino group, and an isocyanate group.

In formula (2), n represents an integer of 1 or more. Especially, 1-19 are preferable, 2-9 are more preferable, and 3-7 are more preferable at the point which is easy to synthesize | combine and the initial adhesiveness of an insulating resin layer is more excellent.
In formula (2), m represents an integer of 1 or more. Especially, 1-19 are preferable, 1-9 are more preferable, and 1-5 are more preferable at the point which is easy to synthesize | combine and the initial adhesiveness of an insulating resin layer is more excellent.
n + m is not particularly limited, but is preferably 3 or more, more preferably 3 to 20, still more preferably 4 to 10, and particularly preferably 4 to 8.

In the formula (2), X represents an n + m-valent hydrocarbon group that may contain a sulfur atom, a nitrogen atom, or an oxygen atom.
The number of carbon atoms of the hydrocarbon group is not particularly limited, but is preferably 1 to 20 carbon atoms, and more preferably 1 to 8 carbon atoms from the viewpoints of handleability and solubility in a solvent. More specifically, examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group obtained by combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic, and preferably has 1 to 10 carbon atoms and 1 carbon atom in terms of excellent handleability and better solubility in a solvent. ~ 8 is more preferred.
It does not restrict | limit especially as an aromatic hydrocarbon group, C1-C10 is preferable and C1-C7 is more preferable at the point which is excellent in handleability and more soluble in a solvent.

  A more preferred embodiment of the thiol compound is a thiol compound represented by the following formula (3). If it is this compound, the initial adhesiveness of an insulating resin layer or the temporal stability of the adhesiveness of an insulating resin layer will improve more.

In formula (3), L ¹ has the same meaning as L ¹ in formula (1) described above, and the preferred range is also the same as above.
In formula (3), L ² has the same meaning as L ² in formula (2) described above, and the preferred range is also the same as above.
In formula (3), Y represents a p-valent aliphatic hydrocarbon group which may contain a sulfur atom, a nitrogen atom, or an oxygen atom. The definition of an aliphatic hydrocarbon group is synonymous with the definition of the aliphatic hydrocarbon group in said X, and its suitable range is also the same.

  In addition, as a suitable aspect of Y, group represented by the following formula | equation (4)-Formula (6) is mentioned.

In formula (5), L ⁴ represents an oxygen atom or a divalent aliphatic hydrocarbon group that may contain an oxygen atom (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Represents the total number of carbon atoms contained in the group).
In the formulas (4) to (6), * represents a bonding position.

  In formula (3), p represents an integer of 4 or more. Especially, 4-20 are preferable and 4-6 are more preferable at the point which is easy to synthesize | combine and the initial adhesiveness of an insulating resin layer is more excellent.

  A thiol compound may be used individually by 1 type, and may use 2 or more types simultaneously.

  Specific examples of the thiol compound include the compounds shown below. Among them, Pentaerythritol tetrakis (3-mercaptopropionate), Dipentaerythritol hexakis (3-mercaptopropionate), tetrakis- (7-mercapto-2,5-dithiaheptyl) methane and the like are preferably mentioned in that the initial adhesion of the insulating resin layer is more excellent. Tetrakis- (7-mercapto-2,5-dithiaheptyl) methane is particularly preferred.

(Process procedure)
In this step, the insulating substrate surface and the metal wiring surface of the insulating substrate with metal wiring are covered with a thiol compound.
The method in this step is not particularly limited as long as the insulating substrate with metal wiring can be brought into contact with the thiol compound, and the thiol compound is applied onto the insulating substrate with metal wiring, or the metal wiring is included in the liquid thiol compound. A known method such as dipping the insulating substrate can be employed. More specifically, dip dipping, shower spraying, spray coating, spin coating and the like can be mentioned, and dip dipping, shower spraying, and spray coating are preferred from the viewpoint of simplicity of processing and easy adjustment of processing time.

In addition, if necessary, a surface treatment liquid containing a thiol compound and a solvent is applied onto an insulating substrate with metal wiring (on the surface on the metal wiring side), or an insulating substrate with metal wiring is placed in the surface treatment liquid. It may be immersed. If it is this aspect, it will be easy to control the quantity of the thiol compound couple | bonded on a metal wiring, and it will be easier to improve the initial adhesiveness of an insulating resin layer.
Hereinafter, the configuration of the surface treatment liquid used will be described in detail.

  The content of the thiol compound in the surface treatment liquid is not particularly limited, but is 0.01 to 10 mM (mmol) in that the initial adhesion of the insulating resin layer or the temporal stability of the adhesion of the insulating resin layer is more excellent. Is preferable, 0.05-3 mM is more preferable, and 0.1-1 mM is further more preferable. When the content of the thiol compound is too large, it becomes difficult to control the amount of the thiol compound bonded to the metal wiring, and it is uneconomical. If the content of the thiol compound is too small, it takes time to bond the thiol compound and the productivity is poor.

The kind of the solvent contained in the surface treatment liquid is not particularly limited, and examples thereof include water, alcohol solvents (for example, methanol, ethanol, isopropanol), ketone solvents (for example, acetone, methyl ethyl ketone, cyclohexanone), amide solvents (for example, , Formamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), nitrile solvents (eg acetonitrile, propionitrile), ester solvents (eg methyl acetate, ethyl acetate, γ-butyrolactone), carbonate solvents (Eg dimethyl carbonate, diethyl carbonate), ether solvents (eg cellosolve, tetrahydrofuran), halogen solvents, glycol ether solvents (eg dipropylene glycol methyl ether), glycosyl Ester solvents (e.g., propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate) and the like. Two or more of these solvents may be mixed and used.
Of these, ketone solvents, glycol ester solvents, and alcohol solvents are preferred from the viewpoint of solubility of the thiol compound.

  The content of the solvent in the surface treatment liquid is not particularly limited, but is preferably 50 to 99.99% by mass, more preferably 90 to 99.99% by mass, and 95 to 99.99% by mass with respect to the total amount of the treatment liquid. Is particularly preferred.

It is preferable that the surface treatment liquid does not substantially contain a resin having a functional group that reacts with the thiol compound (hereinafter also referred to as resin X. For example, an epoxy resin, an acrylic resin having an acrylate group, or the like). When the resin X is contained in the surface treatment liquid, the reaction proceeds with the thiol compound, and the stability of the treatment liquid itself is impaired. Furthermore, it becomes difficult to bond a desired amount of thiol compound on the metal wiring, and as a result, the initial adhesion of the insulating resin layer is lowered.
In addition, that the resin X is substantially not included means that the content of the resin X in the surface treatment liquid is 1% by mass or less with respect to the total amount of the treatment liquid. In particular, it is preferable that the resin X is not contained (0% by mass).

  The treatment liquid may contain additives such as a pH adjuster, a surfactant, a preservative, and a precipitation inhibitor.

The temperature of the thiol compound or the surface treatment liquid when contacting the insulating substrate with metal wiring is preferably in the range of 5 to 75 ° C., and in the range of 10 to 45 ° C. Is more preferable, and the range of 15-35 degreeC is further more preferable.
Further, the contact time is preferably in the range of 30 seconds to 120 minutes, more preferably in the range of 3 minutes to 60 minutes, and more preferably in the range of 5 minutes to 30 minutes in terms of productivity and control of the attached amount (bound amount) of the thiol compound. The range of is more preferable.

[First cleaning step]
This step is a step of removing the thiol compound on the surface of the insulating substrate by cleaning the insulating substrate with metal wiring using a solvent (first cleaning solvent). By performing this step, thiol compounds other than the thiol compound bonded to the metal wiring, in particular, thiol compounds on the surface of the insulating substrate can be washed away. Specifically, as shown in FIG. 1C, the thiol compound layer 16 on the insulating substrate 12 is substantially removed, and the excess thiol compound on the metal wiring 14 is also removed. A layer of thiol compound (thiol compound layer) 18 bonded to the surface is formed. In addition, after the completion of this step, the thiol compound may remain on the insulating substrate 12 as long as the effects of the present invention are not impaired.
First, the material (first cleaning solvent) used in this step will be described, and then the procedure of this step will be described.

(First cleaning solvent)
The kind of the solvent (first cleaning solvent) used in the first cleaning step for cleaning the insulating substrate with metal wiring is not particularly limited as long as the solvent can remove the thiol compound on the insulating substrate. Especially, it is preferable that it is a solvent in which a thiol compound dissolves. By using the solvent, it is possible to more efficiently remove excess thiol compounds deposited on the insulating substrate, excess thiol compounds on the metal wiring, and the like.
Examples of the solvent include water, alcohol solvents (for example, methanol, ethanol, propanol), ketone solvents (for example, acetone, methyl ethyl ketone, cyclohexanone), amide solvents (for example, formamide, dimethylacetamide, N-methylpyrrolidone). N-ethylpyrrolidone), nitrile solvents (eg acetonitrile, propionitrile), ester solvents (eg methyl acetate, ethyl acetate, γ-butyrolactone), carbonate solvents (eg dimethyl carbonate, diethyl carbonate), Ether solvents (eg cellosolve, tetrahydrofuran), halogen solvents, glycol ether solvents (eg dipropylene glycol methyl ether), glycol ester solvents (eg propylene) Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate) and the like. Two or more of these solvents may be mixed and used.
Of these, alcohol solvents, ketone solvents (preferably cyclohexanone), glycol ester solvents (preferably propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate), amide solvents, because thiol compounds are more easily removed. (Preferably N-ethylpyrrolidone) or a mixed solvent of these solvents and water is preferable.

  Although the boiling point (25 degreeC, 1 atmosphere) of the solvent used is not restrict | limited in particular, 75-200 degreeC is preferable and 80-180 degreeC is more preferable from a safety viewpoint.

(Process procedure)
The cleaning method is not particularly limited, and a known method can be employed. Examples thereof include a method of applying a first cleaning solvent on an insulating substrate with metal wiring (on the surface on the metal wiring side), a method of immersing the insulating substrate with metal wiring in the first cleaning solvent, and the like.
Moreover, as a liquid temperature of a 1st washing | cleaning solvent, the range of 5-60 degreeC is preferable at the point of adhesion amount (bonding amount) control of a thiol compound, and the range of 15-35 degreeC is more preferable.
The contact time between the insulating substrate with metal wiring and the first cleaning solvent is preferably in the range of 10 seconds to 10 minutes in terms of productivity and control of the amount of thiol compound attached (bonding amount), and 15 seconds. A range of ˜5 minutes is more preferred.

(Thiol compound layer)
As shown in FIG. 1C, the thickness of the thiol compound layer 18 bonded to the surface of the metal wiring obtained through the first cleaning step is not particularly limited, but the initial adhesion of the insulating resin layer is more excellent. Is preferably 0.1 to 10 nm, more preferably 0.1 to 3 nm, and still more preferably 0.1 to 2 nm.
In addition, in order to control the thickness and coverage of the thiol compound layer 18, the first covering step and the first cleaning step may be performed twice or more continuously. In that case, the thiol compound used in the first first coating step may be different from the thiol compound used in the second first coating step.

[Second coating step]
This step is a step of covering the surface of the metal wiring covered with the thiol compound and the surface of the insulating substrate using a polymer having at least three or more reactive functional groups Y that react with the reactive functional group X in the molecule. . In other words, it is a step of covering the surface of the insulating substrate with metal wiring (in particular, the surface on the metal wiring side) with the polymer. More specifically, as shown in FIG. 1D, a polymer layer (polymer layer) 20 is formed on the surface of the insulating substrate 12 and on the surface of the metal wiring 14 covered with the thiol compound layer 18. . In particular, the polymer on the thiol compound layer 18 is bonded to the thiol compound layer 18 through the reactive functional group Y.
By this step, the polymer is bonded so as to cover the surface of the metal wiring to which the thiol compound is bonded, and the initial adhesiveness of the insulating resin layer described later or the temporal stability of the adhesiveness of the insulating resin layer is improved.
First, the material (polymer) used in this step will be described, and then the procedure of the step will be described.

(polymer)
The polymer used in this step is a polymer having at least three or more reactive functional groups Y that react with the reactive functional group X in the molecule. The polymer is bonded to the unreacted reactive functional group X of the thiol compound bonded to the metal wiring described above via the reactive functional group Y. The bonded polymer plays a role of stress relaxation between the metal wiring and the insulating resin layer formed thereon, and contributes to the initial adhesion of the insulating resin layer and the improvement of the temporal stability of the adhesion of the insulating resin layer. .

The reactive functional group Y is not particularly limited as long as it is a functional group that reacts with the reactive functional group X described above. Examples thereof include a hydroxyl group, a primary amino group, a secondary amino group, an epoxy group (particularly preferably, a glycidyl group), an acrylate group, and a methacrylate group.
Among these, an epoxy group, an acrylate group, or a methacrylate group is preferable, and an epoxy group is more preferable in that the reactivity is more excellent and the initial adhesion of the insulating resin layer is further improved.

The number of reactive functional groups Y contained in the polymer molecule is 3 or more. Especially, 10 or more are preferable, 50 or more are more preferable, and 200 or more are especially preferable at the point which the temporal stability of the adhesiveness of an insulating resin layer improves more. The upper limit is not particularly limited, but is preferably 1000 or less from the viewpoint of the solubility of the polymer and the ease of reaction.
If the number of reactive functional groups Y contained in the polymer is less than 3, the network structure with the thiol compound cannot be sufficiently formed, and the temporal stability of the adhesiveness of the insulating resin layer is extremely inferior.

The reactive functional group Y equivalent (g / eq) of the polymer is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less, and even more preferably 200 or less, from the viewpoint that the temporal stability of the adhesiveness of the insulating resin layer is more excellent. preferable. In addition, although it does not restrict | limit in particular regarding a minimum, Usually, it is 40 or more from the point on the synthesis | combination of a polymer.
In addition, reactive functional group Y equivalent represents the magnitude | size of the molecule | numerator per unit quantity of the reactive functional group Y contained in a polymer.

The number average molecular weight of the polymer is not particularly limited, but is preferably 5000 or more, more preferably 7500 or more, further preferably 10,000 or more, and particularly preferably 17500 or more in terms of further improving the temporal stability of the adhesiveness of the insulating resin layer. 36000 or more is most preferable. The upper limit is not particularly limited, but is preferably 500,000 or less, and more preferably 150,000 or less in terms of excellent handling properties such as polymer solubility.
In addition, you may use together the epoxy resin of a different number average molecular weight.

  The type of polymer is not particularly limited, and examples thereof include polyimide resin, epoxy resin, urethane resin, polyethylene resin, polyester resin, urethane resin, novolac resin, cresol resin, acrylic resin, methacrylic resin, and styrene resin. Of these, acrylic resins and methacrylic resins are preferable in terms of availability of materials and film formability.

(Preferred embodiment of polymer)
As a preferred embodiment of the polymer, a polymer having a repeating unit represented by the following formula (7) can be mentioned. If it is this polymer, the time-dependent stability of the adhesiveness of an insulating resin layer will improve more.

In formula (7), R ² represents a hydrogen atom or an alkyl group. As an alkyl group, C1-C5 is preferable and C1-C3 is more preferable at the point which is easy to synthesize | combine.

In formula (7), L ⁵ represents a single bond or a divalent linking group. Definition of the divalent linking group are the same as those defined divalent linking group represented by L ² and L ³ in formula (2).
L ⁵ is preferably a divalent aliphatic hydrocarbon group, —CO—, —O—, or a group obtained by combining these, in that the stability over time of the adhesiveness of the insulating resin layer is more excellent.

  In formula (7), Z represents an epoxy group, an acrylate group, and a methacrylate group. Among these, an epoxy group is preferable in that the initial adhesion of the insulating resin layer or the temporal stability of the adhesion of the insulating resin layer is more excellent.

  Another preferred embodiment of the polymer is an epoxy resin. The epoxy resin used is not particularly limited as long as it is a resin having at least three epoxy groups, and is a known resin (for example, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, polymethacrylic acid). Glycidyl etc.) can be used.

(Process procedure)
In this step, the insulating substrate surface and the metal wiring surface of the insulating substrate with metal wiring are covered with a polymer.
The method of this step is not particularly limited as long as the insulating substrate with metal wiring can be brought into contact with the polymer, and the polymer is applied onto the insulating substrate with metal wiring (coating method) or on the insulating substrate with metal wiring. A known method such as laminating a polymer (lamination method) can be employed. Examples of the coating method include dip dipping, shower spraying, spray coating, spin coating and the like, and dip dipping, shower spraying, and spray coating are preferable from the standpoint of easy processing and easy adjustment of processing time.

In addition, if necessary, a polymer composition containing a polymer and a solvent is applied on an insulating substrate with metal wiring (on the surface on the metal wiring side), or the insulating substrate with metal wiring is immersed in the polymer composition. May be. If it is this aspect, it will be easy to control the quantity of the polymer couple | bonded on the metal wiring covered with the thiol compound, and it will be easier to improve the temporal stability of the adhesiveness of an insulating resin layer.
Hereinafter, the constitution of the polymer composition used will be described in detail.

  The content of the polymer in the polymer composition is not particularly limited, but it is easy to control the amount of the polymer to be bonded, and the stability over time of the adhesiveness of the insulating resin layer is further improved, with respect to the total amount of the polymer composition, 0.01-80 mass% is preferable, 0.1-50 mass% is more preferable, 0.5-20 mass% is further more preferable.

Although the kind in particular of solvent contained in a polymer composition is not restrict | limited, For example, the solvent etc. which are used with the said surface treatment liquid are illustrated.
Among them, alcohol solvents, ketone solvents (preferably cyclohexanone), glycol ester solvents (preferably propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate), amide solvents (preferably N) are preferred because of their excellent solubility. -Ethylpyrrolidone) is preferred.

In addition, it is preferable that the inorganic filler is not substantially contained in the polymer composition. When the inorganic filler is contained in the polymer composition, the inorganic filler is laminated together with the polymer on the metal wiring covered with the thiol compound, and the stress relaxation function of the polymer is lowered. As a result, the initial adhesion of the insulating resin layer may be deteriorated. Examples of the inorganic filler include known materials such as alumina (aluminum oxide), magnesia (magnesium oxide), calcium oxide, titania (titanium oxide), zirconia (zirconium oxide), talc, and silica (silicon oxide).
In addition, that the inorganic filler is substantially not included, the content of the inorganic filler in the polymer composition is 0.9% by mass or less with respect to the total amount of the polymer and the inorganic filler in the polymer composition. It means that. In particular, it is preferable that no inorganic filler is contained (0% by mass).

  The contact time between the polymer or polymer composition and the insulating substrate with metal wiring is preferably in the range of 30 seconds to 120 minutes in terms of productivity and control of the amount of polymer attached (bonding amount), and preferably 3 minutes to 60 minutes. The range is more preferable, and the range of 5 minutes to 30 minutes is more preferable.

[Second cleaning step]
This step is a step of removing the polymer on the surface of the insulating substrate by cleaning the insulating substrate with metal wiring using a solvent (second cleaning solvent). By performing this step, a polymer other than the polymer bonded to the thiol compound on the metal wiring, particularly a polymer on the surface of the insulating substrate can be washed away. Specifically, as shown in FIG. 1 (E), the polymer 16 on the insulating substrate 12 is removed, and the excess polymer on the metal wiring 14 is also removed and bonded to the metal wiring covered with the thiol compound. The polymer layer (polymer layer) 22 is formed. In addition, the polymer may remain on the insulating substrate 12 as long as the effect of the present invention is not impaired after the completion of this step.
First, the material (second cleaning solvent) used in this step will be described, and then the procedure of this step will be described.

(Second cleaning solvent)
The kind of the solvent (second cleaning solvent) used in the second cleaning step for cleaning the insulating substrate with metal wiring is not particularly limited as long as it can remove the polymer on the insulating substrate. Especially, it is preferable that it is a solvent which a polymer melt | dissolves. By using the solvent, it is possible to more efficiently remove excess polymer deposited on the insulating substrate, excess polymer on the metal wiring, and the like.
The type of the solvent is not particularly limited as long as the polymer can be removed, and examples thereof include the solvents exemplified in the first washing solvent used in the first washing step.
Among these, from the viewpoint of polymer removability, alcohol solvents, ketone solvents (preferably cyclohexanone), glycol ester solvents (preferably propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate), amide solvents (preferably N-ethylpyrrolidone) or a mixed solvent of these solvents and water is preferable.

  Although the boiling point (25 degreeC, 1 atmosphere) of the solvent used is not restrict | limited in particular, 75-200 degreeC is preferable and 80-180 degreeC is more preferable from a safety viewpoint.

(Process procedure)
The cleaning method is not particularly limited, and a known method can be employed. Examples thereof include a method of applying a second cleaning solvent on an insulating substrate with metal wiring (particularly on the surface on the metal wiring side), a method of immersing the insulating substrate with metal wiring in the second cleaning solvent, and the like.
In addition, the liquid temperature of the second cleaning solvent is preferably in the range of 5 to 60 ° C., more preferably in the range of 15 to 35 ° C., from the viewpoint of controlling the adhesion amount (bond amount) of the polymer.
In addition, the contact time between the insulating substrate with metal wiring and the second cleaning solvent is preferably in the range of 10 seconds to 10 minutes in terms of productivity and polymer adhesion amount (bonding amount) control. A range of 5 minutes is more preferred.

By performing the above process, a laminated structure of the thiol compound layer 18 and the polymer layer 22 is formed on the metal wiring (FIG. 1E).
The thickness of the polymer layer 22 provided on the thiol compound layer 18 is not particularly limited, but is preferably 1 μm or less from the viewpoint that the layer can be easily removed at the time of mounting an electronic component, and is 0.2 μm or less. More preferably, it is 0.1 μm or less. In addition, although a minimum in particular is not restrict | limited, 0.005 micrometer or more is preferable at the point which the time-dependent stability improvement of the adhesiveness of the insulating resin layer by the polymer layer 22 is exhibited more.
The polymer layer 22 preferably does not substantially contain an inorganic filler. The fact that the inorganic filler is not substantially contained means that the content of the inorganic filler in the polymer layer 22 is 0.9% by mass or less with respect to the total amount of the polymer layer 22. In particular, it is preferable that no inorganic filler is contained (0% by mass).

  Further, by performing the above steps, the thiol compound and the polymer on the insulating substrate are substantially removed, and the insulating resin layer and the insulating substrate, which will be described later, can come into contact with each other, resulting in the initial adhesion of the insulating resin layer. And after completion | finish of this process, the temporal stability of adhesiveness improves.

[Insulating resin layer forming process]
This step is a step of forming an insulating resin layer on the surface on the metal wiring side of the insulating substrate with metal wiring having the metal wiring covered with the polymer layer obtained in the above step. More specifically, as shown in FIG. 1 (F), an insulating resin layer 24 is provided on the insulating substrate 10 with metal wiring so as to be in contact with the metal wiring 14 covered with the polymer layer 22, and a printed wiring board. 26 is obtained. By providing the insulating resin layer 24, the insulation reliability between the metal wirings 14 is ensured. Further, since the insulating substrate 12 and the insulating resin layer 24 can be in direct contact, the adhesiveness of the insulating resin layer 24 is excellent.
First, the material of the insulating resin layer is described, and then the method for forming the insulating resin layer is described.

As a material of the insulating resin layer, a known insulating material can be used. For example, a material used as a so-called interlayer insulating resin layer can be used. Specifically, epoxy resin, aramid resin, crystalline polyolefin resin, amorphous polyolefin resin, fluorine-containing resin (polytetrafluoroethylene) can be used. Perfluorinated polyimide, perfluorinated amorphous resin, etc.), polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, acrylate resin and the like. As an interlayer insulation resin layer, Ajinomoto Fine Techno Co., Ltd. product, ABF GX-13, GX-92 etc. are mentioned, for example.
A so-called solder resist layer may be used as the insulating resin layer. As the solder resist, commercially available products may be used. Specific examples include PFR800, PSR4000 (trade name) manufactured by Taiyo Ink Manufacturing Co., Ltd., SR7200G, SR7300G manufactured by Hitachi Chemical Co., Ltd., and the like.
Further, a photosensitive film resist may be used as the insulating layer. Specific examples include SUNFORT manufactured by Asahi Kasei E-Materials Co., Ltd., and Fotec manufactured by Hitachi Chemical Co., Ltd.

Especially, it is preferable that an insulating resin layer contains resin which has an epoxy group or a (meth) acrylate group. The resin easily binds to the polymer layer described above, and as a result, the temporal stability of the adhesiveness of the insulating resin layer is further improved.
The resin is preferably the main component of the insulating resin layer. The main component means that the total amount of the resin is 50% by mass or more with respect to the total amount of the insulating resin layer, and is preferably 60% by mass or more. In addition, as an upper limit, it is 100 mass%.

A known epoxy resin can be used as the resin having an epoxy group. For example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, or the like can be used.
As the resin having a (meth) acrylate group, a known resin can be used. For example, an acrylate resin or a methacrylate resin can be used.

The insulating resin layer preferably contains an inorganic filler. By including an inorganic filler in the insulating resin layer, the insulation is further improved and the CTE (thermal linear expansion coefficient) is lowered. In addition, the kind of inorganic filler can use a well-known material as mentioned above.
The content of the inorganic filler in the insulating resin layer is preferably 1 to 85% by mass and more preferably 15 to 80% by mass with respect to the total amount of the insulating resin layer in terms of further improving the insulating properties. Preferably, it is 40-75 mass%.

The method for forming the insulating resin layer on the insulating substrate with metal wiring is not particularly limited, and a known method can be adopted. For example, a method of laminating a film of an insulating resin layer directly on an insulating substrate with metal wiring, a method of applying an insulating resin layer forming composition containing a component constituting the insulating resin layer on an insulating substrate with metal wiring, Examples include a method of immersing an insulating substrate with metal wiring in the insulating resin layer forming composition.
In addition, the said composition for insulating resin layer formation may contain the solvent as needed. When using the composition for insulating resin layer formation containing a solvent, after arrange | positioning this composition on a board | substrate, you may heat-process in order to remove a solvent as needed.
Further, after providing the insulating resin layer on the insulating substrate with metal wiring, energy may be applied (for example, exposure or heat treatment) to the insulating resin layer as necessary.

The thickness of the insulating resin layer to be formed is not particularly limited, and is preferably 5 to 50 μm and more preferably 15 to 40 μm from the viewpoint of insulation reliability between wirings.
In FIG. 1F, the insulating resin layer 24 is described as a single layer, but may have a multilayer structure.

[Drying process]
This process is a process of heating and drying the insulating substrate with metal wiring in a process provided between the above processes as necessary. If moisture remains on the insulating substrate with metal wiring, migration of metal ions is promoted, and as a result, the insulation between the metal wirings may be impaired. Therefore, it is preferable to remove the moisture by providing this step. . In addition, this process is an arbitrary process, and when the solvent used at the said process is a solvent excellent in volatility etc., this process does not need to implement.

Heat drying conditions are 70 to 120 ° C. (preferably 80 ° C. to 110 ° C.) for 15 seconds to 10 minutes (preferably 30 seconds to 5 minutes) in terms of suppressing metal oxidation in the metal wiring. It is preferable to implement. If the drying temperature is too low or the drying time is too short, moisture removal may not be sufficient, and if the drying temperature is too high or the drying time is too long, a metal oxide film may be formed. is there.
The apparatus used for drying is not particularly limited, and a known heating apparatus such as a constant temperature layer or a heater can be used.

[Printed wiring board]
By passing through the above steps, as shown in FIG. 1 (F), an insulating substrate 10 with metal wiring, and an insulating resin layer 26 disposed on the surface of the insulating substrate 10 with metal wiring on the metal wiring 14 side, A printed wiring board 26 in which the thiol compound layer 18 and the polymer layer 22 are interposed between the metal wiring 14 and the insulating resin layer 24 can be obtained. In other words, the thiol compound and the polymer are bonded to the surface of the metal wiring 14 facing the insulating resin layer 24. The obtained printed wiring board 26 is excellent in adhesion between the insulating resin layer 26 and the insulating substrate 10 with metal wiring.
As shown in FIG. 1F, in the above, the printed wiring board 26 in which the metal wiring 14 has a single-layer wiring structure is taken as an example, but the present invention is not limited to this. For example, a printed wiring board having a multilayer wiring structure can be manufactured by using a multilayer wiring board (for example, the multilayer wiring board shown in FIG. 2) in which a plurality of insulating substrates 12 and metal wirings 14 are alternately stacked. .

  The printed wiring board obtained by the manufacturing method of the present invention can be used for various uses and structures. For example, a mother board, a semiconductor package board, an IC package board, an LSI package board, a MID (Molded Interconnect). (Device) substrate. The manufacturing method of the present invention can be applied to rigid substrates, flexible substrates, flex-rigid substrates, molded circuit substrates, and the like.

Further, a part of the insulating resin layer in the obtained printed wiring board may be removed, and a semiconductor chip may be mounted and used as a printed circuit board.
For example, when using a solder resist as the insulating resin layer, place a mask with a predetermined pattern on the insulating resin layer, apply energy to cure, remove the insulating resin layer in the non-energy-applied area, and wire To expose. Next, the exposed wiring surface is cleaned by a known method (for example, cleaning using sulfuric acid, soft etching agent, alkali, and surfactant), and then the semiconductor chip is mounted on the wiring surface.
When a known interlayer insulating resin layer is used as the insulating resin layer, the insulating resin layer can be removed by drilling or laser processing.

Moreover, you may provide a metal wiring (wiring pattern) further on the insulating resin layer of the obtained printed wiring board. The method for forming the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, etc.) can be used.
In the present invention, a substrate in which metal wiring (wiring pattern) is further provided on the insulating resin layer of the obtained printed wiring board is used as a new insulating substrate with metal wiring (inner layer substrate). Metal wiring can be stacked in several layers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

<Example 1>
Using a copper-clad laminate (MCL-E-679F manufactured by Hitachi Chemical Co., Ltd., substrate: glass epoxy substrate), an insulating substrate A with metal wiring having a copper wiring of L / S = 1000 μm / 500 μm is formed by a semi-additive method did. The insulating substrate A with metal wiring was produced by the following method.
After the copper-clad laminate is acid washed, washed with water, and dried, a dry film resist (DFR, trade name: RY3315, manufactured by Hitachi Chemical Co., Ltd.) is adjusted to 70 ° C. at a pressure of 0.2 MPa with a vacuum laminator. And laminated. After lamination, the copper pattern forming portion was subjected to mask exposure with an exposure machine having a central wavelength of 365 nm under the condition of 70 mJ / cm ² . Then, it developed with 1% sodium hydrogen carbonate aqueous solution, washed with water, and obtained the plating resist pattern.
Through plating pretreatment and water washing, electrolytic plating was performed on the copper exposed between the resist patterns. At this time, an acidic solution of copper (II) sulfate was used as an electrolytic solution, a crude copper plate having a purity of about 99% was used as an anode, and a copper clad laminate was used as a cathode. By electrolysis at 50 to 60 ° C. and 0.2 to 0.5 V, copper was deposited on the cathode copper. Then, it washed with water and dried.
In order to remove the resist pattern, the substrate was immersed in a 4% NaOH aqueous solution at 45 ° C. for 60 seconds. Thereafter, the obtained substrate was washed with water and immersed in 1% sulfuric acid for 30 seconds. Thereafter, it was washed again with water. The conductive copper between the copper patterns was quickly etched with an etching solution mainly composed of hydrogen peroxide and sulfuric acid, washed with water and dried. The thickness of the copper wiring of the obtained copper wiring board (insulating substrate A with metal wiring) was 15 μm, and the surface roughness Rz of the copper wiring was Rz = 0.4 μm.

Next, the obtained insulating substrate A with metal wiring was immersed in an ethanol solution (thiol compound concentration: 0.1 mM) containing 1,10-decanedithiol (manufactured by Wako Pure Chemical Industries, Ltd.) for 60 minutes, and then washed with ethanol (No. 1). 1 wiring process). The reactive functional group X equivalent (g / eq) of 1,10-decanedithiol was 103, the molecular weight was 206, and the sulfur atom content was 31 wt%.
Next, the insulating substrate A with metal wiring subjected to the above-described treatment was subjected to polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48000). ) -Containing cyclohexanone solution (polymer concentration: 5 wt%) for 10 minutes at room temperature. Thereafter, the insulating substrate A with metal wiring was washed with cyclohexanone and dried at room temperature (second wiring processing).
Thereafter, an insulating resin layer (GX-13 manufactured by Ajinomoto Fine Techno Co.) was laminated on the surface of the insulating substrate A with metal wiring on the metal wiring side. Next, a pattern (L-shaped pattern) of the insulating resin layer (layer thickness of the insulating resin layer: 35 μm) was produced by laser processing, and the residue generated by the laser processing was removed by desmear treatment. The insulating resin layer contained an inorganic filler (silica).
From the above, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was produced (hereinafter, this substrate is referred to as substrate B). In addition, in the board | substrate B, copper was partially exposed in the part without the pattern of an insulating resin layer. The obtained substrate B was subjected to a tape peeling test according to the following procedure.

(Ni plating)
The obtained substrate B was subjected to a cleaning treatment at a liquid temperature of 50 ° C. for 5 minutes using a cleaner liquid (trade name: ACL-009, manufactured by Uemura Kogyo Co., Ltd.). Further, the substrate B was immersed in a soft etching solution obtained by mixing 10% sulfuric acid (Wako Pure Chemical Industries) and peroxodisulfide Na (Wako Pure Chemical Industries) at room temperature for 1.5 minutes for cleaning. Further, the treated substrate B was immersed in 2% sulfuric acid (Wako Pure Chemical Industries) for 1 minute, and immersed in an activator solution in which 10% sulfuric acid and MFD-5 (manufactured by Uemura Kogyo Co., Ltd.) were mixed and diluted for 1 minute. . Thereafter, the copper surface was plated with Ni (nickel) by immersing in Ni plating solution of NPR-4 (manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C. for 16 minutes (nickel plating thickness: 3 μm).

(Tape peeling test)
As an evaluation method, a tape peeling test was performed after the Ni plating, and the number of grids remaining on the insulating substrate A with metal wiring without the insulating resin layer pattern being peeled was counted. Table 1 shows the results of the copper wiring board obtained in Example 1. The tape peeling test was performed according to JIS K5600-5-6. In Table 1, the results are shown in the “initial adhesion” column.
The obtained results were evaluated according to the following criteria. In practice, it is desirable not to be “C”.
“A”: When 90 squares or more of 100 squares remain “B”: When 60 squares or more and less than 90 squares remain among 100 squares “C”: Less than 60 squares remain among 100 squares Case

(Aging adhesion test)
Next, the sample for which the tape peeling test was completed was left for 200 hours in an environment of 85% humidity, 130 ° C., and 1.2 atm pressure (use apparatus: EHS-221MD, manufactured by espec). After 200 hours, a sample was taken out, and the tape peeling test was performed again to conduct an adhesion test over time. In Table 1, the results are shown in the “Stability with time” column.
Next, the ratio between the number of remaining squares of the obtained grid and the number of residual grids in the above-mentioned peeling test performed before the high temperature and high humidity treatment (the residual mass in the peeling test after leaving in a high temperature and high humidity environment). Number / number of remaining masses in the peel test before standing in a high-temperature and high-humidity environment) was determined and evaluated according to the following criteria. In practice, it is desirable not to be “C”.
“A”: When the ratio is 0.9 or more “B”: When the ratio is 0.7 or more and less than 0.9 “C”: When the ratio is less than 0.7

<Example 2>
Instead of the first wiring process performed in Example 1, the insulating substrate A with metal wiring was immersed in an ethanol solution (thiol compound concentration: 1 mM) containing Pentaerythritol tetrakis (3-mercaptoacetate) for 10 minutes and washed with ethanol. Except for the above, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was prepared according to the same procedure as in Example 1, and various evaluations were performed. Table 1 summarizes the results.
Pentaerythritol tetrakis (3-mercaptoacetate) had a reactive functional group X equivalent (g / eq) of 122, a molecular weight of 488, and a sulfur atom content of 26 wt%.

<Example 3>
Instead of the first wiring process performed in Example 1, the insulating substrate A with metal wiring was immersed in an ethanol solution (thiol compound concentration: 1 mM) containing Dipentaerythritol hexakis (3-mercaptopropionate) for 10 minutes and washed with ethanol. Except for the above, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was prepared according to the same procedure as in Example 1, and various evaluations were performed. Table 1 summarizes the results.
Dipentaerythritol hexakis (3-mercaptopropionate) had a reactive functional group X equivalent (g / eq) of 131, a molecular weight of 783, and a sulfur atom content of 24 wt%.

<Example 4>
Instead of the first wiring process performed in Example 1, the insulating substrate A with metal wiring was changed to a tetrakis- (7-mercapto-2,5-dithiaheptyl) methane-containing cyclohexanone solution (thiol compound concentration: 0.1 mM). Except for immersion for 20 minutes and washing with cyclohexanone, an insulating substrate A with metal wiring having an insulating resin layer pattern provided on the surface was prepared according to the same procedure as in Example 1, and various evaluations were performed. Table 1 summarizes the results.
The reactive functional group X equivalent (g / eq) of tetrakis- (7-mercapto-2,5-dithiaheptyl) methane was 170, the molecular weight was 681, and the sulfur atom content was 56 wt%.

<Comparative Example 1>
Instead of the first wiring process and the second wiring process performed in Example 1, a tetrakis- (7-mercapto-2,5-dithiaheptyl) methane-containing cyclohexanone solution (thiol compound concentration: 0.1 mM) is used in advance. Insulating substrate A with metal wiring is dipped in a mixed solution obtained by mixing polyglycidyl methacrylate-containing cyclohexanone solution (polymer concentration: 5 wt%) for 5 hours, and then insulating substrate A with metal wiring is washed with cyclohexanone. Then, according to the same procedure as in Example 1 except that it was dried at room temperature, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on its surface was prepared and subjected to various evaluations. Table 1 summarizes the results.

<Comparative example 2>
Instead of the second wiring process of the first embodiment, the insulating substrate with metal wiring subjected to the first wiring process is treated with an ethanol solution containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by AMAX Co.). Insulating substrate A with metal wiring having an insulating resin layer pattern provided on the surface was prepared according to the same procedure as in Example 1 except that it was immersed in (compound concentration: 10 mM) for 5 minutes and washed with ethanol. Evaluation was performed. Table 1 summarizes the results.
In Comparative Example 2, a polymer having at least three reactive functional groups Y that react with the reactive functional group X is not used.

<Comparative Example 3>
Instead of the second wiring process in Example 2, the insulating substrate with metal wiring subjected to the first wiring process was treated with an ethanol solution containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Amax Co.). Insulating substrate A with metal wiring having an insulating resin layer pattern provided on the surface was prepared according to the same procedure as in Example 2 except that it was immersed in (compound concentration: 10 mM) for 5 minutes and washed with ethanol. Evaluation was performed. Table 1 summarizes the results.
In Comparative Example 3, a polymer having at least three reactive functional groups Y that react with the reactive functional group X is not used.

<Comparative example 4>
Instead of the first wiring process of Example 1, the insulating substrate A with metal wiring was immersed in a 3-mercaptopropyltrimethoxysilane-containing ethanol solution (compound concentration: 10 mM) for 5 minutes and washed with ethanol. According to the procedure similar to Example 1, the insulated substrate A with a metal wiring in which the insulating resin layer pattern was provided on the surface was produced, and various evaluation was performed. Table 1 summarizes the results.
In Comparative Example 4, a predetermined thiol compound is not used.

<Comparative Example 5>
Example 1 except that the insulating substrate A with metal wiring was immersed in a triazine thiol-containing ethanol solution (compound concentration: 0.1 mM) for 60 minutes and washed with ethanol instead of the first wiring process of Example 1. Insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was prepared according to the same procedure as described above, and various evaluations were performed. Table 1 summarizes the results.
In Comparative Example 5, a predetermined thiol compound is not used.

<Comparative Example 6>
According to the same procedure as in Example 1 except that the second wiring process of Example 1 was not performed, an insulating substrate A with metal wiring having an insulating resin layer pattern provided on the surface was prepared, and various evaluations were performed. It was. Table 1 summarizes the results.

In addition, when the copper wiring board after performing the 2nd wiring process implemented in the said Examples 1-4 was measured by XPS, presence of a sulfur atom was confirmed on copper wiring and a thiol compound couple | bonded with copper wiring It was confirmed that
The thickness of the layer of the thiol compound formed on the copper wiring in Examples 1 to 4 was about 0.1 to 2 nm from the XPS measurement result. Moreover, the thickness of the formed epoxy resin layer was about 10-100 nm from the AFM measurement result.

  In Table 1, “Yes” in the “first wiring processing” column and “second wiring processing” column means that the processing has been performed, and “−” means that the processing has not been performed.

As shown in Table 1, the printed wiring board obtained by the production method of the present invention exhibited excellent initial adhesion and stability over time of adhesion.
In particular, from the comparison between Example 1 and Example 2 (or Example 3 or 4), the number of reactive functional groups X is 4 or more, and the reactive functional group X is represented by the formula (1). When a compound having a functional group is used, it was confirmed that better initial adhesion was exhibited.
Furthermore, from comparison between Example 2 and Example 4, it was confirmed that the stability of adhesiveness with time was more excellent as the content of sulfur atoms in the thiol compound was larger.

On the other hand, in the comparative example 1 which mixed and used the thiol compound and the polymer, it was inferior to initial stage adhesiveness. This is presumably because the thiol compound and the polymer reacted in the mixed solution and the reactivity to the metal wiring decreased.
Further, in Comparative Examples 2 and 3 in which the predetermined polymer was not used, the adhesion stability with time was inferior. This is presumed to be due to the progress of the adsorption of moisture to the metal wiring and the corrosion of the metal wiring due to the network structure formed by the silane coupling agent.

Furthermore, in Comparative Examples 4 and 5 using the triazine thiol described in Patent Document 2 and mercaptopropyltrimethoxysilane described in Patent Document 1, the adhesion stability with time was inferior. In particular, in Comparative Example 4, it is presumed that due to the network structure formed by the silane coupling agent, the adsorption of moisture to the metal wiring progressed and the corrosion of the metal wiring progressed.
Furthermore, in Comparative Example 6 in which the polymer layer was not formed, the initial adhesion was inferior.

<Example 5>
Instead of polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48000) in Example 2 instead of cyclohexanone solution (polymer concentration: 5 wt%) And polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) -containing cyclohexanone solution (polymer concentration: 2.5 wt%), Insulating layer is laminated with Taiyo Ink PFR-800 instead of Ajinomoto Fine Techno Co., Ltd., ABF GX-13, then exposed through a pattern mask (L-shaped pattern), developed, baked, and further exposed Then, an SR (solder resist) pattern was produced on the copper wiring board (film thickness of the insulating layer: 30 μm). The obtained copper wiring substrate with SR pattern was subjected to Ni plating and then subjected to the tape peeling test. Thereafter, an adhesion test with time was performed. Table 2 summarizes the results. Note that the SR contained an inorganic filler (silica).

<Example 6>
In Example 5, polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) -containing cyclohexanone solution (polymer concentration: 5 wt%) A cyclohexanone solution (polymer concentration: 2.5 wt%) containing polyglycidyl methacrylate (Polymer Source, number of reactive functional groups Y: 122, reactive functional group Y equivalent: 143, number average molecular weight: 17500) was used. Except for the above, a copper wiring board with an SR pattern was prepared according to the same procedure as in Example 5, and various evaluations were performed. Table 2 summarizes the results.

<Example 7>
In Example 5, polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) -containing cyclohexanone solution (polymer concentration: 5 wt%) Except that polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 251, reactive functional group Y equivalent: 143, number average molecular weight: 36000) -containing cyclohexanone solution (polymer concentration: 5 wt%) was used. According to the same procedure as in Example 5, a copper wiring board with SR pattern was produced and various evaluations were performed. Table 2 summarizes the results.

<Comparative Example 7>
In Example 5, polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) -containing cyclohexanone solution (polymer concentration: 5 wt%) A cyclohexanone solution (compound concentration: 2.5 wt%) containing trimethylolpropane triglycidyl ether (manufactured by Aldrich, number of reactive functional groups Y: 3, reactive functional group Y equivalent: 100, number average molecular weight: 302) A copper wiring board with an SR pattern was prepared according to the same procedure as in Example 5 except that it was used, and various evaluations were performed. Table 2 summarizes the results.

  The “number average molecular weight” in Table 2 means the number average molecular weight of the polymer used in the second wiring process. In Comparative Example 7, the molecular weight of the used trimethylolpropane triglycidyl ether is shown.

As shown in Table 2, the printed wiring board obtained by the production method of the present invention exhibited excellent initial adhesion and stability over time of adhesion.
In particular, in Examples 6 and 7 in which the number average molecular weight of the polymer used was large, it was confirmed that the stability over time was more excellent. This is presumably because the stress relaxation ability was improved by increasing the number average molecular weight of the polymer.
On the other hand, in Comparative Example 7 in which the second wiring process using the polymer was not performed, the temporal stability was inferior.

<Example 8>
Silver was vapor-deposited on the silicon substrate to form a silver wiring substrate having a silver wiring of L / S = 1000 μm / 100 μm. The thickness of the silver wiring of the obtained silver wiring board was 0.3 μm, and the surface roughness Rz of the silver wiring was Rz = 0.02 μm.
Next, the obtained silver wiring board is immersed in a 0.1 mM tetrakis- (7-mercapto-2,5-dithiaheptyl) methane-containing cyclohexanone solution for 20 minutes, and then the silver wiring is formed using cyclohequinone as a cleaning solvent. The substrate was washed, further washed with water, and then dried at room temperature. After the above treatment, polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48000) -containing cyclohexanone solution (polymer concentration: 5 wt%) ) For 10 minutes at room temperature, washed with cyclohexanone, and dried at room temperature.
Thereafter, an insulating layer (PFR-800 manufactured by Taiyo Ink Co., Ltd.) is laminated on the treated silver wiring substrate, then exposed through a pattern mask (L-shaped pattern), developed, baked, and further exposed. An SR (solder resist) pattern (SR film thickness: 30 μm) was produced on a silver wiring board. The obtained silver wiring board with SR pattern was left for 100 hours in a humid environment (temperature 130 °, humidity 85% RH, pressure 1.2 atm) (use apparatus: EHS-221MD, EHS-221MD), and then a sample was taken out. The tape peeling test was conducted. Table 3 summarizes the results.

<Comparative Example 8>
In Example 8, the silver wiring board was made of polyhexidyl methacrylate (Polymer Source, manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48000) containing cyclohexanone solution (polymer concentration: 5 wt%) for 10 minutes at room temperature, and instead of washing with cyclohexanone, the silver wiring board was treated with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by AMAX Co.) ethanol solution (compound concentration: 10 mM) The sample was taken out for 100 hours after being left in a humid environment in the same procedure except that it was immersed in 5 minutes and washed with ethanol. Table 3 summarizes the results.

In Table 3, the “initial adhesion” column is a result of a tape peeling test performed on the silver wiring board with SR pattern before being left for 100 hours in a wet environment, and the same evaluation as the above (tape peeling test). Evaluation was made according to criteria.
In Table 3, the “Stability with time” column shows the number of remaining masses before and after being left in a wet environment by performing a tape peeling test on the silver wiring board with SR pattern after being left for 100 hours in a wet environment. The ratio (the number of remaining masses in the peeling test after being left in a wet environment / the number of remaining masses in the peeling test before being left in a wet environment) was determined and evaluated according to the same evaluation criteria as described above (time-dependent adhesion test).

As shown in Table 3, even when silver wiring was used as the metal wiring, the printed wiring board obtained by the production method of the present invention showed excellent initial adhesion and stability over time.
On the other hand, in Comparative Example 8 in which the second wiring process using the polymer was not performed, the temporal stability was inferior.

10: Insulating substrate with metal wiring 12: Insulating substrate 14: Metal wiring 16: Layer of thiol compound 18: Layer of thiol compound bonded to the surface of the metal wiring 20: Layer of polymer 22: Metal wiring covered with thiol compound Bonded polymer layer 24: insulating resin layer 26: printed wiring board 40: other insulating board 50: other metal wiring 60: silane coupling agent 62: polymer

Claims (8)

It has two or more reactive functional groups X (excluding silanol groups and silicon atom-bonded hydrolyzable groups), and at least one of the reactive functional groups X is a functional group represented by the formula (1) A first covering step of covering the insulating substrate surface and the metal wiring surface of the insulating substrate with a metal wiring having an insulating substrate and a metal wiring disposed on the insulating substrate using the thiol compound having
A first cleaning step of cleaning the insulating substrate with metal wiring using a solvent to remove the thiol compound on the surface of the insulating substrate;
A second coating step for covering the insulating substrate surface and the metal wiring surface covered with the thiol compound using a polymer having at least three reactive functional groups Y that react with the reactive functional group X;
A second cleaning step of cleaning the insulating substrate with metal wiring using a solvent to remove the polymer on the surface of the insulating substrate;
A method of manufacturing a printed wiring board having an insulating resin layer formed on an insulating substrate with metal wiring, comprising: an insulating resin layer forming step of forming an insulating resin layer on a surface on the metal wiring side of the insulating substrate with metal wiring. .

(In formula (1), L ¹ represents a divalent aliphatic hydrocarbon group. * Represents a bonding position.)   The method for producing a printed wiring board according to claim 1, wherein the number average molecular weight of the polymer is 10,000 or more.   The reactive functional group X is a group selected from the group consisting of a functional group represented by the formula (1), a primary amino group, a secondary amino group, and an isocyanate group. The manufacturing method of the printed wiring board of description.   The method for manufacturing a printed wiring board according to claim 1, wherein the reactive functional group Y is a group selected from the group consisting of an epoxy group, an acrylate group, and a methacrylate group.   The second coating step is a step of covering the surface of the metal wiring covered with the thiol compound and the surface of the insulating substrate using a polymer composition containing the polymer and substantially free of an inorganic filler. The manufacturing method of the printed wiring board in any one of Claims 1-4.   The manufacturing method of the printed wiring board of Claim 5 whose content of the polymer in the said polymer composition is 0.01-80 mass% with respect to the polymer composition whole quantity.   The manufacturing method of the printed wiring board in any one of Claims 1-6 whose number of the said reactive functional groups X is four or more.   The IC package board | substrate which has a printed wiring board obtained by the manufacturing method in any one of Claims 1-7.