TWI542270B - Method for manufacturing printed wiring board and ic package substrate - Google Patents

Description

Printed wiring substrate manufacturing method and IC package substrate

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

In recent years, with the demand for higher functionality of electronic devices, the high-density integration of electronic components has been promoted, and printed wiring boards and the like used in these electronic components have been reduced in size and density. Under such circumstances, the width of the metal wiring in the printed wiring board is also narrower.

Usually, the printed wiring board is obtained by laminating one or more layers of the metal wiring and the insulating resin layer. In this case, when the adhesion between the metal wiring and the insulating resin layer is insufficient, a gap is formed between the metal wiring and the insulating resin layer, and when water vapor or the like penetrates into the gap, electrical insulation is lowered or short-circuited between wirings is caused. .

Conventionally, as a method of improving the adhesion between the metal wiring and the insulating resin layer, a method of roughening the surface of the metal wiring to generate an anchor effect has been employed. However, in the case where the width of the metal wiring is now narrow, it is difficult to roughen the surface of the metal wiring, and the high-frequency characteristics are deteriorated due to the unevenness formed.

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, there has been proposed a method of using a triazine thiol derivative for metal wiring. A method of treating a surface (Patent Document 1) or a method of treating a surface of a metal wiring by a decane coupling agent having a mercapto group (Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-156563

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-354922

The inventors of the present invention used the triazine thiol compound (thiocyanuric acid) specifically disclosed in Patent Document 1 or the mercaptopropyltrimethoxydecane specifically disclosed in Patent Document 2, for the insulating resin layer. The adhesion was investigated, and it was found that the strength of the adhesion greatly decreased with the passage of time, and further improvement was required.

In view of the above-described actual circumstances, an object of the present invention is to provide a method for producing a printed wiring board, which is excellent in initial adhesion of the insulating resin layer of the printed wiring board and adhesion stability of the insulating resin layer.

As a result of intensive studies, the inventors of the present invention have found that by treating a metal wiring with a thiol compound having a predetermined functional group, the metal wiring is further processed using a polymer having a predetermined functional group, and the metal wiring is The stability with time of the adhesion of the insulating resin layer is improved.

That is, the inventors of the present invention have found that the above problems can be solved by the following configuration.

(1) A method of manufacturing a printed wiring board, wherein the printed wiring board is provided with an insulating resin layer on an insulating substrate with metal wiring, and the method for manufacturing the printed wiring board includes a first covering step and two or more used Reactive functional group X (in which silanol group and ruthenium atom bond hydrolyzable group) (a silicon-bonded hydrolyzable group), and at least one of the reactive functional groups X having a functional group represented by the following formula (1), and an insulating substrate surface and a metal having an insulating substrate with a metal wiring The wiring surface is covered, and the insulating substrate with the metal wiring has an insulating substrate and a metal wiring disposed on the insulating substrate. In the first cleaning step, the insulating substrate with the metal wiring is cleaned using a solvent to form a surface of the insulating substrate. The thiol compound is removed; and the second coating step uses a polymer having at least three or more reactive functional groups Y reactive with the reactive functional group X to cover the surface of the insulating substrate and the surface of the metal wiring covered with the thiol compound; In the second cleaning step, the insulating substrate with the metal wiring is cleaned with a solvent to remove the polymer on the surface of the insulating substrate; and the insulating resin layer forming step is performed on the surface of the metal wiring side of the insulating substrate with the metal wiring An insulating resin layer is formed.

(2) The method for producing a printed wiring board according to the above aspect, wherein the polymer has a number average molecular weight of 10,000 or more.

(3) The method for producing a printed wiring board according to the above aspect, wherein the reactive functional group X is a functional group selected from the formula (1) described below, a primary amino group, and a secondary amino group. And a group in the group consisting of isocyanate groups.

(4) The method for producing a printed wiring board according to any one of (1), wherein the reactive functional group Y is selected from the group consisting of an epoxy group, an acrylate group, and a methacrylate group. The base in the group.

(5) The printed wiring board according to any one of (1) to (4) In the manufacturing method, the second coating step is a step of covering the surface of the insulating substrate and the surface of the metal wiring covered with the thiol compound using a polymer composition containing a polymer and substantially containing no inorganic filler.

(6) The method for producing a printed wiring board according to (5), wherein the content of the polymer in the polymer composition is 0.01% by weight to 80% by weight based on the total amount of the polymer composition.

The method for producing a printed wiring board according to any one of the above aspects, wherein the number of the reactive functional groups X is four or more.

(8) An IC package substrate having the printed wiring board obtained by the production method according to any one of (1) to (7).

According to the present invention, it is possible to provide a method for producing a printed wiring board, which is excellent in initial adhesion of the insulating resin layer of the printed wiring board and adhesion stability of the insulating resin layer.

Hereinafter, a suitable embodiment of the method for producing a printed wiring board of the present invention will be described.

First, the feature points compared with the prior art of the present invention will be described in detail.

In the present invention, a thiol compound having at least one functional group having two or more reactive functional groups X and having a functional group represented by the following formula (1) (hereinafter also After the metal wiring is treated as a thiol compound, a polymer having three or more reactive functional groups Y in the molecule (hereinafter also referred to simply as a polymer) is further used. The metal wiring is treated wherein the reactive functional group Y is reacted with a reactive functional group X. That is, the surface of the metal wiring is covered by a layer of a thiol compound, and the layer of the thiol compound is covered by a layer of the polymer. The thiol compound and the polymer function to support the adhesion between the metal wiring and the insulating resin layer (the function of the adhesion support layer).

The thiol compound is bonded to the metal wiring via the reactive functional group X (particularly the group represented by the formula (1)). Further, the polymer is bonded to the thiol compound via the reactive functional group Y to form a network structure (network structure) of the thiol compound and the polymer on the metal wiring.

When the network structure of the thiol compound and the polymer is formed between the metal wiring and the insulating resin layer as described above, moisture or the like is less likely to be close to the metal wiring, and oxidation or corrosion of the metal wiring is suppressed, and as a result, the adhesion of the insulating resin layer is improved. The stability over time is improved.

Further, the polymer is inserted between the metal wiring and the insulating resin layer, thereby functioning to alleviate the difference in thermal expansion between the two. In other words, the polymer exhibits a so-called stress relaxation effect, and as a result, the stability with time of the adhesion of the insulating resin layer is improved.

Further, other features of the production method of the present invention include a method in which a thiol compound or a polymer is brought into contact with an insulating substrate with a metal wiring, and then washed with a solvent (washing solvent). The inventors of the present invention have found that if an unreacted physically adsorbed thiol compound or polymer remains on the insulating substrate, a poor adhesion or the like occurs between the insulating resin layer and the insulating substrate, resulting in a short circuit. According to the above findings, it was found that sulfur can be applied to the insulating substrate by performing the treatment as in the present invention. The alcohol compound or the polymer is removed, and the adhesion of the metal wiring to the insulating resin layer can be ensured.

Further, for example, when a decane coupling agent having a halogen atom-bonding hydrolyzable group (specifically, an alkoxyalkyl group) such as mercaptopropyltrimethoxydecane used in the prior art is used in place of the above-described thiol compound, The decane coupling agent not only chemically reacts with the metal wiring but also chemically reacts with the insulating substrate. Therefore, it is difficult to remove the decane coupling agent from the insulating substrate even if the solvent is used for the cleaning treatment. Specifically, as shown in FIG. 3(A), not only the metal wiring 14 is covered with the decane coupling agent 60, but also the insulating substrate 12 is covered with the decane coupling agent 60.

Further, when the polymer is deposited on the insulating substrate, the decane coupling agent is chemically bonded to the polymer, and the polymer on the insulating substrate cannot be removed by the solvent. Specifically, as shown in FIG. 3(B), the polymer 62 is deposited on the decane coupling agent 60.

When such a decane coupling agent or a polymer is deposited on the surface of an insulating substrate, a poor adhesion or the like occurs between the insulating resin layer and the insulating substrate as described above, resulting in a short circuit.

First, the method of manufacturing the printed wiring board of the present invention will be described in detail, and then the aspect of the printed wiring board to be manufactured will be described in detail.

The method for producing a printed wiring board according to the present invention includes a first coating step, a first cleaning step, a second coating step, a second cleaning step, and an insulating resin layer forming step.

Hereinafter, the materials used in the respective steps and the order of the steps will be described in detail with reference to the drawings.

[1st covering step]

The first coating step is a step of covering the surface of the insulating substrate and the surface of the metal wiring of the insulating substrate with the metal wiring, which has an insulating substrate and is disposed on the insulating substrate, using a thiol compound. In the metal wiring, the thiol compound has two or more reactive functional groups X (excluding a sulfonyl group and a ruthenium atom-bonding hydrolyzable group), and at least one of the reactive functional groups has a formula (1) to be described later. Functional group. In other words, this step is a step of covering the surface (particularly the surface on the metal wiring side) of the insulating substrate with the metal wiring with a thiol compound. By this step, a layer of a thiol compound (thiol compound layer) 16 is formed on the surface of the insulating substrate 12 of the metal wiring-attached insulating substrate 10 shown in FIG. 1(A) and on the surface of the metal wiring 14. Figure 1 (B)). In particular, the thiol compound on the metal wiring 14 is mainly bonded to the surface of the metal wiring 14 via the group represented by the formula (1).

First, the material used in the step (insulating substrate with metal wiring, thiol compound) will be described, and the order of the steps will be described.

(Insulated substrate with metal wiring)

The insulating substrate (inner substrate) with metal wiring used in this step has an insulating substrate and metal wiring disposed on the insulating substrate. In other words, the insulating substrate with the metal wiring may have a laminated structure including at least an insulating substrate and metal wiring, and a metal wiring may be disposed on the outermost layer. FIG. 1(A) shows an aspect of an insulating substrate with metal wiring, and the insulating substrate 10 with metal wiring has an insulating substrate 12 and is disposed in insulation. Metal wiring 14 on the substrate 12. The metal wiring 14 is provided on only one side of the substrate in Fig. 1(A), but may be provided on both sides. That is, the insulating substrate 10 with the metal wiring may be a single-sided substrate or a double-sided substrate.

In the case where the metal wiring 14 is present on both surfaces of the insulating substrate 10, the first coating step, the first cleaning step, the second coating step, the second cleaning step, and the insulating resin layer forming step are performed on both surfaces of the substrate.

The insulating substrate is not particularly limited as long as it is insulating and can support the metal wiring. For example, an organic substrate, a ceramic substrate, a glass substrate, or the like can be used.

The material of the organic substrate may, for example, be a resin. For example, a thermosetting resin, a thermoplastic resin or a resin obtained by mixing the resins is preferably used. Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy resin, an anthrone resin, and a furan resin. , ketone resin, xylene resin, benzocyclobutene resin, and the like. Examples of the thermoplastic resin include a polyimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, an aromatic polyamide resin, a liquid crystal polymer, and the like.

Furthermore, the material of the organic substrate may also be a glass woven fabric, a glass non-woven fabric, an aromatic polyamide woven fabric, an aromatic polyamide woven fabric, an aromatic polyamide woven fabric, or a cloth impregnated with the above resin. Materials, etc.

Metal wiring mainly contains metal. The type of the metal is not particularly limited, and examples thereof include copper or a copper alloy, silver or a silver alloy, tin, palladium, gold, nickel, chromium, platinum, iron, gallium, indium, or a combination of these metals.

The method of forming the metal wiring on the insulating substrate is not particularly limited, and a known method can be employed. A representative method may be a subtractive process using an etching process or a semi-additive process using electroplating.

Further, in the metal wiring, an organic substance such as a binder resin may be contained in a range that does not impair the effects of the present invention.

The width of the metal wiring is not particularly limited, and is preferably from 0.1 μm to 1000 μm, more preferably from 0.1 μm to 25 μm, even more preferably from 0.1 μm to 10 μm, in terms of high integration of the printed wiring board.

The interval between the metal wirings is not particularly limited, and is preferably from 0.1 μm to 1000 μm, more preferably from 0.1 μm to 25 μm, even more preferably from 0.1 μm to 10 μm, in terms of high integration of the printed wiring board.

Further, the pattern shape of the metal wiring is not particularly limited, and may be any pattern. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, etc. are mentioned.

The thickness of the metal wiring is not particularly limited, and is preferably from 1 μm to 1000 μm, more preferably from 3 μm to 25 μm, even more preferably from 10 μm to 20 μm, in terms of high integration of the printed wiring board.

In the present invention, the initial adhesion of the 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, and is preferably 10 μm or less, more preferably 0.001 μm to 2.0 μm, and still more preferably 0.01 μm in terms of high-frequency characteristics of the printed wiring board. 0.9 μm, particularly preferably 0.02 μm to 0.5 μm.

Further, Rz is measured in accordance with JIS B 0601 (1994).

Other aspects of the insulating substrate with metal wiring used in this step include a multilayer wiring board in which two or more insulating substrates and two or more metal wires are alternately arranged. For example, in the multilayer wiring board, another metal wiring 50 (metal wiring layer) and another insulating substrate 40 (see FIG. 2) may be sequentially provided between the insulating substrate 12 and the metal wiring 14. Further, two or more other metal wirings 50 and other insulating substrates 40 may be alternately arranged between the insulating substrate 12 and the metal wiring 14 in this order.

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

Further, a through hole may be formed in the insulating substrate. In the case where metal wiring is provided on both surfaces of the insulating substrate, the metal wirings on both sides may be electrically connected by filling a metal (for example, copper or copper alloy) in the through holes.

(thiol compound)

The thiol compound used in this step has two or more reactive functional groups X (excluding a sulfonyl group and a ruthenium atom-bonded hydrolyzable group), and at least one of the reactive functional groups X has the following formula (1) The functional group represented. By surface-treating the metal wiring by using the compound, the initial adhesion of the insulating resin layer laminated thereon and the stability with time of the adhesion of the insulating resin layer can be improved.

The reactive functional group X of the thiol compound may be a functional group that reacts with the reactive functional group Y of the polymer described later. For example, 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 may, for example, be mentioned.

Among them, the reactivity is more excellent, and the adhesion of the insulating resin layer is over time. In terms of further improving the stability, 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 is preferred. In particular, it is more preferably a group represented by the formula (1).

Among them, the reactive functional group X does not include a decyl alcohol group and a ruthenium atom-bonded hydrolyzable group. The stanol group refers to a group (-Si-OH) in which a hydroxyl group is directly bonded to a ruthenium atom. Further, the hydrazine atom-bonding hydrolyzable group means a hydrolyzable group bonded to a ruthenium atom (for example, an alkoxy fluorenyl group in which an alkoxy group is directly bonded to a ruthenium atom (-Si-OR (R: alkane) The hydrolyzable group may, for example, be an alkoxy group; a hydrocarbyloxy group; a decyloxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an isocyanate group; a cyano group; an amine group; Base.

When these groups are contained in the thiol compound, a network (network) structure of hydrophilic cerium oxide is formed on the surface of the metal wiring. When such a network is provided, 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 stability with respect to the adhesion to the insulating resin layer is deteriorated with time. In addition, a network structure of germanium dioxide is also formed on the insulating substrate, and the insulation reliability is remarkably lowered.

The thiol compound contains two or more of the above reactive functional groups X. By containing two or more reactive functional groups X, one reactive functional group X can be mainly used to form a bond with the surface of the metal wiring, and another reactive functional group X can be bonded to the polymer described later.

In particular, the number of reactive functional groups X is preferably three or more, and more preferably three, in terms of the initial adhesion of the insulating resin layer and the stability with time of the adhesion of the insulating resin layer. 20, and then better 4 to 10, especially 4 to 6.

When the number of the reactive functional groups X is one, the initial adhesion of the insulating resin layer is remarkably deteriorated.

The reactive functional group X of the thiol compound contains at least one functional group represented by the formula (1). When the thiol compound contains at least one such functional group, the initial adhesion of the insulating resin layer is improved.

HS-L ¹ -* type (1)

L ¹ in the formula (1) represents a divalent aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group or an alkynylene group. In particular, in terms of further improving the stability of the adhesiveness of the insulating resin layer, the carbon number is preferably from 1 to 20, more preferably from 2 to 10, and particularly preferably from 4 to 8. .

More specifically, the divalent aliphatic hydrocarbon group may, for example, be a methylene group, an ethyl group, a propyl group, an extended isopropyl group or a butyl group.

Among them, the HS group in the formula (1) is preferably a primary thiol (i.e., preferably L ¹ directly bonded to the HS group) in terms of further improvement in the stability of the adhesiveness of the insulating resin layer. The partial structure in is -CH ₂ -).

On the other hand, in the case where 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, in the case of using a compound having such a group, the initial adhesion of the insulating resin layer is extremely poor.

The reactive functional group X equivalent (g/eq) of the thiol compound is not particularly limited, and the initial adhesion of the insulating resin layer or the adhesion of the insulating resin layer is not particularly limited. In terms of more excellent stability over time, it is preferably 2,100 or less, more preferably 400 or less, and still more preferably 250 or less. Further, the lower limit is not particularly limited, and in many cases, from the viewpoint of the synthesis of the thiol compound, it is usually more than 40.

In addition, the reactive functional group X equivalent represents the size of the molecule per unit number of the reactive functional group X contained in the thiol compound.

The molecular weight of the thiol compound is not particularly limited, and the insulating resin layer is more excellent in initial adhesion and is excellent in solubility in a solvent or the like, and is preferably 8400 or less, more preferably 3,000 or less, and particularly preferably 2000. the following. Further, the lower limit is not particularly limited, and in many cases, from the viewpoint of the synthesis of the thiol compound, it is usually more than 80.

The content of the sulfur atom in the thiol compound (the content of the sulfur atom) is not particularly limited, and is preferably 20% by weight or more, and more preferably 24%, in terms of the stability of the adhesiveness of the insulating resin layer. ~70wt%. In particular, it is preferably 35 wt% or more, and more preferably 35 wt% to 64 wt%, from the viewpoint that the adhesion stability of the insulating resin layer is particularly excellent.

Further, the sulfur atom content indicates the content (wt%) of sulfur atoms in the total molecular weight of the thiol compound.

(suitable aspect of thiol compound)

A suitable form of the thiol compound is a thiol compound represented by the following formula (2). In the case of this compound, the initial adhesion of the insulating resin layer or the adhesion stability of the insulating resin layer is more excellent with time.

Formula (2), L ¹ is of the formula L ¹ is the same meaning, a suitable range is also the same as above (1).

In the formula (2), L ² and L ³ each independently represent a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8), a divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12), -O-, and -S. -, -SO ₂ -, -N(R)-(R:alkyl), -CO-, -NH-, -COO-, -CONH- or a combination of these groups (for example, alkylene oxide) a group, an alkoxycarbonyl group, an alkylcarbonyloxy group, etc.).

The divalent aliphatic hydrocarbon group (for example, an alkylene group) may, for example, be a methylene group, an exoethyl group, a propyl group or a butyl group.

Examples of the divalent aromatic hydrocarbon group include a stretched phenyl group and an extended naphthyl group.

In particular, L ² and L ^{3 are} preferably a divalent aliphatic hydrocarbon group, —CO—, —O—, —S— or a combination of these groups, in terms of excellent initial adhesion of the insulating resin layer. The basis of the formation.

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

In the formula (2), n represents an integer of 1 or more. In particular, from the viewpoint of easy synthesis and excellent initial adhesion of the insulating resin layer, it is preferably from 1 to 19, more preferably from 2 to 9, and still more preferably from 3 to 7.

In the formula (2), m represents an integer of 1 or more. In particular, from the viewpoint of easy synthesis and excellent initial adhesion of the insulating resin layer, it is preferably from 1 to 19, more preferably from 1 to 9, and even more preferably from 1 to 5.

n+m is not particularly limited, and is preferably 3 or more, more preferably 3 to 20. Furthermore, the best is 4~10, and the best is 4~8.

In the formula (2), X represents an n+m-valent hydrocarbon group which may contain a sulfur atom, a nitrogen atom or an oxygen atom.

The carbon number of the hydrocarbon group is not particularly limited, and the carbon number is preferably from 1 to 20, more preferably from 1 to 8, in terms of workability, solubility in a solvent, and the like. More specifically, the hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a group in which the groups are combined.

The aliphatic hydrocarbon group may be any of a linear chain, a branched form, and a cyclic form, and is preferably a carbon number of 1 to 10, more preferably carbon, in terms of excellent workability and solubility in a solvent. The number is 1~8.

The aromatic hydrocarbon group is not particularly limited, and is preferably from 1 to 10, more preferably from 1 to 7, in terms of excellent workability and superior solubility in a solvent.

A more suitable aspect of the thiol compound is exemplified by the thiol compound represented by the following formula (3). In the case of this compound, the initial adhesion of the insulating resin layer or the stability of the adhesiveness of the insulating resin layer is further improved.

Of formula (3), L ¹ and L ¹ is the same meaning, a suitable range is also the same as described above in the formula (1).

Of formula (3), L ² is also the same as the range of the above formula (2) in the same meaning as L ^2, the right.

In the formula (3), Y represents a sulfur atom, a nitrogen atom or an oxygen atom. A p-valent aliphatic hydrocarbon group. The definition of the aliphatic hydrocarbon group has the same meaning as the definition of the aliphatic hydrocarbon group in the above X, and the suitable range is also the same.

Further, examples of suitable aspects of Y include the groups represented by the following formulas (4) to (6).

In the formula (5), L ⁴ represents an oxygen atom or a divalent aliphatic hydrocarbon group which may contain an oxygen atom (the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 10. Further, the carbon number means the group) The total value of the number of carbons contained in the base).

In the formulas (4) to (6), * indicates the bonding position.

In the formula (3), p represents an integer of 4 or more. In particular, it is preferably 4 to 20, and more preferably 4 to 6, in terms of easy synthesis and excellent initial adhesion of the insulating resin layer.

The thiol compound may be used alone or in combination of two or more.

Specific examples of the thiol compound include the compounds shown below. Among them, in terms of the excellent initial adhesion of the insulating resin layer, pentaerythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexa(3-mercaptopropene) are preferably mentioned. Dipentaerythritol hexakis (3-mercaptopropionate), tetrakis-(7-mercapto-2,5-dithiazepine Methyl (tetrakis (7-mercapto-2, 5-dithiaheptyl) methane), etc., particularly preferably tetrakis-(7-fluorenyl-2,5-dithiaheptyl)methane.

(order of steps)

In this step, the surface of the insulating substrate and the surface of the metal wiring of the insulating substrate with the metal wiring described above are covered with a thiol compound.

The method of this step is not particularly limited as long as the insulating substrate with the metal wiring is brought into contact with the thiol compound, and the thiol compound or the liquid thiol may be applied to the insulating substrate with the metal wiring. A known method of immersing an insulating substrate with a metal wiring in a compound is known. More specific The immersion immersion, the spray coating, the spray coating, the spin coating, and the like are preferably soaking, spraying, and spray coating in terms of ease of handling and ease of adjustment of the treatment time.

Further, a surface treatment liquid containing a thiol compound and a solvent may be applied to an insulating substrate with metal wiring (on the surface of the metal wiring side) as needed, or metal wiring may be immersed in the surface treatment liquid. Insulating substrate. In this case, it is easy to control the amount of the thiol compound bonded to the metal wiring, and the initial adhesion of the insulating resin layer is more easily improved.

Hereinafter, the configuration of the surface treatment liquid to be used will be described in detail.

The content of the thiol compound in the surface treatment liquid is not particularly limited, and is preferably 0.01 mM to 10 mM in terms of excellent initial adhesion of the insulating resin layer or adhesion stability of the insulating resin layer. More preferably, it is 0.05 mM to 3 mM, and more preferably 0.1 mM to 1 mM. If the content of the thiol compound is too large, control of the amount of the thiol compound bonded to the metal wiring becomes difficult and uneconomical. When the content of the thiol compound is too small, the bonding of the thiol compound takes time and the productivity is poor.

The type of the solvent to be contained in the surface treatment liquid is not particularly limited, and examples thereof include water, an alcohol solvent (for example, methanol, ethanol, or isopropanol), and a ketone solvent (for example, acetone, methyl ethyl ketone, and cyclohexanone). , amide-based solvents (such as formamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), nitrile solvents (such as acetonitrile, propionitrile), ester solvents (such as methyl acetate) , ethyl acetate, γ-butyrolactone), carbonate-based solvent (for example, dimethyl carbonate, diethyl carbonate), ether solvent (for example, cellosolve, tetrahydrofuran), halogen solvent, glycol ether solvent (eg dipropylene glycol methyl ether), glycol ester A solvent (for example, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate) or the like. These solvents may be used in combination of two or more kinds.

Among these, a ketone solvent, a glycol ester solvent, and an alcohol solvent are preferable in terms of solubility of a thiol compound.

The content of the solvent in the surface treatment liquid is not particularly limited, and is preferably from 50% by weight to 99.99% by weight, more preferably from 90% by weight to 99.99% by weight, particularly preferably from 95% by weight to 99.99% by weight, based on the total amount of the treating liquid.

The surface treatment liquid preferably contains a resin having a functional group reactive with a thiol compound (hereinafter also referred to as a resin X. For example, an epoxy resin or an acrylic resin having an acrylate group). When the surface treatment liquid contains the resin X, it reacts with the above-mentioned thiol compound, and the stability of the treatment liquid itself is impaired. Further, it is difficult to bond a required amount of the thiol compound to the metal wiring, and as a result, the initial adhesion of the insulating resin layer is lowered.

In addition, the term "substantially free of the resin X" means that the content of the resin X in the surface treatment liquid is 1% by weight or less based on the total amount of the treatment liquid. It is particularly preferred to be free of resin X (0 wt%).

Further, the treatment liquid may further contain an additive such as a pH adjuster, a surfactant, a preservative, or an anti-precipitation agent.

In terms of controlling the amount of adhesion (bonding amount) of the thiol compound, the temperature of the thiol compound or the surface treatment liquid when it is in contact with the insulating substrate with the metal wiring is preferably in the range of 5 ° C to 75 ° C, and more preferably It is preferably in the range of 10 ° C to 45 ° C, and more preferably in the range of 15 ° C to 35 ° C.

Further, in terms of productivity and control of the amount of bonding (bonding amount) of the thiol compound, the contact time is preferably in the range of 30 seconds to 120 minutes, and more It is preferably in the range of 3 minutes to 60 minutes, and is preferably in the range of 5 minutes to 30 minutes.

[1st cleaning step]

This step is a step of cleaning the insulating substrate with the metal wiring using a solvent (first cleaning solvent) to remove the thiol compound on the surface of the insulating substrate. By performing this step, a thiol compound other than the thiol compound bonded to the metal wiring, in particular, a thiol compound on the surface of the insulating substrate can be removed by washing. Specifically, as shown in FIG. 1(C), the thiol compound layer 16 on the insulating substrate 12 is substantially removed, and excess thiol compound on the metal wiring 14 is also removed to form a bond to the metal wiring 14. A layer of a thiol compound (thiol compound layer) 18 on the surface. Further, after the completion of the step, the thiol compound may remain on the insulating substrate 12 within a range that does not impair the effects of the present invention.

First, the material (first cleaning solvent) used in this step will be described, and the order of the steps will be described later.

(1st cleaning solvent)

The type of the solvent (first cleaning solvent) to be used in the first cleaning step of cleaning the insulating substrate with the metal wiring is not particularly limited, and may be any solvent that can remove the thiol compound on the insulating substrate. Among them, a solvent which dissolves a thiol compound is preferred. By using this solvent, excess thiol compound deposited on the insulating substrate or excess thiol compound on the metal wiring can be removed more efficiently.

Examples of the solvent include water, an alcohol solvent (for example, methanol, ethanol, or propanol), and a ketone solvent (for example, acetone, methyl ethyl ketone, and cyclohexanone). a guanamine-based solvent (for example, formamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone), a nitrile solvent (for example, acetonitrile, propionitrile), an ester solvent (for example, methyl acetate, Ethyl acetate, γ-butyrolactone), carbonate-based solvent (for example, dimethyl carbonate or diethyl carbonate), ether solvent (for example, cellosolve, tetrahydrofuran), halogen solvent, glycol ether solvent ( For example, dipropylene glycol methyl ether), a glycol ester solvent (for example, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate) or the like. These solvents may be used in combination of two or more kinds.

Among them, an alcohol solvent, a ketone solvent (preferably cyclohexanone), a glycol ester solvent (preferably propylene glycol monomethyl ether acetate) is preferred in terms of more excellent thiol compound removal property. An ester, a diethylene glycol monoethyl ether acetate, a guanamine solvent (preferably N-ethylpyrrolidone) or a mixed solvent of the solvent and water.

The boiling point of the solvent to be used (25 ° C, one atmosphere) is not particularly limited, and from the viewpoint of safety, it is preferably from 75 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C.

(order of steps)

The washing method is not particularly limited, and a known method can be employed. For example, a method of applying a first cleaning solvent on an insulating substrate with a metal wiring (on the surface on the metal wiring side), a method of immersing an insulating substrate with a metal wiring in the first cleaning solvent, and the like may be mentioned.

In addition, the liquid temperature of the first cleaning solvent is preferably in the range of 5 ° C to 60 ° C, and more preferably in the range of 15 ° C to 35 ° C, in terms of controlling the amount of bonding (bonding amount) of the thiol compound.

In addition, in terms of productivity and control of the amount of adhesion (bonding amount) of the thiol compound, the contact time between the insulating substrate with the metal wiring and the first cleaning solvent is preferably in the range of 10 seconds to 10 minutes. More preferably in the range of 15 seconds to 5 minutes.

(thiol compound layer)

As shown in Fig. 1(C), 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, and the initial adhesion of the insulating resin layer is more excellent. In particular, it is preferably 0.1 nm to 10 nm, more preferably 0.1 nm to 3 nm, and still more preferably 0.1 nm to 2 nm.

Further, in order to control the thickness or the coverage of the thiol compound layer 18, the first coating step and the first washing step may be carried out twice or more continuously. In this 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.

[2nd covering 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 reactive with the reactive functional group X in the molecule. In other words, this step is a step of covering the surface of the insulating substrate with the metal wiring (particularly the surface on the metal wiring side) with the polymer. More specifically, as shown in FIG. 1(D), 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 via 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 adhesion of the insulating resin layer or the temporal stability of the adhesion of the insulating resin layer described later is improved.

First, the material (polymer) used in the step will be described, and the order of the steps will be described.

(polymer)

The polymer used in this step is a polymer having at least three or more reactive functional groups Y reactive with the above-mentioned reactive functional group X in the molecule. The polymer is bonded to the unreacted reactive functional group X of the above-described thiol compound bonded to the metal wiring via the reactive functional group Y. The bonded polymer serves to relax the stress of the metal wiring and the insulating resin layer formed thereon, and contributes to improving the initial adhesion of the insulating resin layer and the stability of the insulating resin layer with time.

The reactive functional group Y is not particularly limited as long as it is a functional group reactive with the above reactive functional group X. For example, a hydroxyl group, a primary amino group, a secondary amino group, an epoxy group (particularly a glycidyl group), an acrylate group, a methacrylate group, etc. are mentioned.

In particular, an epoxy group, an acrylate group or a methacrylate group is preferred from the viewpoint of further improving the reactivity and further improving the initial adhesion of the insulating resin layer, and more preferably an epoxy group.

The number of reactive functional groups Y contained in the polymer molecule is three or more. In particular, in view of further improving the stability with time of the adhesiveness of the insulating resin layer, it is preferably 10 or more, more preferably 50 or more, and particularly preferably 200 or more. The upper limit is not particularly limited, and the solubility and reaction of the polymer are In terms of easiness, it is preferably 1000 or less.

When the number of the reactive functional groups Y contained in the polymer is less than three, the network structure of the thiol compound cannot be sufficiently formed, and the stability with time of the adhesiveness of the insulating resin layer is extremely poor.

The Y-equivalent (g/eq) of the reactive functional group of the polymer is not particularly limited, and is preferably 2,000 or less, more preferably 1,000 or less, from the viewpoint of further excellent stability of the adhesiveness of the insulating resin layer. Further, it is preferably 200 or less. Further, the lower limit is not particularly limited, and in many cases, from the viewpoint of the synthesis of the polymer, it is usually 40 or more.

In addition, the reactive functional group Y equivalent represents the size of the molecule per unit number of the reactive functional group Y contained in the polymer.

The number average molecular weight of the polymer is not particularly limited, and is preferably 5,000 or more, more preferably 7,500 or more, and still more preferably 10,000 or more, from the viewpoint of further improving the stability of the adhesiveness of the insulating resin layer. It is 17500 or more, and the best is 36000 or more. The upper limit is not particularly limited, and is preferably 500,000 or less, and more preferably 150,000 or less, from the viewpoint of more excellent workability such as solubility of the polymer.

Further, an epoxy resin having a different number and average molecular weight may be used in combination.

The type of the polymer is not particularly limited, and examples thereof include a polyimide resin, an epoxy resin, a urethane resin, a polyethylene resin, a polyester resin, a novolac resin, a cresol resin, an acrylic resin, and a Acrylic resin, styrene resin, and the like. Among them, an acrylic resin or a methacrylic resin is preferable in terms of material availability, film formability, and the like.

(suitable aspect of the polymer)

A suitable form of the polymer is a polymer having a repeating unit represented by the following formula (7). When it is this polymer, the stability with respect to the adhesiveness of the insulating resin layer is further improved.

In the formula (7), R ² represents a hydrogen atom or an alkyl group. In terms of ease of synthesis, the alkyl group preferably has a carbon number of from 1 to 5, more preferably a carbon number of from 1 to 3.

In the formula (7), L ⁵ represents a single bond or a divalent linking group. The definition of the divalent linking group has the same meaning as the definition of the divalent linking group represented by L ² and L ³ in the formula (2).

L ^{5 is} preferably a divalent aliphatic hydrocarbon group, -CO-, -O- or a group in which these groups are combined, in terms of more excellent stability with respect to the adhesion of the insulating resin layer.

In the formula (7), Z represents an epoxy group, an acrylate group, and a methacrylate group. In particular, an epoxy group is preferred in terms of excellent initial adhesion of the insulating resin layer or adhesion stability of the insulating resin layer.

Other suitable aspects of the polymer include epoxy resins. The epoxy resin to be used is not particularly limited as long as it has at least three epoxy groups, and a known resin (for example, a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, or a shrinkage) can be used. Glyceramine type epoxy resin, poly Glycidyl methacrylate, etc.).

(order of steps)

In this step, the surface of the insulating substrate and the surface of the metal wiring on which the metal wiring-attached insulating substrate is attached are covered with a polymer.

The method of this step is not particularly limited as long as the insulating substrate with the metal wiring is brought into contact with the polymer, and the polymer may be coated on the insulating substrate with the metal wiring (coating method) or attached thereto. A known method such as laminating a polymer (lamination method) on an insulating substrate of a metal wiring is used. Examples of the method of the coating method include soaking, spraying, spray coating, spin coating, etc., and in terms of ease of handling and easiness of adjusting the treatment time, it is preferred to soak the dipping and spraying the spray. , spray coating.

Further, if necessary, a polymer composition containing a polymer and a solvent may be applied onto an insulating substrate with a metal wiring (on the surface of the metal wiring side), or a metal is impregnated in the polymer composition. Insulated substrate for wiring. In this case, the amount of the polymer bonded to the metal wiring covered with the thiol compound can be easily controlled, and the stability with time of the adhesion of the insulating resin layer can be further improved.

Hereinafter, the configuration of the polymer composition to be used will be described in detail.

The content of the polymer in the polymer composition is not particularly limited, and it is easy to control the amount of the bonded polymer and the temporal stability of the adhesion of the insulating resin layer is further improved with respect to the polymer composition. The total amount of the particles is preferably from 0.01% by weight to 80% by weight, more preferably from 0.1% by weight to 50% by weight, even more preferably from 0.5% by weight to 20% by weight.

The kind of the solvent contained in the polymer composition is not particularly limited, and examples thereof For example, a solvent or the like used in the above surface treatment liquid can be exemplified.

Among them, in terms of excellent solubility, an alcohol solvent, a ketone solvent (preferably cyclohexanone), a glycol ester solvent (preferably propylene glycol monomethyl ether acetate, diethylene glycol) is preferred. Alcohol monoethyl ether acetate, a guanamine solvent (preferably N-ethylpyrrolidone).

Further, the polymer composition preferably contains substantially no inorganic filler. When the polymer composition contains an inorganic filler, the inorganic filler and the polymer are laminated to 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, magnesia, calcium oxide, titania, zirconia, talc, and silica.

In addition, the term "containing substantially no inorganic filler" means that the content of the inorganic filler in the polymer composition is 0.9% by weight or less based on the total amount of the polymer and the inorganic filler in the polymer composition. Particularly preferred is no inorganic filler (0 wt%).

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

[2nd cleaning step]

This step is a step of cleaning the insulating substrate with the metal wiring using a solvent (second cleaning solvent) to remove the polymer on the surface of the insulating substrate. By performing this step, the thiol compound on the metal wiring can be Polymers other than the bonded polymer, particularly the polymer on the surface of the insulating substrate, are removed by cleaning. Specifically, as shown in FIG. 1(E), the polymer 16 on the insulating substrate 12 is removed, and excess polymer on the metal wiring 14 is also removed to form a metal wiring bonded to the thiol compound. A layer of polymer (polymer layer) 22. Further, after the completion of the step, the polymer may remain on the insulating substrate 12 within a range that does not impair the effects of the present invention.

First, the material used in this step (second cleaning solvent) will be described, and the order of the steps will be described.

(2nd cleaning solvent)

The type of the solvent (second cleaning solvent) used in the second cleaning step of cleaning the insulating substrate with the metal wiring is not particularly limited, and may be any solvent that can remove the polymer on the insulating substrate. Among them, a solvent which dissolves the polymer is preferred. By using this solvent, excess polymer deposited on the insulating substrate or excess polymer on the metal wiring can be removed more efficiently.

The type of the solvent is not particularly limited as long as the polymer can be removed, and examples thereof include a solvent exemplified in the first cleaning solvent used in the first washing step.

Among them, in terms of polymer removability, an alcohol solvent, a ketone solvent (preferably cyclohexanone), a glycol ester solvent (preferably propylene glycol monomethyl ether acetate, and two) are preferred. Ethylene glycol monoethyl ether acetate, a guanamine solvent (preferably N-ethylpyrrolidone) or a mixed solvent of the solvent and water.

The boiling point of the solvent used (25 ° C, one atmosphere) is not limited The system is preferably from 75 ° C to 200 ° C, more preferably from 80 ° C to 180 ° C from the viewpoint of safety.

(order of steps)

The washing method is not particularly limited, and a known method can be employed. For example, a method of applying a second cleaning solvent to an insulating substrate with a metal wiring (particularly, a surface on a metal wiring side), a method of immersing an insulating substrate with a metal wiring in a second cleaning solvent, and the like may be mentioned.

Further, the liquid temperature of the second cleaning solvent is preferably in the range of 5 ° C to 60 ° C, and more preferably in the range of 15 ° C to 35 ° C, in terms of controlling the amount of bonding (bonding amount) of the polymer.

In addition, in terms of productivity and control of the amount of bonding (bonding amount) of the polymer, the contact time between the insulating substrate with the metal wiring and the second cleaning solvent is preferably in the range of 10 seconds to 10 minutes. Good range of 15 seconds to 5 minutes.

By performing the above steps, a laminated structure of the thiol compound layer 18 and the polymer layer 22 is formed on the metal wiring (Fig. 1(E)).

The thickness of the polymer layer 22 provided on the thiol compound layer 18 is not particularly limited, and is preferably 1 μm or less, more preferably 0.2 μm or less, from the viewpoint of easily removing the layer when the electronic component is mounted. Further preferably, it is 0.1 μm or less. In addition, the lower limit is not particularly limited, and it is preferably 0.005 μm or more from the viewpoint of further improving the stability of the adhesiveness of the insulating resin layer obtained from the polymer layer 22 over time.

Further, it is preferred that the polymer layer 22 be substantially free of inorganic fillers. The term "substantially free of inorganic filler" means the inorganic filler in the polymer layer 22. The content is 0.9% by weight or less based on the total amount of the polymer layer 22. Particularly preferred is no inorganic filler (0 wt%).

Further, by performing the above steps, the thiol compound and the polymer on the insulating substrate are substantially removed, and the insulating resin layer described later can be brought into contact with the insulating substrate, and as a result, the initial adhesion of the insulating resin layer and the adhesion after the end of the step are obtained. The stability over time is improved.

[Insulating resin layer forming step]

This step is a step of forming an insulating resin layer on the surface of the metal wiring side of the insulating substrate with the metal wiring, and the insulating substrate with the metal wiring has the metal wiring covered by the polymer layer obtained in the above step. More specifically, as shown in FIG. 1(F), the insulating resin layer 24 is provided on the insulating substrate 10 with the metal wiring so as to be in contact with the metal wiring 14 covered with the polymer layer 22, thereby obtaining a printed wiring substrate. 26. By providing the insulating resin layer 24, insulation reliability between the metal wirings 14 can be ensured. Further, since the insulating substrate 12 and the insulating resin layer 24 can be in direct contact with each other, the insulating resin layer 24 is excellent in adhesion.

First, the material of the insulating resin layer will be described, and then the method of forming the insulating resin layer will be described.

As the 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, and specific examples thereof include an epoxy resin, an aromatic polyamide resin, a crystalline polyolefin resin, an amorphous polyolefin resin, and a fluorine-containing resin (polytetrafluoroethylene). , perfluoropolyimine, perfluorinated amorphous resin, etc.), polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyetheretherketone resin, acrylate resin, and the like. Interlayer insulating resin Examples of the layer include ABF GX-13 and ABF GX-92 manufactured by Ajinomoto Fine-Techno Co., Ltd.

Further, a so-called solder resist layer can also be used as the insulating resin layer. A commercially available product may be used as the solder resist. Specific examples thereof include PFR800, PSR4000 (trade name) manufactured by Sun Ink Manufacturing Co., Ltd., and SR7200G and SR7300G manufactured by Hitachi Chemical Co., Ltd.

Further, a photosensitive film resist can also be used as the insulating layer. Specific examples include SUNFORT manufactured by ASAHI KASEI E-materials, and Photek manufactured by Hitachi Chemical Co., Ltd.

Among them, the insulating resin layer is preferably a resin containing an epoxy group or a (meth) acrylate group. This resin is easily bonded to the above polymer layer, and as a result, the stability with time of the adhesion of the insulating resin layer is further improved.

The resin is preferably a main component of the insulating resin layer. The term "main component" means that the total amount of the resin is 50% by weight or more, preferably 60% by weight or more, based on the total amount of the insulating resin layer. Furthermore, the upper limit is 100% by weight.

As the epoxy group-containing resin, a known epoxy resin can be used. For example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine 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, a methacrylate resin, or the like can be used.

Further, it is preferable that the insulating resin layer contains an inorganic filler. By containing an inorganic filler in the insulating resin layer, the insulating property is further improved, and the coefficient of thermal expansion (CTE) is lowered. Further, as the type of the inorganic filler, a known material can be used as described above.

The content of the inorganic filler in the insulating resin layer is preferably from 1% by weight to 85% by weight, more preferably from 15% by weight to 80% by weight, even more preferably 40% by weight, based on the total amount of the insulating resin layer. ~75wt%.

The method of forming the insulating resin layer on the insulating substrate with the metal wiring is not particularly limited, and a known method can be employed. For example, a method in which a film of an insulating resin layer is directly laminated on an insulating substrate with a metal wiring; or a composition for forming an insulating resin layer containing a component constituting the insulating resin layer is applied to an insulating layer with metal wiring A method on a substrate; or a method of immersing an insulating substrate with a metal wiring in the composition for forming an insulating resin layer.

Further, the insulating resin layer-forming composition may contain a solvent as needed. When a composition for forming an insulating resin layer containing a solvent is used, the composition may be placed on a substrate, and then heat-treated as necessary to remove the solvent.

Further, after the insulating resin layer is provided on the insulating substrate with the metal wiring, the insulating resin layer may be subjected to energy application (for example, exposure or heat treatment).

The thickness of the insulating resin layer to be formed is not particularly limited, and is preferably 5 μm to 50 μm, and more preferably 15 μm to 40 μm from the viewpoint of insulation reliability between wirings.

In FIG. 1(F), the insulating resin layer 24 is described as one layer, but may have a multilayer structure.

[Drying step]

This step is a step disposed between the above steps as needed, and A step of heating and drying an insulating substrate with metal wiring. When moisture remains on the insulating substrate with the metal wiring, the migration of the metal ions is promoted, and as a result, the insulation between the metal wirings may be impaired. Therefore, it is preferable to remove the water by providing this step. In addition, this step is an arbitrary step, and when the solvent used in the above step is a solvent having excellent volatility, the step may not be carried out.

In terms of suppressing oxidation of the metal in the metal wiring, the heat drying condition is preferably carried out at 70 ° C to 120 ° C (preferably 80 ° C to 110 ° C) for 15 seconds to 10 minutes (preferably 30 seconds). Clock ~ 5 minutes). If the drying temperature is too low or the drying time is too short, the removal of moisture may be insufficient. If the drying temperature is too high or the drying time is too long, an oxide film of a metal may be formed.

The apparatus used for drying is not particularly limited, and a known heating device such as a constant temperature layer or a heater can be used.

[Printed wiring board]

By the above-described steps, as shown in FIG. 1(F), the printed wiring board 26 is provided, and the printed wiring board 26 includes the insulating substrate 10 with the metal wiring and the insulating resin layer 24, and the insulating resin layer 24 is disposed with the insulating resin layer 24 attached thereto. The thiol compound layer 18 and the polymer layer 22 are interposed between the metal wiring 14 and the insulating resin layer 24 on the surface of the insulating substrate 10 of the metal wiring on the metal wiring 14 side. 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. In the obtained printed wiring board 26, the insulating resin layer 24 is excellent in adhesion to the insulating substrate 10 to which the metal wiring is attached.

Furthermore, as shown in FIG. 1(F), the metal wiring 14 is listed above. The printed wiring board 26 of the wiring structure of one layer is taken as an example, but it is of course 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 the multilayer insulating substrate 12 and the metal wiring 14 are alternately laminated.

The printed wiring board obtained by the manufacturing method of the present invention can be used for various applications and structures, and examples thereof include a mother board substrate, a semiconductor package board, an integrated circuit (IC) package board, and a large-scale integrated circuit (Large). Scale Integration, LSI) package substrate, Molded Interconnect Device (MID) substrate, and the like. The manufacturing method of the present invention can be applied to a rigid substrate, a flexible substrate, a flexible bonded substrate, a molded circuit substrate, and the like.

Further, the insulating resin layer in the obtained printed wiring board may be partially removed, and a semiconductor wafer may be mounted and used as a printed circuit board.

For example, when a solder resist is used as the insulating resin layer, a predetermined pattern-shaped mask is placed on the insulating resin layer, energy is applied to cure the insulating resin layer, and the insulating resin layer in the region where no energy is applied is removed. The wiring is exposed. Then, the surface of the exposed wiring is cleaned (for example, by using sulfuric acid, a soft etchant, an alkali, or a surfactant) by a known method, and then the semiconductor wafer is mounted on the wiring surface.

In the case where 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.

Further, a metal wiring (wiring pattern) may be further provided on the insulating resin layer of the obtained printed wiring board. The method of forming the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, or the like) can be used.

In the present invention, a substrate in which a metal wiring (wiring pattern) is further provided on the insulating resin layer of the obtained printed wiring board can be used as a new insulating substrate (inner substrate) with metal wiring, or a new layer can be used. A layer of insulating resin and metal wiring.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

<Example 1>

Using a copper clad laminate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679F, substrate: glass epoxy substrate), a metal wiring-attached insulating substrate having copper wiring of L/S = 1000 μm / 500 μm was formed by a semi-additive method. A. The insulating substrate A with the metal wiring is produced by the following method.

After the copper-clad laminate is subjected to acid cleaning, water washing, and drying, a dry film resist (DFR, trade name: RY3315, manufactured by Hitachi Chemical Co., Ltd.) is laminated by a vacuum laminator under the pressure of 0.2 MPa and 70 °C. ). After lamination, the copper pattern forming portion was mask exposed at 70 mJ/cm ² using an exposure machine having a center wavelength of 365 nm. Thereafter, development was carried out with a 1% aqueous sodium hydrogencarbonate solution, followed by washing with water to obtain a plating resist pattern.

The plating is performed on the copper exposed between the resist patterns by pre-plating treatment and water washing. At this time, the electrolytic solution was an acidic sulfuric acid solution using copper (II) sulfate, a plate of crude copper having a purity of about 99% was used as an anode, and a copper-clad laminate was used as a cathode. Electrolysis was carried out at 50 ° C to 60 ° C at 0.2 V to 0.5 V to precipitate copper on the copper of the cathode. Thereafter, it is washed with water and dried.

In order to peel off 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. Then, wash again. The conductive copper between the copper patterns is quickly etched by an etching solution containing hydrogen peroxide and sulfuric acid as a main component, and washed with water and dried. The thickness of the copper wiring of the obtained copper wiring board (insulating board A with metal wiring) was 15 μm, and the surface roughness Rz of the copper wiring was Rz=0.4 μm.

Then, the obtained insulating substrate A with metal wiring was impregnated in an ethanol solution (thiol compound concentration: 0.1 mM) containing 1,10-decanedithiol (manufactured by Wako Pure Chemical Industries, Ltd.). After 60 minutes, it was washed with ethanol (first wiring treatment). Further, 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% by weight.

Then, the metal substrate-attached insulating substrate A subjected to the above treatment was subjected to polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group) at room temperature. Y equivalent: 143, a number average molecular weight: 48,000) of a cyclohexanone solution (polymer concentration: 5 wt%) was immersed for 10 minutes. Thereafter, the insulating substrate A with the metal wiring attached thereto was washed with cyclohexanone, and dried at room temperature (second wiring treatment).

Thereafter, an insulating resin layer (GX-13, manufactured by Ajinomoto Fine Chemical Co., Ltd.) was laminated on the surface of the metal wiring side of the insulating substrate A to which the metal wiring was attached. Then, by laser processing, a pattern (L-shaped pattern) of the insulating resin layer (layer thickness of the insulating resin layer: 35 μm) is formed, and further, by the slag removing place The residue generated by laser processing is removed. Further, the insulating resin layer contains an inorganic filler (cerium oxide).

By the above operation, the insulating substrate A with the metal wiring provided with the pattern of the insulating resin layer on the surface (hereinafter referred to as the substrate B) is produced. Further, in the substrate B, copper is partially exposed in a portion where the pattern of the insulating resin layer is not present. The obtained substrate B was subjected to a tape peeling test in the following order.

(Ni plating)

The obtained substrate B was subjected to a cleaning treatment at a liquid temperature of 50 ° C for 5 minutes using a cleaning liquid (trade name: ACL-009, manufactured by Uemura Industrial Co., Ltd.). Further, in a soft etching solution obtained by mixing 10% sulfuric acid (Wako Pure Chemical Industries, Ltd.) with sodium persulfide (Wako Pure Chemical Industries, Ltd.), the substrate B was immersed for 1.5 minutes at room temperature for cleaning. Furthermore, the substrate B subjected to the treatment was immersed in 2% sulfuric acid (Wako Pure Chemical Industries, Ltd.) for 1 minute, and immersed in an activation solution obtained by mixing and diluting 10% sulfuric acid and MFD-5 (manufactured by Uemura Kogyo Co., Ltd.) for 1 minute. . Then, it was immersed in a Ni-plated liquid of NPR-4 (manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C for 16 minutes to thereby plate a copper surface (nickel plating thickness: 3 μm) with Ni (nickel).

(tape peeling test)

As a method of evaluation, a tape peeling test was performed after the above-described Ni plating, and the number of meshes remaining on the insulating substrate A with the metal wiring not peeled off from the insulating resin layer pattern was counted. The results of the copper wiring substrate obtained in Example 1 are shown in Table 1. Further, the tape peeling test was carried out in accordance with JIS K5600-5-6. Table 1 shows the column of "Initial Adhesion" result.

Furthermore, the results obtained were evaluated according to the following criteria. In practical terms, the ideal is not "C".

"A": In the case of 100 cells, more than 90 cells remain.

"B": In the case of 100 cells, more than 60 cells and less than 90 cells remain.

"C": in the case of 100 cells, less than 60 cells remain

(time-series test)

Then, the sample which completed the tape peeling test was placed in an environment of a humidity of 85%, a temperature of 130 degrees, and a pressure of 1.2 atm (using a device: manufactured by Espec Corporation, EHS-221MD) for 200 hours. After 200 hours, the sample was taken out, and the tape peeling test described above was again carried out and subjected to a time-sensitive adhesion test. The results are shown in Table 1 in the column "Performance Stability".

Then, the ratio of the number of remaining cells of the obtained mesh to the number of remaining cells of the mesh in the peeling test performed before the high-temperature and high-humidity treatment was determined (the number of remaining cells in the peeling test after standing in a high-temperature and high-humidity environment/ The number of remaining cells in the peeling test before leaving in a high-temperature and high-humidity environment was evaluated according to the following criteria. In practical terms, the ideal is not "C".

"A": The ratio is above 0.9

"B": the ratio is 0.7 or more and less than 0.9

"C": a ratio less than 0.7

<Example 2>

Instead of the first wiring treatment carried out in Example 1, the insulating substrate A with the metal wiring was attached to an ethanol solution containing Pentaerythritol tetrakis (3-mercaptoacetate). In the same procedure as in Example 1, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was prepared in the same manner as in Example 1 except that the mixture was immersed for 10 minutes in a thiol compound concentration: 1 mM. And carry out various evaluations. The results are summarized in Table 1.

Further, 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% by weight.

<Example 3>

The insulating substrate A with the metal wiring was immersed in an ethanol solution (thiol compound concentration: 1 mM) containing dipentaerythritol hexakis(3-mercaptopropionate) for 10 minutes instead of the first wiring treatment carried out in Example 1. In the same procedure as in Example 1, an insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface thereof was prepared and subjected to various evaluations. The results are summarized in Table 1.

Further, 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% by weight.

<Example 4>

Instead of the first wiring treatment carried out in Example 1, the insulating substrate A with metal wiring attached to a cyclohexanone solution containing tetrakis-(7-fluorenyl-2,5-dithiaheptyl)methane (thiol compound) In the same procedure as in Example 1, an insulating substrate A with metal wiring provided with a pattern of an insulating resin layer on the surface was prepared and immersed in the same manner as in Example 1 except that the mixture was immersed for 20 minutes in a concentration of 0.1 mM). Various evaluations. The results are summarized in Table 1.

Further, tetra-(7-fluorenyl-2,5-dithiaheptyl)methane has a reactive functional group X equivalent (g/eq) of 170, a molecular weight of 681, and a sulfur atom content of 56wt%.

<Comparative Example 1>

Instead of the first wiring treatment and the second wiring treatment performed in Example 1, a cyclohexanone solution containing tetrakis-(7-fluorenyl-2,5-dithiaheptyl)methane was previously added (thiol compound concentration: 0.1 mM) In a mixed solution obtained by mixing a cyclohexanone solution (polymer concentration: 5 wt%) containing polyglycidyl methacrylate for 5 hours, the insulating substrate A with the metal wiring was immersed for 20 minutes, and thereafter In the same procedure as in Example 1, except that the insulating substrate A with the metal wiring was washed with cyclohexanone, the metal wiring with the pattern of the insulating resin layer on the surface was prepared. The substrate A was insulated and subjected to various evaluations. The results are summarized in Table 1.

<Comparative Example 2>

In place of the second wiring treatment of Example 1, the insulating substrate with metal wiring subjected to the first wiring treatment was contained in 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Azmax Corporation). Insulating substrate A with metal wiring provided with an insulating resin layer pattern on the surface was prepared in the same order as in Example 1 except that the ethanol solution (the compound concentration: 10 mM) was immersed for 5 minutes and washed with ethanol. And conduct various evaluations. The results are summarized in Table 1.

Further, in Comparative Example 2, a polymer having at least three or more reactive functional groups Y reactive with the reactive functional group X was not used.

<Comparative Example 3>

In place of the second wiring treatment of the example 2, the insulating substrate with the metal wiring subjected to the first wiring treatment contains 2-(3,4-epoxycyclohexyl). An epoxy resin was prepared by immersing in an ethanol solution (compound concentration: 10 mM) of ethyltrimethoxydecane (manufactured by Azmax Co., Ltd.) for 5 minutes and washing with ethanol, except that in the same procedure as in Example 2, an insulating resin was formed on the surface. The insulating substrate A with the metal wiring attached to the layer pattern was subjected to various evaluations. The results are summarized in Table 1.

Further, in Comparative Example 3, a polymer having at least three or more reactive functional groups Y reactive with the reactive functional group X was not used.

<Comparative Example 4>

In place of the first wiring treatment of Example 1, the insulating substrate A with the metal wiring was immersed in an ethanol solution (compound concentration: 10 mM) containing 3-mercaptopropyltrimethoxydecane for 5 minutes, and washed with ethanol. In the same manner as in Example 1, an insulating substrate A with a metal wiring provided with an insulating resin layer pattern on its surface was prepared and subjected to various evaluations. The results are summarized in Table 1.

Further, in Comparative Example 4, a predetermined thiol compound was not used.

<Comparative Example 5>

In place of the first wiring treatment of Example 1, the insulating substrate A with the metal wiring was immersed in an ethanol solution (compound concentration: 0.1 mM) containing triazine thiol for 60 minutes, and washed with ethanol. In the same procedure as in Example 1, an insulating substrate A with a metal wiring provided with an insulating resin layer pattern on its surface was prepared and subjected to various evaluations. The results are summarized in Table 1.

Further, in Comparative Example 5, a predetermined thiol compound was not used.

<Comparative Example 6>

In the same manner as in the example 1, the insulating substrate A with the metal wiring provided with the insulating resin layer pattern on the surface was prepared in the same manner as in the example 1, and various evaluations were performed. The results are summarized in Table 1.

Further, X-ray photoelectron spectroscopy (XPS) measurement was performed on the copper wiring board subjected to the second wiring treatment performed in the above-described Examples 1 to 4, and it was confirmed that a sulfur atom was present on the copper wiring. It was confirmed that the thiol compound was bonded to the copper wiring.

According to the results of the XPS measurement described above, the thickness of the layer of the thiol compound formed on the copper wiring in Examples 1 to 4 was about 0.1 nm to 2 nm. Further, the thickness of the formed epoxy resin layer was about 10 nm to 100 nm as measured by an Atomic Force Microscope (AFM) measurement.

In addition, in Table 1, "Yes" in the column of "1st wiring processing" and "2nd wiring processing" means that processing is performed, and "-" means that it is not implemented.

As shown in Table 1, the printed wiring board obtained by the production method of the present invention exhibits excellent initial adhesion and stability with time.

In particular, it was confirmed by comparison of Example 1 and Example 2 (or Example 3 or Example 4) that the number of reactive functional groups X used was four or more and the functional group represented by the formula (1) was used as the In the case of the compound of the reactive functional group X, it exhibits more excellent initial adhesion.

Further, from the comparison between Example 2 and Example 4, it was confirmed that the more the content of the sulfur atom in the thiol compound, the more excellent the stability with time of adhesion.

On the other hand, in Comparative Example 1 in which a thiol compound was mixed with a polymer, initial adhesion was inferior. It is presumed that the reason is that the thiol compound reacts with the polymer in the mixed solution, resulting in a decrease in reactivity with the metal wiring.

Further, in Comparative Example 2 and Comparative Example 3 in which a predetermined polymer was not used, the stability with time of adhesion was poor. It is presumed that the reason is that the network structure formed by using the decane coupling agent causes moisture to adsorb to the metal wiring and promotes corrosion of the metal wiring.

Further, in Comparative Example 4 and Comparative Example 5 in which triazine thiol described in Patent Document 2 and decyl propyl trimethoxy decane described in Patent Document 1 were used, the stability with time of adhesion was poor. In particular, in Comparative Example 4, it is presumed that the mesh structure formed by the decane coupling agent causes moisture to adsorb to the metal wiring and promotes corrosion of the metal wiring.

Further, in Comparative Example 6 in which the polymer layer was not formed, the initial adhesion was inferior.

<Example 5>

In Example 2, cyclohexanone containing polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) was used. Solution (polymer concentration: 2.5 wt%) 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: 48,000) a cyclohexanone solution (polymer concentration: 5 wt%), and PFR-800 manufactured by Laminated Sun Ink Co., Ltd. replaced ABF GX-13 manufactured by Ajinomoto Fine Chemical Co., Ltd. as an insulating layer, and then passed through a pattern mask. (L-shaped pattern) was exposed, developed, baked, and further exposed, and an SR (solder resist) pattern was formed on a copper wiring board (film thickness of insulating layer: 30 μm). After the obtained copper wiring board with the SR pattern obtained was subjected to Ni plating, the tape peeling test was performed. Thereafter, a time-lapse adhesion test was performed. The results are summarized in Table 2. Further, the SR contains an inorganic filler (cerium oxide).

<Example 6>

In Example 5, cyclohexanone containing polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 122, reactive functional group Y equivalent: 143, number average molecular weight: 17500) was used. Solution (polymer concentration: 2.5 wt%) instead of polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) A cyclohexanone solution (polymer concentration: 2.5 wt%) was prepared, except that the SR pattern was attached in the same order as in Example 5. A copper wiring board was subjected to various evaluations. The results are summarized in Table 2.

<Example 7>

In Example 5, cyclohexanone containing polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 251, reactive functional group Y equivalent: 143, number average molecular weight: 36,000) was used. Solution (polymer concentration: 5 wt%) instead of polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) A copper wiring board with an SR pattern was prepared in the same procedure as in Example 5 except that the cyclohexanone solution (polymer concentration: 2.5 wt%) was used, and various evaluations were performed. The results are summarized in Table 2.

<Comparative Example 7>

In Example 5, a cyclohexane 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) was used. Ketone solution (compound concentration: 2.5 wt%) instead of polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 52, reactive functional group Y equivalent: 143, number average molecular weight: 7500) A copper wiring board with an SR pattern was prepared in the same procedure as in Example 5 except that the cyclohexanone solution (polymer concentration: 2.5 wt%) was used, and various evaluations were performed. The results are summarized in Table 2.

In addition, the "number average molecular weight" in Table 2 means the number average molecular weight of the polymer used for the 2nd wiring process. In Comparative Example 7, the molecular weight of the trimethylolpropane triglycidyl ether used was shown.

As shown in Table 2, the printed wiring board obtained by the production method of the present invention exhibits excellent initial adhesion and stability with time.

In particular, in Examples 6 and 7 in which the number average molecular weight of the polymer to be used was large, it was confirmed that the stability with time was more excellent. It is presumed that the reason is that the stress relaxation ability is improved due to an increase in the number average molecular weight of the polymer.

On the other hand, in Comparative Example 7 in which the second wiring treatment using the polymer was not carried out, the stability with time was poor.

<Example 8>

Silver was deposited on the tantalum substrate to form a silver wiring board having 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.

Then, the obtained silver wiring substrate was immersed in a cyclohexanone solution containing 0.1 mM of tetrakis-(7-fluorenyl-2,5-dithiaheptyl)methane for 20 minutes, after which, cyclohexanone was used for washing. The silver wiring substrate was washed with a solvent, and after washing with water, the substrate was dried at room temperature. After the above treatment, cyclohexanone containing polyglycidyl methacrylate (manufactured by Polymer Source, number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48,000) The solution (polymer concentration: 5 wt%) was immersed at room temperature for 10 minutes to form cyclohexanone The cells were cleaned and the substrate was dried at room temperature.

Thereafter, an insulating layer (PFR-800 manufactured by Sun Ink Co., Ltd.) is laminated on the treated silver wiring substrate, and then exposed through a pattern mask (L-shaped pattern), developed, baked, and further exposed to silver. An SR (solder resist) pattern was formed on the wiring board (film thickness of SR: 30 μm). The obtained silver wiring board with the SR pattern was placed in a humid environment (temperature: 130 degrees, humidity: 85% RH, pressure: 1.2 atm) (using a device: manufactured by Espec Co., Ltd., EHS-221MD) for 100 hr, and then the sample was taken out to carry out the above. Tape peel test. The results are summarized in Table 3.

<Comparative Example 8>

In Example 8, instead of the silver wiring substrate containing polyglycidyl methacrylate (manufactured by Polymer Source, the number of reactive functional groups Y: 335, reactive functional group Y equivalent: 143, number average molecular weight: 48,000) The cyclohexanone solution (polymer concentration: 5 wt%) was immersed at room temperature for 10 minutes and washed with cyclohexanone, and the silver wiring substrate was contained in 2-(3,4-epoxycyclohexyl). Ethyl trimethoxy decane (manufactured by Azmax Co., Ltd.) was immersed in an ethanol solution (compound concentration: 10 mM) for 5 minutes, and washed with ethanol, and then placed in a wet environment for 100 hr in the same order, and then the sample was taken out. The tape peeling test described above was carried out. The results are summarized in Table 3.

In addition, in Table 3, the "initial adhesion" column is a result of performing a tape peeling test on a silver wiring board with an SR pattern placed in a wet environment for 100 hr, and is the same as the above (tape peeling test). Evaluation criteria to evaluate.

In addition, in Table 3, the "Time Stability" column is a tape peeling test for a silver wiring board with an SR pattern placed in a wet environment for 100 hours, and the number of remaining cells before and after being placed in a wet environment is determined. The ratio (the number of remaining cells in the peeling test after standing in a wet environment/the number of remaining cells in the peeling test before leaving in a wet environment) was evaluated in accordance with the same evaluation criteria as the above (time-sensitive test).

As shown in Table 3, when a silver wiring is used as the metal wiring, the printed wiring board obtained by the manufacturing method of the present invention also exhibits excellent initial adhesion and stability with time.

On the other hand, in Comparative Example 8 in which the second wiring treatment using the polymer was not carried out, the stability with time was poor.

10‧‧‧Insulated substrate with metal wiring

12‧‧‧Insert 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‧‧‧layer of polymer bonded to metal wiring covered by thiol compound

24‧‧‧Insulating resin layer

26‧‧‧Printed wiring substrate

40‧‧‧Other insulating substrates

50‧‧‧Other metal wiring

60‧‧‧decane coupling agent

62‧‧‧ polymer

1(A) to 1(F) are schematic cross-sectional views showing respective steps from the substrate to the printed wiring board in the method of manufacturing the printed wiring board of the present invention.

Fig. 2 is a schematic cross-sectional view showing another aspect of an insulating substrate with metal wiring.

3(A) and 3(B) are schematic cross-sectional views showing a state in which various steps are carried out using a decane coupling agent having a hydrazine atom-bonding hydrolyzable group.

10‧‧‧Insulated substrate with metal wiring

12‧‧‧Insert substrate

14‧‧‧Metal wiring

18‧‧‧layer of thiol compound bonded to the surface of the metal wiring

22‧‧‧layer of polymer bonded to metal wiring covered by thiol compound

24‧‧‧Insulating resin layer

26‧‧‧Printed wiring substrate

Claims (8)

In a method of manufacturing a printed wiring board, the printed wiring board is provided with an insulating resin layer on an insulating substrate with metal wiring, and the manufacturing method includes a first coating step using two or more reactive functional groups X (wherein a thiol compound having at least one functional group represented by the formula (1) in which at least one of the reactive functional groups X is a thiol group and a ruthenium atom-bonded hydrolyzable group, and the insulating substrate with the metal wiring described above The surface of the insulating substrate and the surface of the metal wiring are covered, and the insulating substrate with the metal wiring includes the insulating substrate and the metal wiring disposed on the insulating substrate. In the first cleaning step, the metal wiring is insulated using a solvent. The substrate is cleaned to remove the thiol compound on the surface of the insulating substrate, and the second coating step is performed by using a polymer having at least three or more reactive functional groups Y reactive with the reactive functional group X. The surface of the substrate and the surface of the metal wiring covered by the thiol compound are covered; the second cleaning step uses a solvent Cleaning the insulating substrate with the metal wiring described above to remove the polymer on the surface of the insulating substrate; and forming an insulating resin layer to form the insulating layer on the surface of the metal wiring side of the insulating substrate with the metal wiring Resin layer; HS-L ¹ -* Formula (1) (In the formula (1), L ¹ represents a divalent aliphatic hydrocarbon group; * represents a bonding position). The method for producing a printed wiring board according to the first aspect of the invention, wherein the polymer has a number average molecular weight of 10,000 or more. The method for producing a printed wiring board according to the above aspect, wherein the reactive functional group X is a functional group selected from the above formula (1), a primary amino group, and a secondary amino group. And a group in the group consisting of isocyanate groups. The method for producing a printed wiring board according to the first or second aspect, wherein the reactive functional group Y is selected from the group consisting of an epoxy group, an acrylate group, and a methacrylate group. Base. The method for producing a printed wiring board according to the first or second aspect of the invention, wherein the second coating step is a polymer composition containing the polymer and substantially containing no inorganic filler, a step of covering the surface of the metal wiring covered with the thiol compound and the surface of the insulating substrate. The method for producing a printed wiring board according to claim 5, wherein a content of the polymer in the polymer composition is 0.01% by weight to 80% by weight based on the total amount of the polymer composition. The method for producing a printed wiring board according to the first or second aspect of the invention, wherein the number of the reactive functional groups X is four or more. An IC package substrate having a printed wiring board obtained by the method for producing a printed wiring board according to any one of the first to seventh aspects of the invention.