JP4850525B2 - Multilayer circuit board and manufacturing method thereof - Google Patents

Description

  The present invention relates to a processing method for improving adhesion between a wiring layer and an insulating resin layer and a multilayer circuit board having the wiring layer subjected to the adhesion processing in a multilayer circuit substrate having an insulating resin layer and a wiring layer.

  In recent years, miniaturization of printed wiring boards, multilayering, and high-density mounting of electronic components have rapidly progressed, and a build-up multilayer wiring structure has been actively studied for printed wiring boards. In the build-up multilayer wiring structure, an insulating layer such as an insulating resin layer is formed between a plurality of wiring layers, and minute holes called via holes are formed in the insulating layer in order to establish conduction between the wiring layers. The via hole can be formed by a method using a photosensitive resin by a photolithography technique or a method of forming a hole by irradiating a laser.

  Next, a conductor is formed on the insulating layer by electroless plating or electroplating, and this is etched to form a new wiring pattern. Thereafter, if the formation process from the formation of the insulating layer to the wiring pattern is repeated as necessary, the degree of circuit integration can be increased.

  In the prior art, most of the wiring of the build-up wiring board is made of copper, but copper is known to have low adhesion to a resin. Therefore, conventionally, the following processing has been performed in order to improve the adhesion between the copper wiring of the build-up wiring board and the insulating layer on the upper side.

  That is, for example, the copper wiring surface is etched (chemical polishing) with cupric chloride solution, ferric chloride solution, sulfuric acid hydrogen peroxide solution, formic acid aqueous solution, etc., and the 10-point average surface roughness is 2 μm or more. A process is performed in which the protrusion is formed and the resin of the insulating layer formed on the upper side of the wiring is firmly fixed to the copper wiring surface by the anchor action of the fine protrusion. Thereby, a peel strength of 0.8 kgf / cm (converted value is 8 N / cm) is obtained.

  However, in recent years, high-frequency signals have also been transmitted to build-up wiring boards, and particularly in the frequency region exceeding 1 GHz, there is a problem that transmission loss due to the skin effect, particularly conductor loss, increases in a wiring structure with fine protrusions. Has arisen.

  The adhesion between the copper wiring and the insulating resin includes chemical adhesion between the copper and the constituent components in the resin, in addition to the adhesion due to the physical anchor effect due to the surface roughening described above. At the molecular level, methods using various triazine thiols are disclosed as known techniques. Specifically, in Cited Document 1, a triazine thiol layer is formed on a conductor. This method is limited to those in which the resin reacts with triazine thiol. Also, a method of forming a thick film of an azole compound by mixing an organic acid (see Cited Document 2) has been proposed, but although it is excellent in adhesion with copper, it does not have a functional group, so an insulating resin There is a problem such as poor adhesion to.

Furthermore, a method for forming a film by organic plating of a triazine thiol film has also been proposed (see Non-Patent Document 1). That is, a reverse bias is first applied to remove the oxide film on the copper surface, and then triazine thiol is organically plated. However, since a seed electrode layer is essential for plating, there is a problem that it is difficult to apply to an isolated part.
Japanese Patent Laid-Open No. 10-335782 (Claims) JP 2002-321310 A (Claims) “Surface Technology”, 2000, Vol. 51, NO. 3, p. 276

  The present invention solves the above-described problems, and provides a novel multilayer circuit board capable of obtaining high adhesion between the wiring and the resin layer thereon, and high adhesion between the wiring and the resin layer thereon. It is an object of the present invention to provide a novel manufacturing method of a multilayer circuit board that can be obtained. Still other objects and advantages of the present invention will become apparent from the following description.

According to one aspect of the present invention, in a multilayer circuit board having a wiring layer and an insulating resin layer,
At least a nitro group, a carboxy group and a cyano group are present on the surface of the wiring layer,
Directly there are organic compounds that can adsorb or react with nitro, carboxy and cyano groups,
Furthermore, the insulating resin layer is present immediately above.
A multilayer circuit board is provided. According to the aspect of the present invention, a multilayer circuit board having excellent adhesion between the wiring and the resin layer thereon can be realized.

According to another aspect of the present invention, in a method for manufacturing a multilayer circuit board having a wiring layer and an insulating resin layer,
The wiring layer surface is treated with a treatment liquid containing a compound containing at least a nitro group, a carboxy group and a cyano group or an alkali metal salt thereof or a mixture thereof to form a first treated body,
Treating the surface of the first treated body with an organic compound capable of adsorbing or reacting with a nitro group, a carboxy group and a cyano group to form a second treated body;
A method for manufacturing a multilayer circuit board is provided, which includes forming an insulating resin layer on the second treatment body. According to the aspect of the present invention, it is possible to realize a method for producing a multilayer circuit board having excellent adhesion between the wiring and the resin layer thereon.

  The compound containing at least the nitro group, carboxy group, and cyano group, or an alkali metal salt thereof, or a mixture thereof includes a compound selected from the group consisting of nitrobenzoic acid, nitrophthalic acid, nitrosalicylic acid, and alkali metal salts thereof. And / or the compound containing at least the nitro group, carboxy group, and cyano group, or an alkali metal salt thereof, or a mixture thereof is cyanobenzoic acid, cyanophenol, dicyanobenzene, cyanoacetic acid, an alkali metal salt thereof, cyanide It is preferable to include a compound selected from the group consisting of sodium and potassium cyanide.

  Further, in common with the above two embodiments, the organic compound is a silane coupling agent or a triazine thiol of formula 1, or a silane coupling agent and a triazine thiol of formula 1.

（式１中、ＳＡのＡは、水素、リチウム、ナトリウム、カリウム、ルビジウムまたはセシウムを表し、Ｘはメチル基、エチル基、プロピル基およびフェニル基からなる群から選ばれた少なくとも一つの基で置換されていてもよいアミノ基またはＳＡを表す。なお、ＳＡの少なくともいずれかにはＳＨが含まれる。）
前記シランカップリング剤が、アミノ基、メルカプト基、エポキシ基、イミダゾール基、ビニル基、ジアルキルアミノ基およびピリジン基からなる群から選ばれた基を少なくとも一つ含むものであること、前記配線層が銅からなるものであること、および、前記絶縁樹脂層が、ポリイミド樹脂、エポキシ樹脂、ビスマレイミド樹脂、マレイミド樹脂、シアネート樹脂、ポリフェニレンエーテル樹脂、オレフィン樹脂、フッ素含有樹脂、液晶ポリマー、ポリエーテルイミド樹脂およびポリエーテルエーテルケトン樹脂からなる群から選ばれた少なくとも一つの樹脂を含むものであることが好ましい。

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.
The silane coupling agent includes at least one group selected from the group consisting of an amino group, a mercapto group, an epoxy group, an imidazole group, a vinyl group, a dialkylamino group, and a pyridine group, and the wiring layer is made of copper. it is composed of one, and the insulating resin layer, a polyimide resin, epoxy resin, bismaleimide resin, maleimide resins, cyanate resins, polyphenylene ether resins, o olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resins and It is preferable that it contains at least one resin selected from the group consisting of polyetheretherketone resins.

  According to still another aspect of the present invention, there is provided a multilayer circuit board manufactured by the above-described multilayer circuit board manufacturing method.

  According to the present invention, it is possible to realize a multilayer circuit board having excellent adhesion between a wiring and a resin layer thereon and a method for manufacturing the same. The surface roughening of the wiring can be omitted.

  Embodiments of the present invention will be described below with reference to the drawings, examples and the like. In addition, these figures, Examples, etc. and description illustrate the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention. In the drawings, the same reference numeral represents the same element.

The multilayer circuit board according to one embodiment of the present invention has a wiring layer and an insulating resin layer,
At least a nitro group, a carboxy group and a cyano group are present on the surface of the wiring layer,
Directly above, an organic compound that can adsorb or react with a nitro group, a carboxy group, and a cyano group (hereinafter, “an organic compound that can adsorb or react with a nitro group, a carboxy group, and a cyano group” is referred to as a “specific organic compound”. ) Exist,
Further, the insulating resin layer is present immediately above.

  With such a structure, a strong bond can be realized between the wiring layer and the insulating resin layer.

As another aspect of the present invention, in a method for manufacturing a multilayer circuit board having a wiring layer and an insulating resin layer,
The wiring layer surface is coated with a compound containing at least a nitro group, a carboxy group and a cyano group or an alkali metal salt thereof or a mixture thereof (hereinafter referred to as a “compound containing at least a nitro group, a carboxy group and a cyano group or an alkali metal salt thereof or the A first treatment body is formed by treating with a treatment liquid containing a mixture of
The surface of the first treated body is treated with a specific organic compound to form a second treated body,
There is a method for manufacturing a multilayer circuit board, which includes forming an insulating resin layer on the second processed body.

  By such a method, a multilayer circuit board having a strong bond between the wiring layer and the insulating resin layer can be realized.

  In any of the above aspects, the multilayer circuit board may include any multilayer board that satisfies the above conditions. Those having an insulating resin layer and a wiring layer on the supporting substrate and those lacking the supporting substrate are included. Other layers other than the above may be included.

  The wiring layer does not need to be subjected to a surface roughening treatment, but may be combined with an anchor effect due to surface roughening. There is no particular limitation on the material of the wiring layer, but in the present embodiment, it is possible to realize high adhesion between the wiring layer and the resin layer thereon without roughening the surface. A preferable effect is obtained.

  There is no particular limitation on the form of the nitro group, carboxy group and cyano group present on the surface of the wiring layer on the surface of the wiring layer. However, the compound having a nitro group, the compound having a carboxy group, cyano It can be considered that a compound having a group, a compound having any two or all of a nitro group, a carboxy group, and a cyano group are chemically reacted, chemically adsorbed, physically adsorbed, etc. on the surface of the wiring layer. The shape of the nitro group, carboxy group and cyano group between the wiring and the specific organic compound is irrelevant to the essence of the present invention. Specifically, the layer may or may not be formed. When a compound having a nitro group, a compound having a carboxy group, a compound having a cyano group, or the like forms a layer, the order of these layers is not particularly limited. When at least the nitro group, carboxy group, and cyano group coexist, the adhesion between the wiring layer and the other layer becomes strong. Compared to the case where these groups are present alone, the adhesion is remarkably strengthened.

  There is no particular limitation on the method of obtaining the first treatment body by treating the wiring layer surface with the treatment liquid containing the specific polar compound, and the surface is immersed in the treatment liquid containing the specific polarity compound or sprayed with such a liquid. Such a method is conceivable.

  In order to achieve strong fixation, washing, heating, drying, etc. are included, repeated treatment, treatment with a compound containing at least one nitro group or an alkali metal salt thereof, and carboxy groups. There are various methods such as performing the treatment with a treatment liquid containing at least one compound or an alkali metal salt thereof separately from the treatment with a treatment liquid containing a compound containing at least one cyano group or an alkali metal salt thereof. Conceivable. In the present invention, a preferable method may be appropriately selected from these arbitrary methods.

  The specific polar compound may consist of a plurality of types of compounds or a single compound. Preferable examples of the compound containing a nitro group and a carboxy group include nitrobenzoic acid, nitrophthalic acid, nitrosalicylic acid or an alkali metal salt thereof. Preferred examples of the compound containing a cyano group include organic compounds such as cyanobenzoic acid, cyanophenol, dicyanobenzene, cyanoacetic acid and alkali metal salts thereof, and inorganic cyan compounds such as sodium cyanide and potassium cyanide. . These compounds may contain a functional group other than a nitro group, a carboxy group, and a cyano group. It may be a mixture. This mixture also includes a mixture of an acid and a salt. Although there is no restriction | limiting in particular also about the solvent used for comprising a process liquid, Usually, water may be sufficient.

  As described above, the first treatment body according to the present invention includes those containing other treatments as described above in addition to the treatment with the treatment liquid containing the specific polar compound.

  The specific organic compound is not particularly limited as long as it is an organic compound that can adsorb or react with a nitro group, a carboxy group, and a cyano group. Elements other than carbon and hydrogen (for example, oxygen, nitrogen, sulfur, silicon, etc.) may be included. Whether or not it can be adsorbed or reacted with nitro, carboxy and cyano groups can be confirmed by improving the adhesion when a multilayer wiring board is actually fabricated. Then, apply a specific polar compound on top of it, treat it with drying, heating, etc., and then wash it with a solvent such as water to confirm that the nitro group, carboxy group, and cyano group do not disappear. May be. In this model confirmation, it is not always necessary to use a material actually used, and a specific polar compound selected in a model manner may be used. In other words, the specific organic compound in the present invention may include those confirmed in a model manner in this way. Further, as understood from the above description, in the present invention, “can be adsorbed or reacted with a nitro group, a carboxy group and a cyano group” does not necessarily mean that all groups of nitro group, carboxy group and cyano group are actually used. It does not require that the species can be adsorbed or reacted.

  As the specific organic compound, a silane coupling agent or a triazine thiol of formula 1 or a silane coupling agent and a triazine thiol of formula 1 realizes stronger bonding between the wiring layer and the insulating resin layer. Preferred above.

（式１中、ＳＡのＡは、水素、リチウム、ナトリウム、カリウム、ルビジウムまたはセシウムを表し、Ｘはメチル基、エチル基、プロピル基およびフェニル基からなる群から選ばれた少なくとも一つの基で置換されていてもよいアミノ基またはＳＡを表す。なお、ＳＡの少なくともいずれかにはＳＨが含まれる。）
上記シランカップリン剤については特に制限はなく、アミノ基、メルカプト基、エポキシ基、イミダゾール基、ビニル基、ジアルキルアミノ基およびピリジン基からなる群から選ばれた基を少なくとも一つ含むものを好ましく例示できる。

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.
The silane coupling agent is not particularly limited, and preferably includes at least one group selected from the group consisting of an amino group, a mercapto group, an epoxy group, an imidazole group, a vinyl group, a dialkylamino group, and a pyridine group. it can.

  There is no restriction | limiting in particular about the method of processing the surface of a 1st process body with a specific organic compound, and obtaining a 2nd process body, An immersion method, a spray method, etc. are employable. Since triazine thiol and silane coupling agents are usually solid, they are often used by dissolving in some solvent. Although there is no restriction | limiting in particular about the solvent in this case, Water is simple.

  When triazine thiol and silane coupling agent are used in common, there is no particular limitation on the method, a method in which treatment with a silane coupling agent is performed after treatment with triazine thiol, a treatment with triazine thiol after treatment with silane coupling agent And a method of simultaneously performing a treatment with triazine thiol and a treatment with a silane coupling agent are conceivable.

  Further, in order to realize strong fixation, various methods such as washing with water, heating, drying, etc., and repeated treatment are also conceivable. In the present invention, a preferable method may be appropriately selected from these arbitrary methods.

  As described above, the second treated body according to the present invention may include other treatments as described above in addition to treating the surface of the first treated body with triazine thiol or a silane coupling agent. included.

  Note that the “silane coupling agent” in the multilayer circuit board means that the structure has already changed due to the reaction, unlike the “silane coupling agent” in the form of the invention according to the manufacturing method. The presence of such a silane coupling agent is due to the presence of silicon element by peeling the resin layer from the multilayer circuit board and analyzing the peeled surface by AES, XPS, etc. This can be confirmed by the presence of amino group, mercapto group, etc.

  In addition, for specific organic compounds such as nitro groups, carboxy groups, cyano groups, and triazine thiols in the multilayer circuit board, the correspondence in the invention according to the above manufacturing method due to the mutual interaction and the interaction with the wiring layer, etc. It is possible that the structure of the object is slightly changed. For example, changes such as removal of hydrogen of the carboxy group and formation of a triple bond between C and N of the cyano group are considered. Specific organic compounds such as nitro groups, carboxy groups, cyano groups, and triazine thiols in the multilayer circuit board according to the present invention include those having such a structure change. The presence of such nitro group, carboxy group, and cyano group can be detected from the multilayer circuit board by exposing the wiring layer by an appropriate method such as etching, and using SIMS (secondary ion mass spectrometry) or the like. it can. At this time, other groups and elements may be detected simultaneously. The presence of triazine thiol is the presence of sulfur and nitrogen by peeling the resin layer from the multilayer circuit board and analyzing the peeled surface by methods such as AES and XPS, and the peeled surface by a method such as TOF-SIMS. It can be confirmed by the presence of a mercapto group and the like by analysis with

  Note that it is irrelevant to the essence of the present invention how the specific organic compound is present in the multilayer circuit board and in what shape is it between the wiring layer and the insulating resin layer. . Specifically, the layer may or may not be formed. When the triazine thiol and the silane coupling agent are used in common, the order between the triazine thiol and the silane coupling agent is not particularly limited. The presence of the specific organic compound immediately above the nitro group, carboxy group and cyano group means that the silicon, amino group, mercapto group, etc. above the part above the part where the nitro group, carboxy group and cyano group are present (wiring) It can be confirmed that the above silicon, amino group, mercapto group, etc. are present in the same part as the nitro group, carboxy group and / or cyano group, or the nitro group. , A carboxy group and / or a cyano group may be present in a portion below (a portion closer to the wiring layer).

There is no particular limitation on the insulating resin used in the insulating resin layer directly above the specific organic compound in the multilayer substrate and the insulating resin used in the invention aspect related to the manufacturing method, but polyimide resin, epoxy resin, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, o olefin resin, fluorine-containing resin, liquid crystal polymer, is generally intended to include at least one resin selected from the group consisting of polyetherimide resins and polyether ether ketone resin It is preferable.

  There is no restriction | limiting in particular about the method of forming the insulating resin layer which concerns on this invention, It can select suitably from well-known methods, such as sticking a resin sheet using a vacuum press and a vacuum lamination.

  The cross-sectional structure of the multilayer circuit board obtained in the above aspects is, for example, as shown in FIG.

  FIG. 1 shows a treatment surface layer 2 of a first treatment body produced by treatment with a treatment liquid containing a specific polar compound on a wiring layer 1, and a surface of the first treatment body on the wiring layer 1 with a specific organic compound. FIG. 2 shows a state in which the treatment surface layer 3 of the second treatment body produced by the treatment and the insulating resin layer 4 are present thereon, and FIG. 2 shows the treatment on the wiring layer 1 with a treatment liquid containing a specific polar compound. The treated surface layer 2 of the first treated body produced on the surface, and the treated surface layer 3 ′ produced by treating the surface of the first treated body with the triazine thiol or silane coupling agent having the structure of Formula 1 on the treated surface layer 2 ′. The surface of the treated surface layer 3 ′ is treated with a silane coupling agent or a triazine thiol having the structure of Formula 1 and the treated surface layer 3 ″ is formed thereon, and the insulating resin layer 4 is present thereon. The second treatment body 3 is composed of a treatment surface layer 3 ′ and a treatment surface layer 3 ″. That. 1 and 2 may or may not be present.

  1 and 2 show the layer structure formed by the inventive aspect of the multilayer substrate manufacturing method according to the present invention. In the case of the invention aspect of the multilayer substrate according to the present invention, the treated surface layer 2 of the first treated body is read as “part 2 in which at least a nitro group, a carboxy group, and a cyano group are present”, and the second treatment. The treated surface layer 3 of the body is read as “part 3 in which a specific organic compound is present”.

  Next, an example of a method for forming a build-up multilayer circuit board using the multilayer circuit board manufacturing method according to the present invention will be described below with reference to FIGS.

  First, the buildup insulating layer 32 is formed on the glass fiber reinforced resin substrate 31 on which the circuit is formed. An appropriate treatment for obtaining adhesion is performed on the surface of the insulating layer 32, and then a metal conductive layer 33 is formed by electroless plating, sputtering, or the like (step 1). Next, in step 2, the resist 34 is patterned, and as in step 3, an electrolytic copper plating 35 is grown in the opening.

  In step 4, after the resist is removed, in step 5, the conductive layer 33 is removed by etching to form a wiring layer 36. Next, in step 6, a surface treatment is performed with a specific polar compound. As the treatment method, an immersion method, a spraying method using a spray, or the like can be used. In this example, the layer 37 of the specific polar compound is shown, but it is unclear what form it is actually in.

  Thereafter, in step 7, the treatment with the specific organic compound is performed to form the specific organic compound layer 38. As this processing method, an immersion method, a spraying method by spraying, or the like can be used. Further, thereafter, the treatment with the specific organic compound may be repeated, or the treatment with another specific organic compound may be performed (steps are not shown). As the treatment method, a dipping method, a spraying method using a spray, or the like can be used.

  Thereafter, in step 8, an upper insulating layer 39, which is the next layer, is formed. Thereafter, via holes are formed in order to establish conduction between the upper and lower wiring layers. By repeating such a process, a multilayer circuit board can be formed. It is also useful to apply Step 6 and subsequent steps to the copper foil on the glass fiber reinforced resin that forms the first buildup insulating layer.

  In each step of FIGS. 3 and 4, the specific polar compound layer 37 and the specific organic compound layer 38 are shown only on the wiring layer 36. This is the case where some cleaning process is included in steps 6 and 7. Is assumed. Without such cleaning, the same layer is formed in other parts, but there is no problem as long as the quality (adhesion etc.) of the multilayer circuit board is not affected.

  Next, examples and comparative examples of the present invention will be described in detail. The peel strength was measured by a 90-degree peel test according to JIS C-6481.

[Example 1]
35 μm thick electroplated copper foil containing 1% by weight of 4-nitrobenzoic acid (Kanto Chemical), 0.5% by weight of sodium hydroxide (Kanto Chemical) and 1% by weight of 4-cyanobenzoic acid (Kanto Chemical) Immersion treatment was performed for 5 minutes with an aqueous solution to obtain a first treated body. Next, this copper foil was immersed in a 1% by weight aqueous solution of γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) for 5 minutes, dried by baking at 100 ° C. for 30 minutes, The processed body was obtained.

  The treatment surface was overlaid so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Example 2]
Instead of 4-cyanobenzoic acid described in Example 1, sodium cyanide was used, and instead of γ-mercaptopropyltrimethoxysilane aqueous solution, γ-aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) aqueous solution Except for the use of, vacuum was applied so that the semi-cured (B stage) thermosetting epoxy resin sheet was in contact with the treated surface of the second treated body obtained by treating in the same manner as in Example 1. Pressing was performed at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Comparative Example 1]
About 35 μm thick electroplated copper foil, 1 wt% 4-nitrobenzoic acid (Kanto Chemical), 0.5 wt% sodium hydroxide (Kanto Chemical) and 1 wt% 4-cyanobenzoic acid (Kanto Chemical) Immersion treatment was carried out with an aqueous solution for 5 minutes. Dried at 100 ° C. for 30 minutes. The treatment surface was overlaid so that a semi-cured (B stage) thermosetting epoxy resin sheet was in contact with the treated surface, and was pressed with a vacuum press at 150 ° C. and 1 MPa for 5 minutes. Thereafter, the epoxy resin was taken out from the vacuum press and cured at 180 ° C. for 1 hour under atmospheric pressure.

  As a result of cutting the copper foil into 1 cm width and measuring the peel strength, only a value of 0.4 kgf / cm (converted value was 4 N / cm) was obtained.

[Comparative Example 2]
An electroplated copper foil having a thickness of 35 μm was immersed in an aqueous solution containing 1% by weight of γ-aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) for 5 minutes at room temperature, 100 ° C., 30 Dry with a bake of minutes. The treatment surface was overlaid so that a semi-cured (B stage) thermosetting epoxy resin sheet was in contact with the treated surface, and was pressed with a vacuum press at 150 ° C. and 1 MPa for 5 minutes. Thereafter, the epoxy resin was taken out from the vacuum press and cured at 180 ° C. for 1 hour under atmospheric pressure.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, only a value of 0.1 kgf / cm (converted value was 1 N / cm) was obtained.

[Example 3]
For the treated surface of the second treated product obtained in the same manner as in Example 1 except that 4-nitrophthalic acid (Kanto Chemical) was used instead of 4-nitrobenzoic acid described in Example 1. The thermosetting epoxy resin sheet in a semi-cured state (B stage) was stacked so as to be in contact with each other, and was pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Example 4]
On the treated surface of the second treated product obtained in the same manner as in Example 1 except that 5-nitro-salicylic acid (manufactured by Kanto Chemical) was used instead of 4-nitrobenzoic acid described in Example 1. On the other hand, it was piled up so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact, and it was pressed for 5 minutes under a vacuum press at 150 ° C. and 1 MP. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Example 5]
Instead of the aqueous solution of 1% by weight of γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) described in Example 1, 0.5% by weight of γ-mercaptopropyltrimethoxysilane and 0.5% by weight Except that an aqueous solution containing γ-aminopropyltriethoxysilane was used, the semi-cured state (B stage) was applied to the treated surface of the second treated body obtained in the same manner as in Example 1. The thermosetting epoxy resin sheets were stacked so that they were in contact with each other, and pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Example 6]
Instead of the aqueous solution of 1% by weight of γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) described in Example 1, 1% by weight of 2,4,6-trimercapto-1,3,5- A semi-cured state (with respect to the treated surface of the second treated product obtained in the same manner as in Example 1 except that an aqueous solution of triazine monosodium salt (Santhiol N-1, Sankyo Kasei) was used. The thermosetting epoxy resin sheet of (B stage) was stacked so as to be in contact with each other, and was pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.8 kgf / cm (converted value: 8 N / cm) was obtained.

[Example 7]
Instead of the 1% by weight γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) aqueous solution described in Example 1, 1% by weight of 2-anilino-4,6-trimercapto-1,3 A semi-cured state (B) was applied to the treated surface of the second treated body obtained in the same manner as in Example 1, except that an aqueous solution of 5-triazine monosodium salt (Disnet AF, manufactured by Sankyo Kasei) was used. The thermosetting epoxy resin sheet of (stage) was placed in contact with each other, and was pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.7 kgf / cm (converted value: 7 N / cm) was obtained.

[Example 8]
35 μm thick electroplated copper foil containing 1% by weight of 4-nitrobenzoic acid (Kanto Chemical), 0.5% by weight of sodium hydroxide (Kanto Chemical) and 1% by weight of 4-cyanobenzoic acid (Kanto Chemical) Immersion treatment was performed for 5 minutes with an aqueous solution to obtain a first treated body. Next, this copper foil was immersed in a 1% by weight aqueous solution of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, manufactured by Sankyo Kasei) for 5 minutes. , Dried at 100 ° C. for 30 minutes, and then immersed in an aqueous solution of 1% by weight of γ-mercaptopropyltrimethoxysilane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) for 5 minutes, at 100 ° C. for 30 minutes. It dried by baking and the 2nd processed body was obtained.

  The treatment surface was overlaid so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed with a vacuum press at 150 ° C. and 1 MP for 5 minutes. Then, it took out from the vacuum press and hardened the epoxy resin by heating at 180 ° C. for 1 hour under atmospheric pressure to obtain an insulating resin layer.

  As a result of cutting the copper foil into a width of 1 cm and measuring the peel strength, a high value of 0.9 kgf / cm (converted value: 9 N / cm) was obtained.

  In addition, the invention shown to the following additional remarks can be derived from the content disclosed above.

(Appendix 1)
In a multilayer circuit board having a wiring layer and an insulating resin layer,
At least a nitro group, a carboxy group and a cyano group are present on the surface of the wiring layer,
Directly there are organic compounds that can adsorb or react with nitro, carboxy and cyano groups,
Furthermore, the insulating resin layer is present immediately above.
Multi-layer circuit board.

(Appendix 2)
The multilayer circuit board according to appendix 1, wherein the organic compound is a silane coupling agent or a triazine thiol of formula 1 or a silane coupling agent and a triazine thiol of formula 1.

（式１中、ＳＡのＡは、水素、リチウム、ナトリウム、カリウム、ルビジウムまたはセシウムを表し、Ｘはメチル基、エチル基、プロピル基およびフェニル基からなる群から選ばれた少なくとも一つの基で置換されていてもよいアミノ基またはＳＡを表す。なお、ＳＡの少なくともいずれかにはＳＨが含まれる。）
（付記３）
前記シランカップリング剤が、アミノ基、メルカプト基、エポキシ基、イミダゾール基、ビニル基、ジアルキルアミノ基およびピリジン基からなる群から選ばれた基を少なくとも一つ含むものである、付記２に記載の多層回路基板。

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.
(Appendix 3)
The multilayer circuit according to appendix 2, wherein the silane coupling agent includes at least one group selected from the group consisting of an amino group, a mercapto group, an epoxy group, an imidazole group, a vinyl group, a dialkylamino group, and a pyridine group. substrate.

(Appendix 4)
The multilayer circuit board according to any one of appendices 1 to 3, wherein the wiring layer is made of copper.

(Appendix 5)
The insulating resin layer, the group consisting of polyimide resins, epoxy resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, o olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resins and polyether ether ketone resin The multilayer circuit board according to any one of appendices 1 to 4, which includes at least one resin selected from the above.

(Appendix 6)
In a method for manufacturing a multilayer circuit board having a wiring layer and an insulating resin layer,
The wiring layer surface is treated with a treatment liquid containing a compound containing at least a nitro group, a carboxy group and a cyano group or an alkali metal salt thereof or a mixture thereof to form a first treated body,
Treating the surface of the first treated body with an organic compound capable of adsorbing or reacting with a nitro group, a carboxy group and a cyano group to form a second treated body;
A method for manufacturing a multilayer circuit board, comprising forming an insulating resin layer on the second treatment body.

(Appendix 7)
The compound containing at least the nitro group, carboxy group, and cyano group, or an alkali metal salt thereof, or a mixture thereof includes a compound selected from the group consisting of nitrobenzoic acid, nitrophthalic acid, nitrosalicylic acid, and alkali metal salts thereof. A method for manufacturing a multilayer circuit board according to appendix 6.

(Appendix 8)
The compound containing at least the nitro group, carboxy group and cyano group, or an alkali metal salt thereof or a mixture thereof is selected from cyanobenzoic acid, cyanophenol, dicyanobenzene, cyanoacetic acid, an alkali metal salt thereof, sodium cyanide, and potassium cyanide. The method for producing a multilayer circuit board according to appendix 6 or 7, comprising a compound selected from the group consisting of:

(Appendix 9)
The method for producing a multilayer circuit board according to any one of appendices 6 to 8, wherein the organic compound is a silane coupling agent or a triazine thiol of formula 1 or a silane coupling agent and a triazine thiol of formula 1.

（式１中、ＳＡのＡは、水素、リチウム、ナトリウム、カリウム、ルビジウムまたはセシウムを表し、Ｘはメチル基、エチル基、プロピル基およびフェニル基からなる群から選ばれた少なくとも一つの基で置換されていてもよいアミノ基またはＳＡを表す。なお、ＳＡの少なくともいずれかにはＳＨが含まれる。）
（付記１０）
前記シランカップリング剤が、アミノ基、メルカプト基、エポキシ基、イミダゾール基、ビニル基、ジアルキルアミノ基およびピリジン基からなる群から選ばれた基を少なくとも一つ含むものである、付記９に記載の多層回路基板の製造方法。

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.
(Appendix 10)
The multilayer circuit according to appendix 9, wherein the silane coupling agent includes at least one group selected from the group consisting of an amino group, a mercapto group, an epoxy group, an imidazole group, a vinyl group, a dialkylamino group, and a pyridine group. A method for manufacturing a substrate.

(Appendix 11)
The method for manufacturing a multilayer circuit board according to any one of appendices 6 to 10, wherein the wiring layer is made of copper.

(Appendix 12)
The insulating resin layer, the group consisting of polyimide resins, epoxy resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, o olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resins and polyether ether ketone resin The manufacturing method of the multilayer circuit board in any one of appendix 6-11 containing at least 1 resin chosen from these.

(Appendix 13)
A multilayer circuit board produced by the method for producing a multilayer circuit board according to any one of appendices 6 to 12.

It is a figure which shows typically the cross-sectional structure of the multilayer circuit board based on this invention. It is another figure which shows typically the cross-section of the multilayer circuit board based on this invention. It is a figure which illustrates the procedure of the method of forming a buildup multilayer circuit board using the manufacturing method of the multilayer circuit board which concerns on this invention. It is another figure which illustrates the procedure of the method of forming a buildup multilayer circuit board using the manufacturing method of the multilayer circuit board which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Wiring layer 2 Processed surface layer of 1st process body 3 Processed surface layer of 2nd process body 3 'Processed surface layer produced | generated by processing with triazine thiol or a silane coupling agent 3 "Silane coupling agent or triazine thiol Surface layer 4 produced by treatment in step 4 Insulating resin layer 6 Substrate 31 Substrate 32 Insulating layer 33 Conductive layer 34 Resist 35 Electro copper plating 36 Wiring layer 37 Layer of specific polar compound 38 Specific organic compound layer 39 Insulating layer

Claims (10)

In a multilayer circuit board having a wiring layer and an insulating resin layer,
At least all of the nitro group, carboxy group and cyano group are present on the surface of the wiring layer,
Directly there are organic compounds that can adsorb or react with nitro, carboxy and cyano groups,
Furthermore, the insulating resin layer is present immediately above.
Multi-layer circuit board. The multilayer circuit board according to claim 1, wherein the organic compound is a silane coupling agent or a triazine thiol of formula 1 or a silane coupling agent and a triazine thiol of formula 1.

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.   The multilayer according to claim 2, wherein the silane coupling agent contains at least one group selected from the group consisting of an amino group, a mercapto group, an epoxy group, an imidazole group, a vinyl group, a dialkylamino group, and a pyridine group. Circuit board.   The multilayer circuit board according to claim 1, wherein the wiring layer is made of copper. The insulating resin layer, the group consisting of polyimide resins, epoxy resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, o olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resins and polyether ether ketone resin The multilayer circuit board according to claim 1, comprising at least one resin selected from the group consisting of: In a method for manufacturing a multilayer circuit board having a wiring layer and an insulating resin layer,
The wiring layer surface is treated with a treatment liquid containing at least one compound containing at least all of nitro group, carboxy group and cyano group , or an alkali metal salt thereof, or a mixture thereof to form a first treated body,
Treating the surface of the first treated body with an organic compound capable of adsorbing or reacting with a nitro group, a carboxy group and a cyano group to form a second treated body;
A method for manufacturing a multilayer circuit board, comprising forming an insulating resin layer on the second treatment body.   The compound containing at least the nitro group, carboxy group, and cyano group, or an alkali metal salt thereof, or a mixture thereof includes a compound selected from the group consisting of nitrobenzoic acid, nitrophthalic acid, nitrosalicylic acid, and alkali metal salts thereof. The manufacturing method of the multilayer circuit board of Claim 6.   The compound containing at least the nitro group, carboxy group and cyano group, or an alkali metal salt thereof or a mixture thereof is selected from cyanobenzoic acid, cyanophenol, dicyanobenzene, cyanoacetic acid, an alkali metal salt thereof, sodium cyanide, and potassium cyanide. The manufacturing method of the multilayer circuit board of Claim 6 or 7 containing the compound chosen from the group which consists of. The manufacturing method of the multilayer circuit board in any one of Claims 6-8 whose said organic compound is a silane coupling agent or the triazine thiol of Formula 1, or a silane coupling agent and the triazine thiol of Formula 1.

(In formula 1, A in SA represents hydrogen, lithium, sodium, potassium, rubidium or cesium, and X is substituted with at least one group selected from the group consisting of methyl, ethyl, propyl and phenyl groups. Represents an optionally substituted amino group or SA, where at least one of SA includes SH.   A multilayer circuit board produced by the method for producing a multilayer circuit board according to claim 6.

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