JP2007016105A - Metal-surface treating liquid, laminated body, and method for manufacturing laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal-surface treating liquid capable of improving the adhesion between a metal surface and an insulating resin; a method for manufacturing a laminated body capable of improving the adhesion between a metal wiring layer and an insulating resin layer; and a laminated body improved in the adhesion between a metal wiring layer and an insulating resin layer. <P>SOLUTION: The metal-surface treating liquid contains a triazine-thiol derivative having a specific structure and is used for treating the metal surface, on which an insulating resin film 2 is to be formed. Preferably, the metal-surface treating liquid is coexisted with an organic acid or a carbonic acid. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a metal surface treatment technique. More specifically, in a laminate having an insulating resin layer in contact with a metal wiring layer, for example, a circuit board having a metal wiring layer and an insulating resin layer on a support substrate, adhesion between the metal wiring layer and the insulating resin layer The present invention relates to a surface treatment technology of a metal wiring layer for improving the resistance.

  In recent years, miniaturization and multilayering of printed wiring boards and high-density mounting of electronic components have rapidly progressed, and a buildup multilayer wiring structure has been actively studied for printed wiring boards.

  In the build-up multilayer wiring structure, an insulating resin layer is formed between a plurality of wiring layers, and fine holes called via holes are formed in the insulating resin layer in order to establish conduction between the wiring layers. The via hole is produced by, for example, 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 resin 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 resin layer to the wiring pattern is repeated as necessary, the degree of circuit integration can be increased.

  Conventionally, 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, in order to improve the adhesion between the copper wiring of the build-up wiring board and the insulating resin layer on the upper side, the following processing is performed.

That is, the surface of the copper wiring is etched (chemically polished) with cupric chloride solution, ferric chloride solution, sulfuric acid / hydrogen peroxide solution, formic acid aqueous solution, etc., and 10-point average surface roughness (R _z ) 2 μm A process is performed in which the fine protrusions are formed and the resin formed on the upper side of the wiring is firmly fixed to the copper wiring surface by the anchor action of the fine protrusions.

  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 insulating resin, in addition to the adhesion due to the physical anchor effect. At the molecular level, methods using various triazine thiols are disclosed. Specifically, in Patent Document 1, a triazine thiol layer is formed on a conductor. In this method, the resin is limited to an ABS resin that can react with triazine thiol. In Patent Document 2, a triazine thiol layer is formed on a conductor, and an organic compound capable of reacting or adsorbing with triazine thiol is further formed to enhance adhesion with the insulating resin. However, since this method cannot avoid oxidation of the copper surface, only a peel strength of 0.5 kgf / cm (converted value is 0.5 kN / m) or less was obtained.

  For this, a method has been proposed in which a triazine thiol film is formed by organic plating to form an insulating resin layer thereon (see Patent Document 3). That is, first, a reverse bias is applied to remove the oxide film on the copper surface, and then triazine thiol is organically plated. However, a seed electrode layer is essential for plating, and there is a problem that it is difficult to apply to an isolated wiring site.

Up to now, the problem regarding the adhesion between the metal surface and the insulating resin has been explained using copper as an example. However, the problem with the adhesion between the metal surface and the insulating resin is more or less the problem that also exists for other metals. It is.

Japanese Patent Laid-Open No. 10-335782 (Claims) JP 2001-203462 A (Claims) Kunio Mori, Surface Technology, 2000, 51, No. 3, p. 276

  An object of the present invention is to solve the above problems and provide a novel technique for improving the adhesion between a metal surface and an insulating resin. Still other objects and advantages of the present invention will become apparent from the following description.

  According to the first aspect of the present invention, there is provided a metal surface treatment liquid comprising at least one triazine thiol derivative having a structure represented by the following formulas (1) to (3).

（式（１）〜（３）において、Ｒは、互いに独立に、メチル基、ヒドロキシ基、メトキシ基またはエトキシ基であり、Ａは、各式内および各式毎に独立に、水素、ＮＨ_４、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であり、ｎは、各式毎に独立に、０〜３の整数であり、Ｘは、各式毎に独立に、ビニル基、グリシドキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、メルカプト基またはイソシアナート基である。）
本発明態様により金属表面と絶縁樹脂との密着性を向上させることができる。具体的には金属配線層に接して絶縁樹脂層を有する積層体において、金属配線層と絶縁樹脂層との間の密着性を向上させることができる。従って、密着性に優れた積層体、たとえば多層配線構造を持つ半導体集積回路装置を得ることができる。

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group.)
According to the embodiment of the present invention, the adhesion between the metal surface and the insulating resin can be improved. Specifically, in a laminate having an insulating resin layer in contact with the metal wiring layer, adhesion between the metal wiring layer and the insulating resin layer can be improved. Therefore, it is possible to obtain a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure.

  The metal surface treatment liquid further contains at least one acid selected from the group consisting of an organic acid and carbonic acid, the pH of the metal surface treatment liquid is 7 or less, and the metal surface treatment liquid comprises water and alcohol. The metal surface treatment liquid is a treatment liquid for improving the adhesion between the metal surface and the insulating resin. In particular, the metal surface treatment liquid comprises the metal wiring layer and the insulating resin. It is preferable that it is a processing liquid for improving adhesiveness with a layer.

  According to another aspect of the present invention, there is provided a laminated body having an insulating resin layer in contact with a metal wiring layer, wherein the following formulas (1) to (3) are provided between the metal wiring surface and the insulating resin layer. And a laminate sandwiching at least one of the triazine thiol derivatives having the structure shown in FIG.

（式（１）〜（３）において、Ｒは、互いに独立に、メチル基、ヒドロキシ基、メトキシ基またはエトキシ基であり、Ａは、各式内および各式毎に独立に、水素、ＮＨ_４、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であり、ｎは、各式毎に独立に、０〜３の整数であり、Ｘは、各式毎に独立に、ビニル基、グリシドキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、メルカプト基またはイソシアナート基である。）。本発明態様により、密着性に優れた積層体、たとえば多層配線構造を持つ半導体集積回路装置を得ることができる。前記金属配線表面と前記絶縁樹脂層との間に、さらに、シランカップリング剤を挟んだ積層体であることが好ましい。

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group). According to the aspect of the present invention, it is possible to obtain a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure. A laminate in which a silane coupling agent is further sandwiched between the metal wiring surface and the insulating resin layer is preferable.

  According to still another aspect of the present invention, a laminate having an insulating resin layer in contact with a metal wiring layer, the metal wiring surface is treated with the metal surface treatment liquid, and the insulating resin is formed thereon. A laminated body formed by forming a layer is provided. According to the aspect of the present invention, it is possible to obtain a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure.

  The treatment of the metal wiring surface with the metal surface treatment liquid is immersion of the metal wiring surface in the metal surface treatment liquid or spraying the metal wiring surface with the metal surface treatment liquid, and the metal surface treatment It is preferable that the surface of the metal wiring treated with the metal surface treatment liquid is treated with a silane coupling agent after the treatment of the metal wiring surface with the liquid and before the formation of the insulating resin layer.

  Further, in common with the two laminated body embodiments, the metal wiring layer is made of copper or a copper alloy, the laminated body is a semiconductor integrated circuit device having a multilayer wiring structure, and the insulating resin layer From the group consisting of polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resin and polyether ether ketone resin It is preferable that it comprises at least one selected resin.

  According to still another aspect of the present invention, in a method for manufacturing a laminate having an insulating resin layer in contact with a metal wiring layer, the metal wiring surface is treated with the metal surface treatment liquid, and the insulating resin is formed thereon. A method of manufacturing a laminate is provided that forms a layer. According to the aspect of the present invention, it is possible to manufacture a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure.

  The treatment of the surface of the metal wiring with the metal surface treatment liquid is immersion of the surface of the metal wiring in the metal surface treatment liquid or spray onto the surface of the metal wiring with the metal surface treatment liquid. After the treatment of the metal wiring surface and before the formation of the insulating resin layer, the metal wiring surface treated with the metal surface treatment liquid is treated with a silane coupling agent, and the metal wiring layer is made of copper or a copper alloy. The laminated body is a semiconductor integrated circuit device having a multilayer wiring structure, and the concentration of the triazine thiol derivative in the metal surface treatment liquid is in the range of 0.1 mmol / L to 1000 mmol / L. Is preferred.

  According to the present invention, the adhesion between the metal surface and the insulating resin can be improved. Specifically, in a laminate having an insulating resin layer in contact with the metal wiring layer, adhesion between the metal wiring layer and the insulating resin layer can be improved. Therefore, it is possible to obtain a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, formulas, examples and the like. In addition, these figures, formulas, examples, etc., and explanations 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.

  The metal surface treatment liquid according to the present invention comprises at least one triazine thiol derivative having a specific chemical structure.

  In the present invention, the metal surface to be treated with the metal surface treatment liquid may be a metal surface produced by any method such as an electroless plating method, an electrolytic plating method, a vapor deposition method, a sputtering method, or a damascene method. Good. In the present invention, “metal” includes alloys. This metal can be appropriately selected from known metals (including alloys). For example, copper, gold, silver, nickel and alloys containing these can be exemplified. There is no restriction | limiting in particular about content of the said metal in an alloy. The effect of the present invention is particularly great when the metal is susceptible to chemical changes such as oxidation in the air. In this sense, in the present invention, the “metal” (for example, the metal wiring according to the present invention) is preferably copper or a copper alloy.

  The metal surface according to the present invention may have been subjected to the anchor treatment described above. In such a case, higher adhesion is often obtained. The metal surface 10-point average surface roughness in the anchor treatment is preferably in the range of 0.5 to 5 μm.

  The triazine thiol derivative having the specific chemical structure can be represented by any of the following formulas (1) to (3).

式（１）〜（３）において、Ｒは、互いに独立に、メチル基、ヒドロキシ基、メトキシ基またはエトキシ基であり、Ａは、各式内および各式毎に独立に、水素、ＮＨ_４、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であり、ｎは、各式毎に独立に、０〜３の整数であり、Ｘは、各式毎に独立に、ビニル基、グリシドキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、メルカプト基またはイソシアナート基である。

In the formulas (1) to (3), R is, independently of each other, a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A is hydrogen, NH ₄ , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, methacryloxy independently for each formula Group, acryloxy group, amino group, ureido group, mercapto group or isocyanate group.

  The reason why the adhesion is improved by the triazine thiol derivative having the above specific chemical structure is that one or more mercapto groups react with the metal, and in addition to the remaining mercapto group, the structural portion represented by the following formula (4) It is presumed that this is because high adhesion can be obtained by reacting with the insulating resin. In addition, n and X in Formula (4) have the same meaning as n and X in Formulas (1) to (3).

このトリアジンチオール誘導体は、公知の任意の方法で合成することができる。たとえば、１，３，５−トリアジン−２，４，６−トリチオンと水酸化アルカリ金属若しくはアルカリ金属ボロンハイドライドとを水若しくは有機溶媒に溶解するか、または、１，３，５−トリアジン−２，４，６−トリチオンとアミンとを水若しくは有機溶媒に溶解することによりトリアジントリチオールやその塩を作製し、このようにして得たトリチオール化合物をシラン化合物と反応させて作製することができる。

This triazine thiol derivative can be synthesized by any known method. For example, 1,3,5-triazine-2,4,6-trithione and alkali metal hydroxide or alkali metal boron hydride are dissolved in water or an organic solvent, or 1,3,5-triazine-2, A triazine trithiol or a salt thereof can be prepared by dissolving 4,6-trithione and an amine in water or an organic solvent, and the trithiol compound thus obtained can be reacted with a silane compound.

  One or more triazine thiol derivatives may be present in the metal surface treatment liquid according to the present invention. As long as it is not contrary to the gist of the present invention, the purity is not particularly limited, and an intermediate or a by-product may be mixed.

  What is necessary is just to determine suitably the density | concentration of the triazine thiol derivative in the metal surface treatment liquid which concerns on this invention according to actual conditions, such as time required for a process. Generally, the range of 0.1 mmol / L to 1000 mmol / L is preferable. When there are a plurality of triazine thiol derivatives, the total is preferably in the range of 0.1 mmol / L to 1000 mmol / L. When the concentration is lower than 0.1 mmol / L, a triazine thiol derivative layer having a sufficient thickness is not formed on the metal surface. When the concentration is higher than 1000 mmol / L, the triazine thiol derivative layer becomes too thick. Since this reaction occurs, it may be difficult to react with the insulating resin.

  The metal surface treatment liquid according to the present invention preferably further contains at least one acid selected from the group consisting of an organic acid and carbonic acid. In the case where the metal surface according to the present invention is susceptible to chemical changes such as oxidation in the air, an oxide film is formed, and the adhesion (measured by peel strength, etc.) due to the triazine thiol derivative may be reduced. However, when the organic acid or carbonic acid according to the present invention (hereinafter referred to as "the acid according to the present invention" collectively refers to "the organic acid or carbonic acid according to the present invention"), the adhesiveness is reduced. It becomes possible to prevent. In the present invention, the “metal surface” includes a surface before undergoing such a chemical change and a surface after undergoing such a chemical change, but the acid according to the present invention coexists. The metal surface treatment liquid can be preferably used for the latter. For example, the case where the copper wiring is formed in the atmosphere, or the case where the copper wiring is formed in an environment where it is not exposed to oxygen and then exposed to air is applicable.

  It is important that the acid according to the present invention acts on the metal surface together with the triazine thiol derivative. For example, in the case of treating with the acid according to the present invention and then treating with a triazine thiol derivative, the effect decreases when exposed to air even for a short time between both treatments. If it is not exposed to air even for a short time between both treatments, it seems that a certain effect can be obtained, but the apparatus becomes complicated and leads to an increase in cost.

  There is no restriction | limiting in particular about the kind of organic acid which concerns on this invention, According to the objective, it can select suitably. Examples thereof include organic acids having 1 to 6 carbon atoms and having saturated or unsaturated aliphatic or alicyclic groups and one or two carboxylic acid groups. A hydroxy group may be included. More specifically, formic acid, acetic acid, propionic acid, octylic acid, glycolic acid, butyric acid, isobutyric acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid And acetylenedicarboxylic acid, lactic acid, tartaric acid, malic acid and citric acid.

  Carbonic acid according to the present invention may be produced by any known method. It may be prepared by neutralizing carbonate with hydrochloric acid or the like, or by blowing carbon dioxide into water.

  The acid according to the present invention exhibits its effect when the system is neutral or acidic. When pH exceeds 7, the speed | rate which melt | dissolves an oxide film will become very slow. That is, the pH of the metal surface treatment liquid according to the present invention is preferably 7 or less. The pH of the system varies depending on the chemical structure of the triazine thiol derivative according to the present invention, its concentration, etc. in addition to the type and concentration of the acid according to the present invention in the metal surface treatment liquid according to the present invention. The type and amount of acid used are preferably determined so that the pH of the metal surface treatment solution according to the present invention is 7 or less in consideration of the type and amount of the triazine thiol derivative according to the present invention. The pH of the metal surface treatment liquid according to the present invention is more preferably in the range of 3-7.

  The triazine thiol derivative according to the present invention is used after being dissolved in a solvent. Although there is no restriction | limiting in particular in the solvent which can be used, The thing containing at least any one of water and alcohol is preferable from solubility and the ease of use. A mixed solvent of water and alcohol or a water solvent is more preferable.

  In the metal surface treatment liquid according to the present invention, other agents may coexist as long as not departing from the spirit of the present invention.

  The metal surface treatment liquid according to the present invention is a metal intended to improve the adhesion between the metal surface and the insulating resin, for example, to improve the adhesion between the metal wiring layer and the insulating resin layer. Suitable for surface treatment. Specifically, in a laminate having an insulating resin layer in contact with the metal wiring layer (for example, a semiconductor integrated circuit device having a multilayer wiring structure), the adhesion between the metal wiring layer and the insulating resin layer can be improved. . Therefore, it is possible to obtain a laminated body having excellent adhesion, for example, a semiconductor integrated circuit device having a multilayer wiring structure.

  Such a laminate can be obtained by treating the metal wiring surface with the metal surface treatment liquid and forming an insulating resin layer thereon. The treatment is not particularly limited, but immersion of the metal wiring surface in the metal surface treatment solution or spraying on the metal wiring surface with the metal surface treatment solution is preferable because it is simple and reliable. In addition, what is necessary is just to make a metal surface treatment liquid into a predetermined composition just before use. In the case of spraying, there are cases where processing liquids having different compositions are present in a plurality of injection sources, and the composition according to the present invention may be obtained by spraying.

  As described above, the metal wiring according to the present invention may be produced by any method such as electroless plating, electrolytic plating, vapor deposition, sputtering, damascene, inner via hole, through hole, connection terminal. Etc. may be included. Since it is not necessary to energize the metal wiring during processing, it can be applied to isolated wiring parts.

  A known material can be selected and used for the resin on the metal surface and the insulating resin layer provided on the metal wiring according to the present invention. Specifically, polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, liquid crystal polymer, polyether having excellent heat resistance and insulation properties Examples thereof include imide resins and polyether ether ketone resins. A plurality of these may be used.

  After the metal wiring surface is treated with the metal surface treatment liquid according to the present invention, the metal wiring surface treated with the metal surface treatment liquid may be treated with a coupling agent before the insulating resin layer is formed. If it does in this way, the mercapto group and group of Formula (4) which do not participate in reaction with the metal of the triazine thiol derivative on the metal surface will react with the coupling agent, and the functional group of the coupling agent will react with the insulating resin. As a result, only the triazine thiol derivative can provide high adhesion to an insulating resin having poor reactivity. Examples of coupling agents that can be used for this purpose include silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like. A silane coupling agent is particularly preferable. It is preferable that the molecule of the coupling agent contains at least one of an amino group, a mercapto group, an epoxy group, an imidazole group, a dialkylamino group, and a pyridine group.

  The silane coupling agent can be appropriately selected from known silane coupling agents. Specific examples include vinyltrichlorosilane, vinyltris (2-methoxy) silane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyl. Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3 -Aminopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane and the like.

  Although there is no restriction | limiting in particular about the process by a coupling agent, The immersion to the copper wiring surface in a coupling agent liquid or the spraying to the copper wiring surface by a coupling agent liquid is simple and reliable, and preferable.

  When the above is reconsidered from the viewpoint of the configuration of the laminate, the laminate has an insulating resin layer in contact with the metal wiring layer, and the above formula (1) is provided between the metal wiring surface and the insulating resin layer. A laminate in which at least one of the triazine thiol derivatives having the structure shown in (3) is sandwiched, or a laminate in which a silane coupling agent is further sandwiched between the metal wiring surface and the insulating resin layer, It can be considered that the laminate has improved adhesion between the layer and the insulating resin layer.

  In this case, the presence of the sandwiched triazine thiol derivative can be confirmed by Auger analysis, X-ray microanalyzer (XMA) analysis, X-ray photoelectron spectrometer (XPS), FT-IR analysis, or the like. It is considered that the triazine thiol derivative sandwiched between the metal wiring layer and the insulating resin layer forms a bond as described above. In addition, it can be said that the silane coupling agent is preferably formed between the triazine thiol derivative layer and the insulating resin layer. However, as long as the adhesion effect according to the present invention is exhibited, it is not necessary to verify whether or not bonding with the metal wiring layer or the insulating resin layer actually occurs or where the silane coupling agent is.

  The laminate obtained by treating the surface of the metal wiring with the metal surface treatment liquid according to the present invention often has a plurality of combinations of metal wiring layers and insulating resin layers in one laminate. A typical example is a build-up multilayer circuit board. Hereinafter, a method for forming a build-up multilayer circuit board using the wiring surface treatment method of the present invention will be described with reference to FIG.

  FIG. 1 is a schematic cross-sectional view when forming a build-up multilayer circuit board. First, as shown in FIG. 1A, a build-up insulating resin layer 2 is formed on a glass fiber reinforced resin substrate 1 on which a circuit is formed. The surface of the insulating resin layer 2 is subjected to a surface roughening treatment for obtaining adhesion, and then a metal conductive layer 3 is formed by electroless plating or sputtering.

  Next, as shown in FIG. 1 (2), a resist 4 is formed by patterning. Then, as shown in FIG. 1 (3), an electroplated metal 5 is grown in the opening. Next, as shown in FIG. 1 (4), after the resist is removed, the conductive layer 3 is removed by etching as shown in FIG. 1 (5).

  Next, as shown in FIG. 1 (6), the surface treatment is performed with the metal surface treatment liquid according to the present invention. As a treatment method, a dipping method, a spraying method using a spray, or the like can be used. After the treatment, when the treated surface is washed with an appropriate liquid such as water, the triazine derivative 6 according to the present invention remains only on the wiring (metal plating portion).

  Thereafter, as shown in FIG. 1 (7), the wiring surface may be treated with a silane coupling agent to form a silane coupling agent layer 7. As a method for the coupling agent treatment, an immersion method, a spraying method using a spray, or the like can be used.

  Thereafter, as shown in FIG. 1 (8), an insulating resin layer 8 as the next layer is formed. For forming the insulating resin layer, a known method such as a method of attaching a semi-cured resin sheet or a method of applying a resin varnish containing a solvent can be employed. Next, a via hole is formed in order to establish conduction between the upper and lower wirings. By repeating this process, a multilayer circuit board can be formed.

  Next, examples and comparative examples of the present invention will be described in detail. The numbers of triazine derivatives in the following examples correspond to the numbers of triazine derivatives in Table 1. All examples were performed in an air atmosphere.

[Example 1]
0.1 mol / L 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, manufactured by Sankyo Kasei) and 0.1 mol / L γ-aminopropyltriethoxy Silane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in methyltetrahydrofuran and refluxed at 80 ° C. for 2 hours to obtain triazine derivative 1 having an amino group.

  An electroplated copper foil having a thickness of 35 μm was immersed for 5 minutes in an aqueous solution in which 1% by weight of triazine derivative 1 and 0.1% by weight of sodium hydroxide for dissolving triazine derivative 1 were dissolved, and then washed with water. And baked at 100 ° C. for 30 minutes and dried. It was confirmed by Auger electron spectroscopy that the triazine derivative remained on the copper foil.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Then, it removed from the vacuum press and the epoxy resin was hardened by heating at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength as adhesion was measured. 1.1 kgf / cm (converted value is 1.1 kN / m), a high peel strength comparable to the existing anchor effect was obtained.

[Example 2]
0.1 mol / L 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Santhiol N-1, manufactured by Sankyo Kasei) and 0.1 mol / L γ-mercaptopropyltrimethoxy Silane (KBM-803: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in methyltetrahydrofuran and refluxed at 80 ° C. for 2 hours to obtain a triazine derivative 2 having a mercapto group.

  An electroplated copper foil having a thickness of 35 μm was immersed in an aqueous solution in which 1% by weight of triazine derivative 2 and 0.1% by weight of sodium hydroxide were dissolved, washed with water, baked at 100 ° C. for 30 minutes, Dried.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Then, it removed from the vacuum press and the epoxy resin was hardened by heating at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. A peel strength as high as 1.0 kgf / cm (converted value is 1.0 kN / m), which is similar to the existing anchor effect, was obtained.

[Example 3]
0.1 mol / L 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, manufactured by Sankyo Kasei) and 0.1 mol / L γ-glycidoxypropyl Trimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in methyltetrahydrofuran and refluxed at 80 ° C. for 2 hours to obtain a triazine derivative 3 having an epoxy group.

  An electroplated copper foil having a thickness of 35 μm was immersed in an aqueous solution in which 1% by weight of triazine derivative 3 and 0.1% by weight of sodium hydroxide were dissolved, washed with water, baked at 100 ° C. for 30 minutes, Dried.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Then, it removed from the vacuum press and the epoxy resin was hardened by heating at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. 0.9 kgf / cm (converted value is 0.9 kN / m), a peel strength as high as the existing anchor effect was obtained.

[Example 4]
0.2 mol / L 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Santhiol N-1, manufactured by Sankyo Kasei) and 0.1 mol / L γ-aminopropyltriethoxy Silane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in methyltetrahydrofuran and refluxed at 80 ° C. for 2 hours to obtain triazine derivative 4 having an amino group.

  An electroplated copper foil having a thickness of 35 μm was immersed in an aqueous solution in which 1% by weight of triazine derivative 4 and 0.1% by weight of sodium hydroxide were dissolved, washed with water, baked at 100 ° C. for 30 minutes, Dried.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Then, it removed from the vacuum press and the epoxy resin was hardened by heating at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. 1.1 kgf / cm (converted value is 1.1 kN / m), a high peel strength comparable to the existing anchor effect was obtained.

[Example 5]
0.3 mol / L 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, manufactured by Sankyo Kasei) and 0.1 mol / L γ-aminopropyltriethoxy Silane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed in methyltetrahydrofuran and refluxed at 80 ° C. for 2 hours to obtain triazine derivative 5 having an amino group.

  An electroplated copper foil having a thickness of 35 μm was immersed in an aqueous solution in which 1% by weight of triazine derivative 5 and 0.1% by weight of sodium hydroxide were dissolved, washed with water, baked at 100 ° C. for 30 minutes, Dried.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Then, it removed from the vacuum press and the epoxy resin was hardened by heating at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. 0.9 kgf / cm (converted value is 0.9 kN / m), a peel strength as high as the existing anchor effect was obtained.

[Comparative Example 1]
A 35 μm-thick electroplated copper foil is immersed in a 1,4% aqueous solution of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Santhiol N-1, Sankyo Kasei) for 5 minutes. After washing with water, it was baked at 100 ° C. for 30 minutes and dried.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Thereafter, the epoxy resin was taken out from the vacuum press and cured at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. Only a peel strength of 0.5 kgf / cm (converted value was 0.5 kN / m) was obtained.

[Comparative Example 2]
An electroplated copper foil having a thickness of 35 μm was immersed in a 1 wt% aqueous solution of γ-aminopropyltriethoxysilane (coupling agent, KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) for 5 minutes at room temperature, washed with water, It was baked at 100 ° C. for 30 minutes, dried, and treated with a coupling agent.

  The treatment surface was overlapped so that the thermosetting epoxy resin sheet in a semi-cured state (B stage) was in contact with the treated surface, and was pressed by a vacuum press under conditions of 150 ° C., 1 MPa, 5 minutes. Thereafter, the epoxy resin was taken out from the vacuum press and cured at 180 ° C. for 1 hour under atmospheric pressure.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength was measured. Only a peel strength of 0.3 kgf / cm (converted value was 0.3 kN / m) was obtained.

  The results of Examples 1 to 5 and Comparative Examples 1 and 2 are summarized in Table 1.

［実施例６］
１重量％のトリアジン誘導体１および水酸化ナトリウム０．１重量％を溶解させた水溶液に代えて、１重量％のトリアジン誘導体１および水酸化ナトリウム０．１重量％および１重量％の酢酸を溶解させた水溶液を使用した以外は、実施例１と同様にして積層体を得た。

[Example 6]
Instead of an aqueous solution in which 1% by weight of triazine derivative 1 and 0.1% by weight of sodium hydroxide are dissolved, 1% by weight of triazine derivative 1 and 0.1% by weight of sodium hydroxide and 1% by weight of acetic acid are dissolved. A laminate was obtained in the same manner as in Example 1 except that an aqueous solution was used.

  The laminate thus obtained was cut into a width of 1 cm, and the peel strength as adhesion was measured. A high peel strength of 1.1 kgf / cm (converted value was 1.1 kN / m) was obtained.

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

(Appendix 1)
A metal surface treatment liquid comprising at least one of triazine thiol derivatives having a structure represented by the following formulas (1) to (3).

（式（１）〜（３）において、Ｒは、互いに独立に、メチル基、ヒドロキシ基、メトキシ基またはエトキシ基であり、Ａは、各式内および各式毎に独立に、水素、ＮＨ_４、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であり、ｎは、各式毎に独立に、０〜３の整数であり、Ｘは、各式毎に独立に、ビニル基、グリシドキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、メルカプト基またはイソシアナート基である。）
（付記２）
さらに、有機酸および炭酸からなる群から選ばれた少なくとも一つの酸を含む、付記１に記載の金属表面処理液。

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group.)
(Appendix 2)
The metal surface treatment solution according to appendix 1, further comprising at least one acid selected from the group consisting of an organic acid and carbonic acid.

(Appendix 3)
The metal surface treatment solution according to Supplementary Note 1 or 2, wherein the pH is 7 or less.

(Appendix 4)
4. The metal surface treatment liquid according to any one of supplementary notes 1 to 3, comprising at least one of water and alcohol.

(Appendix 5)
The metal surface treatment liquid according to any one of appendices 1 to 4, which is a treatment liquid for improving the adhesion between the metal surface and the insulating resin.

(Appendix 6)
The metal surface treatment liquid according to any one of appendices 1 to 5, which is a treatment liquid for improving adhesion between the metal wiring layer and the insulating resin layer.

(Appendix 7)
A laminate having an insulating resin layer in contact with a metal wiring layer,
A laminate in which at least one triazine thiol derivative having a structure represented by the following formulas (1) to (3) is sandwiched between the metal wiring surface and the insulating resin layer.

（式（１）〜（３）において、Ｒは、互いに独立に、メチル基、ヒドロキシ基、メトキシ基またはエトキシ基であり、Ａは、各式内および各式毎に独立に、水素、ＮＨ_４、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であり、ｎは、各式毎に独立に、０〜３の整数であり、Ｘは、各式毎に独立に、ビニル基、グリシドキシ基、スチリル基、メタクリロキシ基、アクリロキシ基、アミノ基、ウレイド基、メルカプト基またはイソシアナート基である。）
（付記８）
前記金属配線表面と前記絶縁樹脂層との間に、さらに、シランカップリング剤を挟んだ積層体。

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group.)
(Appendix 8)
A laminate in which a silane coupling agent is further sandwiched between the metal wiring surface and the insulating resin layer.

(Appendix 9)
A laminate having an insulating resin layer in contact with a metal wiring layer,
The laminated body formed by processing the said metal wiring surface with the metal surface treatment liquid in any one of Additional remarks 1-6, and forming the said insulating resin layer on it.

(Appendix 10)
The laminate according to appendix 9, wherein the treatment of the surface of the metal wiring with the metal surface treatment liquid is immersion of the surface of the metal wiring in the metal surface treatment liquid or spray onto the surface of the metal wiring with the metal surface treatment liquid. .

(Appendix 11)
Additional treatment 9 or 10 wherein the metal wiring surface treated with the metal surface treatment liquid is treated with a silane coupling agent after the treatment of the metal wiring surface with the metal surface treatment liquid and before the formation of the insulating resin layer. The laminated body as described in.

(Appendix 12)
The laminate according to any one of appendices 7 to 11, wherein the metal wiring layer is made of copper or a copper alloy.

(Appendix 13)
The laminated body according to any one of appendices 7 to 12, wherein the laminated body is a semiconductor integrated circuit device having a multilayer wiring structure.

(Appendix 14)
The insulating resin layer is made of polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, liquid crystal polymer, polyetherimide resin, and polyether ether ketone resin. The laminate according to any one of appendices 7 to 13, comprising at least one resin selected from the group consisting of:

(Appendix 15)
In the manufacturing method of the laminate having the insulating resin layer in contact with the metal wiring layer,
The manufacturing method of a laminated body which processes the said metal wiring surface with the metal surface treatment liquid in any one of Additional remarks 1-6, and forms the said insulating resin layer on it.

(Appendix 16)
The laminate according to appendix 15, wherein the treatment of the surface of the metal wiring with the metal surface treatment liquid is immersion of the surface of the metal wiring in the metal surface treatment liquid or spray onto the surface of the metal wiring with the metal surface treatment liquid. Manufacturing method.

(Appendix 17)
Item 15. The supplementary note 15 or 16, wherein the metal wiring surface treated with the metal surface treatment liquid is treated with a silane coupling agent after the treatment of the metal wiring surface with the metal surface treatment liquid and before the formation of the insulating resin layer. The manufacturing method of the laminated body.

(Appendix 18)
The method for manufacturing a laminate according to any one of appendices 15 to 17, wherein the metal wiring layer is made of copper or a copper alloy.

(Appendix 19)
The method for manufacturing a laminate according to any one of appendices 15 to 18, wherein the laminate is a semiconductor integrated circuit device having a multilayer wiring structure.

(Appendix 20)
The manufacturing method of the laminated body in any one of Additional remarks 15-19 in which the density | concentration of the said triazine thiol derivative in the said metal surface treatment liquid exists in the range of 0.1 mmol / L-1000 mmol / L.

It is a typical sectional view at the time of build-up multilayer circuit board formation.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass fiber reinforced resin board | substrate 2 Insulating resin layer 3 Current carrying layer 4 Resist 5 Electroplating metal 6 Triazine derivative 7 Silane coupling agent layer 8 Insulating resin layer

Claims (5)

A metal surface treatment liquid comprising at least one of triazine thiol derivatives having a structure represented by the following formulas (1) to (3).

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group.)   The metal surface treatment solution according to claim 1, further comprising at least one acid selected from the group consisting of an organic acid and carbonic acid. A laminate having an insulating resin layer in contact with a metal wiring layer,
A laminate in which at least one triazine thiol derivative having a structure represented by the following formulas (1) to (3) is sandwiched between the metal wiring surface and the insulating resin layer.

(In the formulas (1) to (3), R independently represents a methyl group, a hydroxy group, a methoxy group or an ethoxy group, and A represents hydrogen, NH ₄ independently in each formula and for each formula. , Lithium, sodium, potassium, rubidium or cesium, n is an integer of 0 to 3 independently for each formula, and X is a vinyl group, glycidoxy group, styryl group, independently of each formula, A methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group or an isocyanate group.) A laminate having an insulating resin layer in contact with a metal wiring layer,
The laminated body formed by processing the said metal wiring surface with the metal surface treatment liquid of Claim 1 or 2, and forming the said insulating resin layer on it. In the manufacturing method of the laminate having the insulating resin layer in contact with the metal wiring layer,
The manufacturing method of a laminated body which processes the said metal wiring surface with the metal surface treatment liquid of Claim 1 or 2, and forms the said insulating resin layer on it.

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