JP2007035995A - Copper surface treatment liquid, method for manufacturing laminate and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper surface treatment liquid capable of enhancing adhesiveness between a copper surface and insulating resin, a method for manufacturing a laminate in which adhesiveness between the copper surface and the insulating resin can be enhanced, and the laminate in which the adhesiveness between the copper surface and the insulating resin is enhanced. <P>SOLUTION: The copper surface is treated with the copper surface treatment liquid containing the triazine thiol of a specific constitution or its derivative and an organic acid or a carbonic acid to form an insulating resin film thereon. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a copper surface treatment technique. More specifically, in a laminate having an insulating resin layer in contact with a copper wiring layer, for example, a circuit board having an insulating resin layer and a copper wiring layer on a support substrate, adhesion between the copper wiring layer and the insulating resin layer The present invention relates to a surface treatment technology of a copper 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 oxidation of the copper surface cannot be avoided by this method, only a peel strength of 0.5 kgf / cm (converted value is 0.049 MPa · cm) 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 Non-Patent Document 1). 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.
Japanese Patent Laid-Open No. 10-335782 (Claims) JP 2001-203462 A (Claims) Kunio Mori, “Surface Technology”, 2000, Vol. 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 copper surface and an insulating resin. Still other objects and advantages of the present invention will become apparent from the following description.

  According to one aspect of the present invention, at least one compound selected from the group consisting of triazine thiol and its derivatives represented by the following formula (1):

（式（１）中、ＸはＮＲ_２またはＳＡであり、ＮＲ_２中のＲは、互いに独立に水素、メチル基、エチル基、n―プロピル基、イソプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基または置換基を有していてもよいフェニル基であり、Ａは、互いに独立に、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る。）
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とを含んでなる銅表面処理液が提供される。

(In the formula (1), X is NR ₂ or SA, and R in NR ₂ is independently of each other hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl. A group, a t-butyl group or an optionally substituted phenyl group, and A is independently of each other hydrogen, NH ₄ , lithium, sodium, potassium, rubidium or cesium.)
There is provided a copper surface treatment solution comprising at least one acid selected from the group consisting of an organic acid and carbonic acid.

  According to the embodiment of the present invention, the adhesion between the copper surface and the insulating resin can be improved. Specifically, in a laminate having an insulating resin layer in contact with a copper wiring layer, adhesion between the copper 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 pH of the copper surface treatment liquid is 7 or less, the copper surface treatment liquid contains at least one of water and alcohol, and the copper surface treatment liquid improves the adhesion between the copper surface and the insulating resin. And a copper surface treatment liquid is preferably a treatment liquid for improving the adhesion between the copper wiring layer and the insulating resin layer.

  According to another aspect of the present invention, in a method for manufacturing a laminate having an insulating resin layer in contact with a copper wiring layer, the copper wiring surface is treated with the copper 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 copper wiring surface with the copper surface treatment liquid is immersion of the copper wiring surface in the copper surface treatment liquid or spraying on the copper wiring surface with the copper surface treatment liquid, by the copper surface treatment liquid After the treatment of the copper wiring surface, before the formation of the insulating resin layer, the copper wiring surface treated with a copper surface treatment liquid is treated with a silane coupling agent, and the insulating resin layer is a polyimide resin, At least one selected from the group consisting of epoxy resins, bismaleimide resins, maleimide resins, cyanate resins, polyphenylene ether resins, polyphenylene oxide resins, olefin resins, fluorine-containing resins, liquid crystal polymers, polyetherimide resins, and polyetheretherketone resins. It is preferable that it comprises two resins.

  According to still another aspect of the present invention, a laminate having an insulating resin layer in contact with a copper wiring layer, wherein the copper wiring surface is treated with the copper 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 copper wiring surface with the copper surface treatment liquid is immersion of the copper wiring surface in the copper surface treatment liquid or spraying on the copper wiring surface with the copper surface treatment liquid, by the copper surface treatment liquid After the treatment of the copper wiring surface and before the formation of the insulating resin layer, the copper wiring surface treated with a copper surface treatment liquid is treated with a silane coupling agent, and the laminate has a multilayer wiring structure. A semiconductor integrated circuit device, and the insulating resin layer is a polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, fluorine-containing resin, liquid crystal polymer, At least one resin selected from the group consisting of polyetherimide resins and polyetheretherketone resins It is made comprise, are preferred.

  According to the present invention, the adhesion between the copper surface and the insulating resin can be improved. Specifically, in a laminate having an insulating resin layer in contact with a copper wiring layer, adhesion between the copper 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 copper surface treatment liquid according to the present invention comprises at least one compound selected from the group consisting of triazine thiol having a specific chemical structure and derivatives thereof and at least one acid selected from the group consisting of organic acids and carbonic acid. Comprising.

  In the present invention, the copper surface to be treated with the copper surface treatment liquid may be a copper 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. Well, it may be the surface before undergoing a chemical change such as copper oxidation in the air, or the surface after undergoing a chemical change, but the latter from the viewpoint of easily exerting the adhesion effect Is preferred. 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. In the present invention, “copper” includes a copper alloy. Although there is no restriction | limiting in particular about copper content in a copper alloy, the one where there are many will show the effect of this invention easily.

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

The reason why adhesion is improved by triazine thiol having a specific chemical structure or a derivative thereof (hereinafter, “triazine thiol or derivative thereof” is collectively referred to as “triazine thiol compound”) is that one or two mercapto groups are This is presumably because high adhesion can be obtained by reacting with copper and the remaining mercapto group and / or NR ₂ group reacting with the insulating resin.

  At this time, the reaction between the mercapto group of the triazine thiol compound and copper is important. If an oxide film is present, this reaction is inhibited, and thus the adhesion that can be measured by peel strength is reduced. (Hereinafter, when “organic acid and carbonic acid according to the present invention” are collectively referred to as “an acid according to the present invention”), it is considered to have a function of removing this oxide film. It is important that the acid according to the present invention acts on the copper surface in coexistence with the triazine thiol compound. For example, in the case of treating with the triazine thiol compound after treating with the acid according to the present invention, 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.

  The triazine thiol compound having the specific chemical structure can be represented by the formula (1).

式（１）中、ＸはＮＲ_２またはＳＡであり、ＮＲ_２中のＲは、互いに独立に水素、メチル基、エチル基、n―プロピル基、イソプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基または置換基を有していてもよいフェニル基であり、Ａは、互いに独立に、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る。ＸがＳＡの場合は、三つのメルカプト基の内銅と反応せずに残ったメルカプト基が絶縁樹脂と反応することにより高い密着力が得られる。ＸがＮＲ_２の場合は、二つのメルカプト基の内銅と反応せずに残ったメルカプト基があればそのメルカプト基とアミノ基とが絶縁樹脂と反応することにより高い密着力が得られることになる。

In the formula (1), X is NR ₂ or SA, and R in NR ₂ is independently of each other hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group. , A t-butyl group or an optionally substituted phenyl group, and A is independently of each other hydrogen, NH ₄ , lithium, sodium, potassium, rubidium or cesium. When X is SA, high adhesion can be obtained by reacting the remaining mercapto group without reacting with the inner copper of the three mercapto groups with the insulating resin. When X is NR ₂ , if there is a mercapto group remaining without reacting with the inner copper of the two mercapto groups, the mercapto group and the amino group react with the insulating resin to obtain high adhesion. Become.

This triazine thiol compound 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, Triazine trithiol or a salt thereof can be prepared by dissolving 4,6-trithione and amine in water or an organic solvent. A compound in which X is NR ₂ can be synthesized by reacting 1,3,5-triazine-2,4,6-trichloride with 1 equivalent of amine and then reacting with sodium hydrosulfide. it can.

  One or more triazine thiol compounds may be present in the copper 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 compound in the copper 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 compounds, 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.

  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 triazine thiol compound and the organic acid and / or carbonic acid according to the present invention are 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.

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 a copper oxide will become very slow. That is, the pH of the copper surface treatment liquid according to the present invention is preferably 7 or less. In addition to the type and concentration of the acid according to the present invention in the copper surface treatment liquid according to the present invention, the pH of the system is the type of NR ₂ in the triazine thiol compound according to the present invention, the type of A, and the triazine according to the present invention. Since it varies depending on the concentration of the thiol compound, the type and amount of the acid according to the present invention take into account the type and amount of the triazine thiol compound according to the present invention and the pH of the copper surface treatment liquid according to the present invention. Is preferably determined to be 7 or less. The pH of the copper surface treatment liquid according to the present invention is more preferably in the range of 3-7.

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

  The copper surface treatment liquid according to the present invention is a copper intended to improve the adhesion between the copper surface and the insulating resin, for example, to improve the adhesion between the copper wiring layer and the insulating resin layer. Suitable for surface treatment. Specifically, in a laminate having an insulating resin layer in contact with the copper wiring layer (for example, a semiconductor integrated circuit device having a multilayer wiring structure), the adhesion between the copper 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 copper wiring surface with the copper surface treatment liquid and forming an insulating resin layer thereon. Although there is no restriction | limiting in particular about this process, The immersion to the copper wiring surface in a copper surface treatment liquid or the spraying to the copper wiring surface by a copper surface treatment liquid is simple and reliable, and preferable. In addition, what is necessary is just to make a copper 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 copper 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 copper wiring during processing, it can be applied to isolated wiring parts.

  A known material can be selected and used for the insulating resin layer provided on the copper 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 treatment of the copper wiring surface with the copper surface treatment liquid according to the present invention, the copper wiring surface treated with the copper surface treatment liquid is preferably treated with a coupling agent before the formation of the insulating resin layer. In this way, the mercapto group or amino group that does not participate in the reaction with the copper of the triazine thiol on the copper surface reacts with the coupling agent, and further the functional group of the coupling agent reacts with the insulating resin, so that only the triazine thiol is reacted. Then, a high adhesive force can be obtained even for 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.

  The laminate obtained by treating the copper wiring surface with the copper surface treatment liquid according to the present invention often has a plurality of combinations of copper 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), electroplated copper 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), surface treatment is performed with the copper 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 treatment surface is washed with an appropriate liquid such as water, the triazine compound 6 according to the present invention remains only on the wiring (copper plating portion).

  Thereafter, as shown in FIG. 1 (7), if the silane coupling agent treatment is performed on the wiring surface to form the silane coupling agent layer 7, the adhesion strength can be further increased. 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 or a method of applying a liquid resin 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. All examples were performed in an air atmosphere.
[Example 1]
2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Kasei Co., Ltd.) and acetic acid were mixed with water and stirred for 1 hour. The latter produced a copper surface treatment solution of 1% by weight. The pH of this copper surface treatment solution was 3.5.

  An electroplated copper foil having a thickness of 35 μm was immersed in the copper surface treatment solution at room temperature for 5 minutes, washed with water, baked at 100 ° C. for 30 minutes, and dried. It was confirmed by Auger electron spectroscopy that the triazine compound remained on the copper foil.

  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 under conditions of 150 ° C. and 1 MPa for 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 as the adhesion. A peel strength equal to 0.8 kgf / cm (converted value is 0.078 MPa · cm), which is the same as the adhesion in the anchor effect by the existing surface roughening, was obtained.
[Example 2]
2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Kasei Co., Ltd.) and acetic acid were mixed with water and stirred for 1 hour. The latter produced a copper surface treatment solution of 1% by weight. The pH of this copper surface treatment solution was 3.5.

  An electroplated copper foil having a thickness of 35 μm was immersed in this copper surface treatment solution at room temperature for 5 minutes, washed with water, and 1% by weight of γ-aminopropyltriethoxysilane (silane coupling agent). , KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) and immersed in an aqueous solution for 5 minutes, washed with water, then baked at 100 ° C. for 30 minutes and dried to carry out a coupling agent treatment.

  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 under conditions of 150 ° C. and 1 MPa for 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. By further using a silane coupling agent for the triazine thiol compound, 1.0 kgf / cm (converted value was 0.098 MPa · cm), which was higher peel strength than Example 1, was obtained.
[Example 3]
Carbon dioxide gas was added at a pressure of 0.1 MPa for 5 minutes in a 0.1 wt% aqueous solution of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Kasei). After blowing, the mixture was stirred for 1 hour to prepare a copper surface treatment liquid. The pH of this copper surface treatment solution was 5.5.

  A 35 μm-thick electroplated copper foil was immersed in this copper surface treatment solution at room temperature for 5 minutes, washed with water, then baked at 100 ° C. for 30 minutes and dried, and the same coupling agent as in Example 2 Processed.

  It piled up so that the thermosetting epoxy resin sheet of a semi-hardened state (B stage) might touch the treated surface, and it pressed at 150 ° C, 1 MPa, and 5 minutes with the vacuum press. 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 equal to 0.8 kgf / cm and the close contact with the existing anchor effect was obtained.
[Comparative Example 1]
Using an aqueous solution containing 1% by weight of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, manufactured by Sankyo Kasei) whose pH was adjusted to 8.5, A 35 μm thick electroplated copper foil was immersed at room temperature for 5 minutes, washed with water, then baked at 100 ° C. for 30 minutes and dried.

  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 under conditions of 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.

  The copper foil was cut into a 1 cm width, and the peel strength was measured. A peel strength of 0.5 kgf / cm was obtained.

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

(Appendix 1)
At least one compound selected from the group consisting of triazine thiol and its derivatives represented by the following formula (1):

（式（１）中、ＸはＮＲ_２またはＳＡであり、ＮＲ_２中のＲは、互いに独立に水素、メチル基、エチル基、n―プロピル基、イソプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチル基または置換基を有していてもよいフェニル基であり、Ａは、互いに独立に、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る。）
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と
を含んでなる銅表面処理液。

(In the formula (1), X is NR ₂ or SA, and R in NR ₂ is independently of each other hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl. group, a phenyl group which may have a t- butyl group or a substituent, a is, independently of one another, hydrogen, NH _4, lithium, sodium, potassium, rubidium or cesium.)
A copper surface treatment liquid comprising at least one acid selected from the group consisting of an organic acid and carbonic acid.

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

(Appendix 3)
The copper surface treatment solution according to appendix 1 or 2, comprising at least one of water and alcohol.

(Appendix 4)
The copper surface treatment liquid according to any one of appendices 1 to 3, which is a treatment liquid for improving adhesion between the copper surface and the insulating resin.

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

(Appendix 6)
In the manufacturing method of the laminate having the insulating resin layer in contact with the copper wiring layer,
Treating the copper wiring surface with the copper surface treatment liquid according to any one of appendices 1 to 5, and forming the insulating resin layer thereon;
A manufacturing method of a layered product.

(Appendix 7)
The laminate according to appendix 6, wherein the treatment of the copper wiring surface with the copper surface treatment liquid is immersion of the copper wiring surface in the copper surface treatment liquid or spraying on the copper wiring surface with the copper surface treatment liquid. Manufacturing method.

(Appendix 8)
Supplementary note 6 or 7, wherein the copper wiring surface treated with the copper surface treatment liquid is treated with a silane coupling agent after the treatment of the copper wiring surface with the copper surface treatment liquid and before the formation of the insulating resin layer. The manufacturing method of the laminated body.

(Appendix 9)
The insulating resin layer is composed 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 method for producing a laminate according to any one of appendices 6 to 8, which comprises at least one resin selected from the group consisting of:

(Appendix 10)
A laminated body having an insulating resin layer in contact with a copper wiring layer, wherein the copper wiring surface is treated with the copper surface treatment liquid according to any one of appendices 1 to 5, and the insulating resin layer is formed thereon. A laminated body.

(Appendix 11)
The laminate according to appendix 10, wherein the treatment of the copper wiring surface with the copper surface treatment liquid is immersion of the copper wiring surface in the copper surface treatment liquid or spraying on the copper wiring surface with the copper surface treatment liquid. .

(Appendix 12)
Additional treatment 10 or 11 wherein the copper wiring surface treated with the copper surface treatment liquid is treated with a silane coupling agent after the treatment of the copper wiring surface with the copper surface treatment liquid and before the formation of the insulating resin layer. The laminated body as described in.

(Appendix 13)
The laminate according to any one of appendices 10 to 12, wherein the laminate is a semiconductor integrated circuit device having a multilayer wiring structure.

(Appendix 14)
The insulating resin layer is composed 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 supplementary notes 10 to 13, comprising at least one resin selected from the group consisting of:

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 Electroplated copper 6 Triazine compound 7 Silane coupling agent layer 8 Insulating resin layer

Claims (5)

At least one compound selected from the group consisting of triazine thiol and its derivatives represented by the following formula (1):

(In the formula (1), X is NR ₂ or SA, and R in NR ₂ is independently of each other hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl. A group, a t-butyl group or an optionally substituted phenyl group, and A is independently of each other hydrogen, NH ₄ , lithium, sodium, potassium, rubidium or cesium.)
A copper surface treatment liquid comprising at least one acid selected from the group consisting of an organic acid and carbonic acid. In the manufacturing method of the laminate having the insulating resin layer in contact with the copper wiring layer,
The copper wiring surface is treated with the copper surface treatment liquid according to claim 1, and the insulating resin layer is formed thereon.
A manufacturing method of a layered product.   The lamination according to claim 2, wherein the treatment of the copper wiring surface with the copper surface treatment liquid is immersion of the copper wiring surface in the copper surface treatment liquid or spraying on the copper wiring surface with the copper surface treatment liquid. Body manufacturing method.   The copper wiring surface treated with the copper surface treatment liquid is treated with a silane coupling agent after the treatment of the copper wiring surface with the copper surface treatment liquid and before the formation of the insulating resin layer. The manufacturing method of the laminated body of description.   A laminate having an insulating resin layer in contact with a copper wiring layer, wherein the copper wiring surface is treated with the copper surface treatment liquid according to claim 1 and the insulating resin layer is formed thereon. .

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