JP6365279B2 - Method for producing metal surface treatment liquid and method for producing laminate - Google Patents

Description

  This case relates to a metal surface treatment liquid, a laminate, and a method for producing the laminate.

  In recent years, miniaturization and multilayering of printed wiring boards and high-density mounting of electronic components have rapidly progressed, and a build-up multilayer wiring structure has been studied for printed wiring boards. In the build-up multilayer wiring structure, copper is applied as a wiring material, and a resin insulating film is applied as an insulating material between wiring layers. By repeatedly laminating these as necessary, a highly integrated multilayer A wiring board is formed.

Adhesion between the wiring material copper and the resin insulating film is low. Therefore, conventionally, adhesion is improved due to the physical anchor effect. That is, the surface of the wiring layer is physically roughened to actively form irregularities, and the resin insulating layer meshes with the irregularities to improve adhesion.
However, in recent years, high-frequency signals have also been transmitted to the build-up wiring board, 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 the uneven wiring structure. Has arisen.

  Therefore, methods other than the physical anchor effect are desired as a method for improving adhesion. In recent years, methods for improving chemical adhesion between copper and constituent components in an insulating resin have been studied.

  For example, methods using various triazine thiols have been proposed (see, for example, Patent Document 1). Specifically, in the proposed technique, a triazine thiol layer is formed on the conductor. However, in this proposed technique, the resin is limited to an ABS resin that can react with triazine thiol.

  Further, a triazine compound and an organic compound capable of reacting or adsorbing with the triazine compound are respectively prepared, and an adhesive layer is formed by sequentially immersing a metal in the triazine compound, and the metal surface and the resin material are interposed through the adhesive layer. The technique which adhere | attaches is proposed (for example, refer patent document 2). However, this proposed technique has a problem that the effect of improving the adhesion cannot be obtained uniformly because of uneven treatment on the metal surface during the immersion treatment of the triazine compound. Moreover, since it is necessary to perform immersion treatment twice, there exists a problem that the number of processes increases.

  Further, a copper surface treatment technique using a compound synthesized in advance from a silane coupling agent having a reactive group with a dry film type resin insulating material and triazine thiol has been proposed (for example, see Patent Document 3). ). However, in recent years, studies on miniaturization of wiring in a build-up multilayer structure have been advanced, and sheet-like dry film materials cannot be applied as resin insulating materials in terms of performance. In the miniaturization study, in place of the dry film, application of a coating type photosensitive material capable of forming a thin film, having high resolution, and having UV functionality is being studied. The main material of the photosensitive material is, for example, a phenol resin. However, in the proposed technique, the adhesion between the insulating resin layer made of the photosensitive material using the phenol resin and the metal wiring layer is improved. There is a problem that you can not.

Japanese Patent Laid-Open No. 10-335782 JP 2007-221099 JP 2007-16105 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, this case is a new metal surface treatment liquid capable of improving the adhesion between the metal wiring layer and the insulating resin layer with a small number of steps, a laminate using the metal surface treatment liquid, and a method for producing the laminate The purpose is to provide.

Means for solving the above-described problems are as described in the following supplementary notes. That is,
The disclosed metal surface treatment liquid is obtained by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2), and contains a triazine derivative having a siloxane bond.
However, the general formula (1), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium.
However, In the general formula (2), ^{R 1} represents an alkyl group having 1 to 3 carbon atoms, ^{R 2} is an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, It represents any of a methacryloxy group, an acryloxy group, and an alkyl-substituted amino group, m represents an integer of 1 to 5, and n represents an integer of 1 to 2.

The disclosed laminate has a metal wiring layer and an insulating resin layer,
The insulating resin layer is formed on the metal wiring via an adhesion layer obtained by applying the disclosed metal surface treatment liquid.

The manufacturing method of the disclosed laminate is as follows:
On the metal wiring layer, applying the disclosed metal surface treatment liquid to form an adhesion layer;
Forming an insulating resin layer on the adhesion layer;
including.

According to the disclosed metal surface treatment solution, a new metal that can solve the above-described problems and can achieve the above-described object and can improve the adhesion between the metal wiring layer and the insulating resin layer with a small number of steps. A surface treatment liquid can be provided.
According to the disclosed laminate, the conventional problems can be solved and the object can be achieved, and a laminate with improved adhesion between the metal wiring layer and the insulating resin layer can be obtained with fewer steps.
According to the disclosed method for manufacturing a laminate, the conventional problems can be solved, the object can be achieved, and a laminate with improved adhesion between a metal wiring layer and an insulating resin layer can be produced with fewer steps. can do.

FIG. 1A is a schematic cross-sectional view (No. 1) for explaining an example of a build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1B is a schematic cross-sectional view (No. 2) for explaining an example of manufacturing a build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1C is a schematic cross-sectional view (part 3) for explaining an example of manufacturing a build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1D is a schematic cross-sectional view (part 4) for explaining an example of manufacturing a build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1E is a schematic cross-sectional view (No. 5) for explaining an example of the build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1F is a schematic cross-sectional view (No. 6) for explaining an example of a build-up multilayer circuit board using the disclosed metal surface treatment liquid. FIG. 1G is a schematic cross-sectional view (No. 7) for explaining an example of manufacturing a build-up multilayer circuit board using the disclosed metal surface treatment liquid.

(Metal surface treatment liquid)
The disclosed metal surface treatment liquid contains at least a triazine derivative, and further contains other components as necessary.

<Triazine derivative>
The triazine derivative is obtained by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2).
The triazine derivative has a siloxane bond (Si—O—Si).

The triazine derivative is different in structure from the triazine derivative described in JP 2007-16105 A in that it has at least the siloxane bond. Further, the triazine derivative has the siloxane bond, so that the effect of further improving the adhesion between the metal wiring layer and the insulating resin layer can be obtained as compared with the triazine derivative described in JP-A-2007-16105. . These are considered to be because the strength of the adhesion layer obtained from the metal surface treatment liquid is increased because the triazine derivative has the siloxane bond.
The details of the metal wiring layer and the insulating resin layer will be described later.

However, the general formula (1), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium.
However, In the general formula (2), ^{R 1} represents an alkyl group having 1 to 3 carbon atoms, ^{R 2} is an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, It represents any of a methacryloxy group, an acryloxy group, and an alkyl-substituted amino group, m represents an integer of 1 to 5, and n represents an integer of 1 to 2.

  Examples of the alkyl group having 1 to 6 carbon atoms in the X of the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and n. -A pentyl group, n-hexyl group, etc. are mentioned.

The alkyl group having 1 to 3 carbon atoms in the R ¹ in the general formula (2), for example, a methyl group, an ethyl group, a n- propyl group.

As the number (4-n) of R ¹ O groups in the general formula (2), 3 is preferable.
Therefore, the n in the general formula (2) is preferably 1.

  It is preferable that the triazine derivative has a silanol group from the viewpoint that adhesion is further improved when the material of the insulating resin layer is a polar resin. Examples of the polar resin include resins having a phenolic hydroxyl group (for example, phenol resin, novolac resin, polyvinyl phenol resin).

The triazine derivative is preferably represented by the following general formula (3) from the viewpoint of excellent adhesion.
However, the in general formula (3), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium, ^{R 2} is Each independently represents an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, a methacryloxy group, an acryloxy group, or an alkyl-substituted amino group, and m is an integer of 1 to 5 P represents an integer of 1 or more.

  The p is not particularly limited as long as it is an integer of 1 or more, and can be appropriately selected according to the purpose.

Examples of the alkyl group in the alkyl-substituted amino group of R ^{2 in} the general formula (2) and the general formula (3) include an alkyl group having 1 to 3 carbon atoms.

In the general formula (2) and the general formula (3), R ² represents an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, a methacryloxy group, an acryloxy group, and an alkyl-substituted amino group. Any group is not particularly limited and may be appropriately selected according to the purpose. However, it is preferably selected according to the main material structure of the insulating resin layer.
For example, when the main material of the insulating resin layer is a phenol resin, R ² is preferably any one of an amino group, a mercapto group, a glycidyl group, an isocyanate group, and a ureido group.
When the main material of the insulating resin layer is an epoxy resin, the R ² is preferably any of an amino group, a mercapto group, a glycidyl group, and an isocyanate group.
When the main material of the insulating resin layer is an unsaturated polyester resin, R ² is preferably any one of a glycidyl group, a vinyl group, a methacryloxy group, and an acryloxy group.

In the general formula (2) and the general formula (3), m is preferably 2 or 3 in terms of reactivity due to steric hindrance and water solubility of each compound. Above all, the general formula (2) and the formula in (3) - _{(CH 2) m} - is 1,2-ethylene, 1,3-propylene group are preferred.

<< Synthesis Method of Triazine Derivative >>
The triazine derivative is obtained by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2).
The reaction is usually performed in a liquid.
The liquid preferably contains water.
The water in the liquid hydrolyzes the compound represented by the general formula (2).

There is no restriction | limiting in particular as temperature in the said reaction, According to the objective, it can select suitably, For example, 20-30 degreeC etc. are mentioned.
There is no restriction | limiting in particular as time of the said reaction, According to the objective, it can select suitably, For example, 1 hour-3 hours etc. are mentioned.

  In the reaction, the liquid preferably contains at least one of methanol and ethanol in addition to the water. The methanol and the ethanol control the rate of the reaction.

When the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted in the liquid, the general formula (1) is added to the liquid. It is preferable that the compound represented by the said general formula (2) satisfy | fills the following formula | equation (1).
A1 × A2> B1 × B2 (1)
Here, the A1 represents the number of moles of the compound represented by the general formula (1). Said A2 represents the number of substituents other than the alkyl group and phenyl group in three X of the compound represented by the said General formula (1). B1 represents the number of moles of the compound represented by the general formula (2). B2 represents (4-n) in the compound represented by the general formula (2).

  By adding the compound represented by the general formula (1) and the compound represented by the general formula (2) to the liquid under the condition satisfying the formula (1), the general formula (3) ) Can be efficiently obtained.

On the condition that the formula (1) does not hold (left side ≦ right side), a plurality of —SX groups in one molecule of the compound represented by the general formula (1) are the compounds represented by the general formula (2). Since it reacts with Si and the reactivity of the resulting triazine derivative to the metal surface is impaired, the original effect of improving the adhesion between the metal wiring layer and the insulating resin layer may not be obtained.
On the other hand, on the condition that the right side is very small (left term >> right term), the reaction amount between the functional group R ² of the compound represented by the general formula (2) and the insulating resin layer is insufficient. Similarly, the effect of improving the adhesion between the metal wiring layer and the insulating resin layer, which is the original purpose, may not be obtained.

  When the compound represented by the general formula (1) and the compound represented by the general formula (2) are added to the liquid, the molar ratio (the compound represented by the general formula (1): The compound represented by formula (2) preferably satisfies 3: 2 to 10: 1.

  There is no restriction | limiting in particular as content of the said triazine derivative in the said metal surface treatment liquid, Although it can select suitably according to the objective, Of the compound represented by the said General formula (1) added to the said liquid The concentration is preferably 0.0001 mol / L to 1 mol / L, more preferably 0.001 mol / L to 0.1 mol / L, and particularly preferably 0.005 mol / L to 0.05 mol / L.

Confirmation of the structure of the triazine derivative (particularly the structure represented by the general formula (3)) can be performed by NMR ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR) or the like.

  The metal surface treatment liquid preferably contains water. This water may be water existing in the system when the triazine derivative is obtained, or may be water added separately.

<Other ingredients>
Examples of the other components include alcohol.

  As said alcohol, C1-C3 alcohol etc. are mentioned, for example. As the alcohol, methanol and ethanol are preferable. These improve the applicability of the metal surface treatment liquid and contribute to the formation of a uniform adhesion layer.

  There is no restriction | limiting in particular as content of the said alcohol, Although it can select suitably according to the objective, 0.1 mass%-50 mass% are preferable, 0.5 mass%-10 mass are more preferable, 1 Mass% to 5 mass% is particularly preferable.

(Laminated body and manufacturing method thereof)
The disclosed laminate includes at least a metal wiring layer, an adhesion layer, and an insulating resin layer, and further includes other members as necessary.
The disclosed laminate manufacturing method includes at least a step of forming an adhesion layer and a step of forming an insulating resin layer, and further includes other steps as necessary.

  The laminate can be manufactured by the method for manufacturing the laminate, the adhesion layer can be produced by a step of forming the adhesion layer, and the insulating resin layer is produced by a step of forming the insulating resin layer. it can.

<Metal wiring layer>
The metal wiring layer is not particularly limited as long as it is a layer having metal wiring, and can be appropriately selected according to the purpose. For example, an insulating base and a metal wiring on the insulating base A metal wiring layer having

<< Insulating base material >>
Examples of the material for the insulating substrate include polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, phenol resin, novolac resin, acrylic resin, methacrylic resin, polyphenylene ether resin, polyphenylene oxide resin, and olefin resin. , Fluorine-containing resins, liquid crystal polymers, polyetherimide resins, polyetheretherketone resins, and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a shape, a magnitude | size, and a structure of the said insulating base material, According to the objective, it can select suitably.

<< Metal wiring >>
There is no restriction | limiting in particular as a material of the said metal wiring, According to the objective, it can select suitably, For example, gold | metal | money, silver, copper etc. are mentioned. Among these, copper is preferable.

  There is no restriction | limiting in particular as a shape, a magnitude | size, and a structure of the said metal wiring, According to the objective, it can select suitably.

  For example, the metal wiring is patterned (wiring) on a metal layer produced by a method such as electroless plating, electrolytic plating, vapor deposition, sputtering, or damascene on the insulating base material. Obtained).

<Adhesion layer and step of forming adhesion layer>
The adhesion layer is obtained by applying the disclosed metal surface treatment liquid on the metal wiring.
The step of forming the adhesion layer is a step of applying the disclosed metal surface treatment liquid on the metal wiring to form the adhesion layer.

  The adhesion layer may be formed on the entire surface of the metal wiring layer, or may be formed only on the metal wiring of the metal wiring layer. That is, the adhesion layer only needs to be formed on at least the metal wiring of the metal wiring layer.

  There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, a dipping method, a spray method, a spin coat method etc. are mentioned. Among these, the immersion method is preferable in that the amount of the metal surface treatment liquid consumed is small and the adhesion layer can be formed uniformly.

  After the application, it is preferable to perform a drying treatment.

<< Dipping method >>
The immersion method is a method of immersing the metal wiring layer in the metal surface treatment solution. At the time of the immersion, the metal wiring layer may be stationary in the metal surface treatment liquid or may be swung.

There is no restriction | limiting in particular as said immersion time, Although it can select suitably according to the objective, 5 seconds-180 seconds are preferable, and 10 seconds-60 seconds are more preferable. If the time is less than 5 seconds, the formation of the adhesion layer may be insufficient, and if the time exceeds 180 seconds, it may become inefficient due to excessive process time.
There is no restriction | limiting in particular as temperature of the said metal surface treatment liquid in the case of the said immersion, It can select suitably according to the objective, 20 degreeC-30 degreeC etc. are mentioned.

After the immersion, it is preferable to perform a rinsing treatment with water or water containing at least one of methanol and ethanol. Since it is necessary to clean the surface as efficiently as possible, the rinsing treatment is preferably performed with running water, a large amount of pool water, a circulated water bath, or the like.
There is no restriction | limiting in particular as time of the said rinse process, Although it can select suitably according to the objective, 10 seconds-600 seconds are preferable, and 30 seconds-400 seconds are more preferable. If the time is less than 10 seconds, a sufficient rinsing process may not be performed. If the time exceeds 600 seconds, the process time may be exceeded, resulting in inefficiency.

<< Spray method and spin coating method >>
In the spray method and the spin coating method, the metal surface treatment liquid is processed so as to come into contact with the surface of the metal wiring layer by the respective methods. It is desirable to optimize the conditions so that they are uniformly processed according to the processing method of each processing apparatus.
After the treatment by the spray method and the spin coating method, the rinsing treatment is preferably performed as in the immersion method. The rinse treatment may be performed by an immersion method, a spray method, or a spin coating method.

<< Drying process >>
The drying treatment can be expected to have an effect of removing moisture by the rinsing treatment, removing an organic solvent, and stabilizing the adhesion layer.
There is no restriction | limiting in particular as temperature of the said drying process, Although it can select suitably according to the objective, 60 to 150 degreeC is preferable and 80 to 110 degreeC is more preferable.
There is no restriction | limiting in particular as time of the said heat processing, Although it can select suitably according to the objective, 30 seconds-1,000 seconds are preferable and 400 seconds-800 seconds are more preferable.

<Process for forming insulating resin layer and insulating resin layer>
The insulating resin layer is formed on the metal wiring via the adhesion layer.

  Examples of the material of the insulating resin layer include polyimide resin, epoxy resin, bismaleimide resin, maleimide resin, cyanate resin, phenol resin, novolac resin, acrylic resin, methacrylic resin, polyphenylene ether resin, polyphenylene oxide resin, olefin resin, Fluorine-containing resins, liquid crystal polymers, polyetherimide resins, polyetheretherketone resins and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as average thickness of the said insulating resin layer, Although it can select suitably according to the objective, 1 micrometer-100 micrometers are preferable, and 2 micrometers-20 micrometers are more preferable.

  The step of forming the insulating resin layer is not particularly limited as long as it is a step of forming an insulating resin layer on the adhesion layer, and can be appropriately selected according to the purpose. The process etc. which apply | coat the coating liquid containing the material to comprise on the said metal wiring layer in which the said contact | adherence layer was formed are mentioned. The application method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray coating method and a spin coating method.

Heat treatment is preferably performed after the coating.
There is no restriction | limiting in particular as temperature in the said heat processing, Although it can select suitably according to the objective, 150 to 300 degreeC is preferable and 200 to 250 degreeC is more preferable.
There is no restriction | limiting in particular as time in the said heat processing, Although it can select suitably according to the objective, 1 minute-5 hours are preferable, and 30 minutes-2 hours are more preferable.
There is no restriction | limiting in particular as atmosphere in the said heat processing, Although it can select suitably according to the objective, Inert gas atmosphere is preferable. Examples of the inert gas include nitrogen gas.

After the application and before the heat treatment, a baking treatment for drying or the like may be performed.
The baking temperature is preferably 90 ° C to 130 ° C.
The baking time is preferably 1 minute to 5 minutes.

The adhesion layer in the laminate includes, for example, NMR ( ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR), Auger analysis, X-ray microanalyzer (XMA) analysis, X-ray photoelectron spectrometer (XPS), This can be confirmed by FT-IR analysis or the like.

  Hereinafter, a method for forming a build-up multilayer circuit board using the disclosed metal surface treatment liquid will be exemplarily described with reference to FIGS. 1A to 1G.

  First, as shown in FIG. 1A, an insulating base material 2 is formed on a glass fiber reinforced resin substrate 1 on which a circuit is formed. The surface of the insulating substrate 2 is subjected to a surface roughening treatment for obtaining adhesion. Thereafter, the metal layer 3 is formed on the surface of the insulating substrate 2 by electroless plating or sputtering.

  Next, as shown in FIG. 1B, a resist 4 is formed by patterning.

  Next, as shown in FIG. 1C, an electroplating metal 5 to be a metal wiring is grown in the opening.

  Next, as shown in FIG. 1D, after the resist 4 is peeled off, the metal layer 3 is removed by etching as shown in FIG. 1E.

  Next, as shown in FIG. 1F, surface treatment is performed with the disclosed metal surface treatment liquid. As the surface 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 adhesion layer 6 remains only on the electroplated metal 5 (metal wiring).

  Next, as shown in FIG. 1G, an insulating resin layer 7 as the next layer is formed. The insulating resin layer 7 can be formed by a known method such as a method of applying a resin varnish containing a solvent.

  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.

  Examples of the disclosed technology will be described below, but the disclosed technology is not limited to the following examples.

  In the following examples, the compound represented by the general formula (1) may be referred to as a triazine compound, and the compound represented by the general formula (2) may be referred to as a silane coupling agent. There is.

Example 1
<Preparation of metal surface treatment solution>
2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Chemical Co., Ltd., triazine compound) 0.02 mol and γ-aminopropyltrimethoxysilane (KBM) -903, manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent) 0.01 mol in a 1 L liquid of water: methanol = 98: 2 (mass ratio), stirred for 2 hours, and metal surface treatment solution 1 Got.
In the obtained metal surface treatment solution, the compound represented by the general formula (3) is present. This is also true for Examples 2-7.

<Production of laminate>
A substrate on which plated copper (assuming copper wiring) was formed was immersed in the obtained metal surface treatment solution 1 for 45 seconds. Thereafter, rinsing was performed with running water for 300 seconds. Furthermore, the drying process was performed for 600 second in 80 degreeC oven, and the contact | adherence layer was formed on the metal wiring layer.
Next, a resin insulating material mainly composed of a phenol resin is applied to the surface subjected to the metal surface treatment by a spin coating method, and baked on a 110 ° C. hot plate for 2 minutes to form an insulating resin layer having an average thickness of 5 μm. Formed. Further, thermosetting treatment was performed in a 230 ° C. nitrogen atmosphere oven for 1 hour, an insulating resin layer was formed on the metal wiring layer via an adhesion layer, and a laminate was obtained.

(Example 2)
<Preparation of metal surface treatment solution>
In Example 1, except that the silane coupling agent was replaced with 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), a metal surface treatment solution was prepared in the same manner as in Example 1. 2 was prepared.

<Production of laminate>
In the obtained metal surface treatment liquid 2, a substrate on which plated copper (assuming copper wiring) was formed was immersed for 45 seconds. Thereafter, rinsing was performed with running water for 300 seconds. Furthermore, the drying process was performed for 600 second in 80 degreeC oven, and the contact | adherence layer was formed on the metal wiring layer.
Next, a resin insulating material mainly composed of an epoxy resin is applied to the surface subjected to the metal surface treatment by spin coating, and baked for 2 minutes on a 110 ° C. hot plate to form an insulating resin layer having an average thickness of 5 μm. Formed. Further, thermosetting treatment was performed in a 230 ° C. nitrogen atmosphere oven for 1 hour, an insulating resin layer was formed on the metal wiring layer via an adhesion layer, and a laminate was obtained.

(Examples 3 to 4)
<Preparation of metal surface treatment liquid and production of laminate>
In Example 2, the amount of the triazine compound, the type of the silane coupling agent, and the amount of the silane coupling agent were changed as shown in Table 1, and in the same manner as in Example 2, the metal surface treatment solution 3 ~ 4 were prepared.
Further, a laminate was produced in the same manner as in Example 2.

(Examples 5-7)
<Preparation of metal surface treatment liquid and production of laminate>
Example 1 The same as Example 1 except that the type of triazine compound, the amount of triazine compound, the type of silane coupling agent, the amount of silane coupling agent, and the solvent composition were changed as shown in Table 1. Thus, metal surface treatment solutions 5 to 7 were prepared.
Furthermore, a laminate was produced in the same manner as in Example 1.

(Comparative Example 1)
<Production of laminate>
A resin insulation material mainly composed of phenol resin is applied to the surface of the substrate on which plated copper (assuming copper wiring) is formed by spin coating, and baked on a hot plate at 110 ° C. for 2 minutes, with an average thickness of 5 μm. An insulating resin layer was formed. Further, thermosetting treatment was performed in a 230 ° C. nitrogen atmosphere oven for 1 hour, an insulating resin layer was formed on the metal wiring layer, and a laminate was obtained.

(Comparative Example 2)
<Preparation of metal surface treatment solution>
0.04 mol of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Chemical Co., Ltd.) was dissolved in 1 L of water, stirred for 2 hours, and the metal surface A treatment liquid 8 was obtained.

<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the metal surface treatment solution 1 was replaced with the metal surface treatment solution 8 in Example 1.

(Comparative Example 3)
<Preparation of metal surface treatment solution>
0.01 mol of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 1 L of water and stirred for 2 hours to obtain a metal surface treatment solution 9.

<Production of laminate>
A laminate was obtained in the same manner as in Example 1 except that the metal surface treatment solution 1 was replaced with the metal surface treatment solution 9 in Example 1.

(Comparative Example 4)
<Preparation of metal surface treatment solution>
0.04 mol of 2,4,6-trimercapto-1,3,5-triazine monosodium salt (Sunthiol N-1, Sankyo Chemical Co., Ltd.) was dissolved in 1 L of water, stirred for 2 hours, and the metal surface A treatment liquid 10-1 was obtained.
0.01 mol of γ-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 1 L of water and stirred for 2 hours to obtain a metal surface treatment solution 10-2.

<Production of laminate>
A substrate on which plated copper (assuming copper wiring) was formed was immersed in the obtained metal surface treatment solution 10-1 for 45 seconds. Thereafter, rinsing was performed with running water for 300 seconds. Furthermore, the drying process was performed for 600 second in 80 degreeC oven. Subsequently, the board | substrate which formed the plated copper which assumed said copper wiring in the obtained metal surface treatment liquid 10-2 was immersed for 45 seconds. Thereafter, rinsing was performed with running water for 300 seconds. Furthermore, the drying process was performed for 600 second in 80 degreeC oven. Thus, an adhesion layer was formed on the metal wiring layer.
Next, a resin insulating material mainly composed of a phenol resin is applied to the surface subjected to the metal surface treatment by a spin coating method, and baked on a 110 ° C. hot plate for 2 minutes to form an insulating resin layer having an average thickness of 5 μm. Formed. Further, thermosetting treatment was performed in a 230 ° C. nitrogen atmosphere oven for 1 hour, an insulating resin layer was formed on the metal wiring layer via an adhesion layer, and a laminate was obtained.

<Evaluation>
The following evaluation was performed. The results are shown in Table 1.

<< Peel Strength >>
Peel strength measurement was performed when a force gauge (DPX-5TR, made by IMADA) installed on a 90 ° peel tester (made by Nisshin Kagaku) was used as a measuring device and peeled off at a speed of about 50 mm / min. This was done by measuring the peel strength of the film.
The evaluation sample was produced by the following method.
In the production of the laminates of the examples and comparative examples, a substrate on which plated copper (assuming copper wiring) was formed was used as a CCL substrate in which Cu plating was formed on a peelable Cu foil (epoxy substrate such as glass cloth) A laminated body was produced in the same manner as in each Example and each Comparative Example, except that it was changed to a laminated substrate for a printed circuit board that was impregnated with an insulating resin such as and laminated with copper foil laminated. Further, a CCL substrate (transfer substrate) was bonded using a thermosetting dry film and peeled off at the peelable Cu foil interface to obtain an evaluation sample.

<< study pull intensity >>
The tensile strength when the evaluation sample was pulled in the vertical direction was measured.
The measurement was performed using a Sebastian test apparatus (Sebastian V type, quad group), a tensile speed of 2.12 kgf / sec, and 14 samples.
The evaluation sample was produced by the following method.
In the production of the laminated body of each example and each comparative example, a substrate on which plated copper (assuming copper wiring) was formed was formed on a substrate for evaluation (on a Si substrate with an oxide film, Ti and Cu seeds were further formed. A laminate was produced in the same manner as in the examples and comparative examples, except that the substrate was changed to a 2 μm Cu-plated substrate. Furthermore, a stud pin (2.7 mm in diameter, 901106 type, manufactured by Phototechnica, with epoxy adhesive) is attached on the insulating resin layer of the laminate, and the adhesive is cured by atmospheric heating at 150 ° C. for 1 hour for evaluation. A sample was obtained.

TT-Na: 2,4,6-trimercapto-1,3,5-triazine monosodium salt, manufactured by Sankyo Kasei Co., Ltd. TT: 2,4,6-trimercapto-1,3,5-triazine, three KBM-903: γ-aminopropyltrimethoxysilane KBM-403: 3-glycidoxypropyltrimethoxysilane KBM-803: 3-mercaptopropyltrimethoxysilane KBE-585: 3-ureidopropyltriethoxy Silane KBM-5103: 3-acryloxypropyltrimethoxysilane KBM-903, KBM-403, KBM-803, KBE-585, and KBM-5103 are all manufactured by Shin-Etsu Chemical Co., Ltd.

Examples 1-7 were excellent in both peel strength and stud pull.
In Comparative Examples 1 to 3, both the peel strength and the stud pull were inferior to those of Examples 1 to 7.
In Comparative Example 4, the peel strength and stud pull were similar to those in Examples 1 to 7, but two steps were required to form the adhesion layer.

Regarding the above embodiment, the following additional notes are disclosed.
(Additional remark 1) It is obtained by making the compound represented by the following general formula (1) react with the compound represented by the following general formula (2), It contains the triazine derivative which has a siloxane bond, It is characterized by the above-mentioned. Metal surface treatment solution.
However, the general formula (1), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium.
However, In the general formula (2), ^{R 1} represents an alkyl group having 1 to 3 carbon atoms, ^{R 2} is an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, It represents any of a methacryloxy group, an acryloxy group, and an alkyl-substituted amino group, m represents an integer of 1 to 5, and n represents an integer of 1 to 2.
(Supplementary note 2) The metal surface treatment solution according to supplementary note 1, wherein R ² is any one of an amino group, a mercapto group, a glycidyl group, a ureido group, a methacryloxy group, and an acryloxy group.
(Supplementary note 3) The metal surface treatment liquid according to any one of supplementary notes 1 and 2, wherein the reaction is performed in a liquid containing water.
(Supplementary Note 4) In the liquid, when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted, the general formula is added to the liquid. The metal surface treatment liquid according to supplementary note 3, wherein the compound represented by (1) and the compound represented by the general formula (2) satisfy the following formula (1):
A1 × A2> B1 × B2 (1)
Here, the A1 represents the number of moles of the compound represented by the general formula (1). Said A2 represents the number of substituents other than the alkyl group and phenyl group in three X of the compound represented by the said General formula (1). B1 represents the number of moles of the compound represented by the general formula (2). B2 represents (4-n) in the compound represented by the general formula (2).
(Supplementary Note 5) When the compound represented by the general formula (1) and the compound represented by the general formula (2) are added to the liquid, a molar ratio (represented by the general formula (1)). And the metal surface treatment liquid according to any one of supplementary notes 3 to 4, wherein the compound is a compound represented by the general formula (2)) and satisfies 3: 2 to 10: 1.
(Supplementary note 6) The metal surface treatment liquid according to any one of supplementary notes 1 to 5, wherein the triazine derivative has a silanol group.
(Supplementary note 7) The metal surface treatment liquid according to any one of supplementary notes 1 to 6, wherein the triazine derivative is represented by the following general formula (3).
However, the in general formula (3), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium, ^{R 2} is Each independently represents an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, a methacryloxy group, an acryloxy group, or an alkyl-substituted amino group, and m is an integer of 1 to 5 P represents an integer of 1 or more.
(Supplementary Note 8) In the liquid, when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted, the liquid further contains methanol and ethanol. The metal surface treatment liquid according to any one of supplementary notes 3 to 7, which contains at least one of them.
(Additional remark 9) It has a metal wiring layer and an insulating resin layer,
A laminated body, wherein the insulating resin layer is formed on an adhesive layer obtained by applying the metal surface treatment liquid according to any one of appendices 1 to 8 on the metal wiring.
(Additional remark 10) The laminated body of Additional remark 9 in which the said metal wiring layer has an insulating base material and a metal wiring on the said insulating base material.
(Additional remark 11) The laminated body in any one of Additional remark 9 to 10 in which the said insulating resin layer contains either a phenol resin and an epoxy resin.
(Additional remark 12) The process of apply | coating the metal surface treatment liquid in any one of Additional remark 1 to 8 on a metal wiring layer, and forming an adhesion layer,
Forming an insulating resin layer on the adhesion layer;
The manufacturing method of the laminated body characterized by including.
(Additional remark 13) The manufacturing method of the laminated body of Additional remark 12 in which the said metal wiring layer has an insulating base material and a metal wiring on the said insulating base material.
(Additional remark 14) The manufacturing method of the laminated body in any one of Additional remark 12 to 13 in which the said insulating resin layer contains either a phenol resin and an epoxy resin.

DESCRIPTION OF SYMBOLS 1 Glass fiber reinforced resin board | substrate 2 Insulating base material 3 Metal layer 4 Resist 5 Electroplating metal 6 Adhesion layer 7 Insulating resin layer

Claims (8)

A method for producing a metal surface treatment liquid containing a triazine derivative having a siloxane bond,
A method for producing a metal surface treatment liquid comprising reacting a compound represented by the following general formula (1) with a compound represented by the following general formula (2) to obtain the triazine derivative having the siloxane bond : .
However, the general formula (1), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium.
However, In the general formula (2), ^{R 1} represents an alkyl group having 1 to 3 carbon atoms, ^{R 2} is an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, It represents any of a methacryloxy group, an acryloxy group, and an alkyl-substituted amino group, m represents an integer of 1 to 5, and n represents an integer of 1 to 2. The method for producing a metal surface treatment liquid according to claim 1, wherein the reaction is performed in a liquid containing water. When the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted in the liquid, the general formula (1) is added to the liquid. The manufacturing method of the metal surface treatment liquid of Claim 2 with which the compound represented and the compound represented by the said General formula (2) satisfy | fill the following formula | equation (1).
A1 × A2> B1 × B2 (1)
Here, the A1 represents the number of moles of the compound represented by the general formula (1). Said A2 represents the number of substituents other than the alkyl group and phenyl group in three X of the compound represented by the said General formula (1). B1 represents the number of moles of the compound represented by the general formula (2). B2 represents (4-n) in the compound represented by the general formula (2). The method for producing a metal surface treatment liquid according to claim 1, wherein the triazine derivative has a silanol group. The method for producing a metal surface treatment liquid according to any one of claims 1 to 4, wherein the triazine derivative is represented by the following general formula (3).
However, the in general formula (3), X independently represents H, NH _4, alkyl group having 1 to 6 carbon atoms, a phenyl group, lithium, sodium, and either potassium, ^{R 2} is Each independently represents an amino group, a mercapto group, a glycidyl group, an imidazole group, an isocyanate group, a ureido group, a vinyl group, a methacryloxy group, an acryloxy group, or an alkyl-substituted amino group, and m is an integer of 1 to 5 P represents an integer of 1 or more. In the liquid, when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted, the liquid further contains at least one of methanol and ethanol. The manufacturing method of the metal surface treatment liquid in any one of Claim 2 to 5 contained. And the metal wiring layer, a method for producing a laminate which have a insulating resin layer,
The insulating resin layer is formed on the metal wiring layer through an adhesion layer obtained by applying a metal surface treatment liquid obtained by the method for producing a metal surface treatment liquid according to any one of claims 1 to 6. method for producing a laminate characterized by be Rukoto. Applying a metal surface treatment liquid obtained by the method for producing a metal surface treatment liquid according to any one of claims 1 to 6 on the metal wiring layer to form an adhesion layer;
Forming an insulating resin layer on the adhesion layer;
The manufacturing method of the laminated body characterized by including.