JP2005109363A - Aluminum plate, its manufacturing method, and aluminum-based printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an aluminum plate which can realize its inline manufacturing and form an accurate pattern in manufacturing an aluminum-based printed wiring board. <P>SOLUTION: A surface layer of the aluminum plate surface-treated for use in the aluminum-based printed wiring board is a triazine dithiol derivative layer, a contact angle thereof is between 40 and 75 degrees, and the triazine dithiol derivative layer is made of an electrolytic polymer of triazine dithiol derivative expressed by formula 1. In formula 1, R is expressed by -N<SP>1</SP>R<SP>1</SP>R<SP>2</SP>, R<SP>1</SP>R<SP>2</SP>indicates an alkyl group or an unsaturated alkyl group, and M indicates a hydrogen atom or an alkyl metal. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a surface-treated aluminum plate used for producing an aluminum-based printed wiring board such as an aluminum conductor printed wiring board and an aluminum core printed wiring board, and a method for producing the same, and in particular, surface treatment with a triazine dithiol derivative, The present invention relates to an aluminum plate on which a thin film that provides a contact angle that can be adhered to the surface is formed, and a method for manufacturing the same.

Conventionally, an aluminum core printed wiring board having an aluminum plate as a core is used for the purpose of flowing a high current that requires heat dissipation characteristics. The aluminum plate is excellent in corrosion resistance and can maintain a metallic luster for a long time. However, aluminum as an element is very active, and it is difficult to exist as a metal in a normal environment. For example, a rolled aluminum material is already in a rolled state and already has a surface oxide film of 1 nm or more. In an environment containing moisture, not an oxide but a hydroxide film may be formed to reduce adhesion.
Therefore, in general, as the surface treatment of the aluminum material, degreasing with an organic solvent or an oxidizing acid or etching with a corrosive acid or alkali is performed after mechanical treatment such as blast polishing or buffing. As a final base treatment, a method of forming an alumite film (porous type anodic oxide film) of several μm to several tens of μm on the material surface in a sulfuric acid bath or a phosphoric acid bath is used. For example, as a surface treatment method of an aluminum plate used for an aluminum-based printed wiring board, a method of cathodic electrolytic treatment of an aluminum plate in a chromic acid aqueous solution containing sulfate ions is known.
JP 2000-22293 A

An aluminum copper-clad board used for an aluminum core printed wiring board will be described with reference to FIG. FIG. 6 is a manufacturing process diagram shown in a sectional view.
An aluminum plate 62 is prepared (FIG. 6A). A drilling process is performed at a required portion of the aluminum plate 62 to form a hole 63, and then a series of adhesion processes from mechanical polishing to base treatment are performed (FIG. 6B). Next, an insulating resin or prepreg 65 and copper foil 66 are overlapped on the perforated aluminum plate surface 64 and a lamination press is performed.

  However, a series of adhesion treatment steps from mechanical polishing to ground treatment in an aluminum surface treatment step of an aluminum copper clad plate is different from a general printed wiring board processing step. In particular, the alumite film treatment process is bad in terms of work environment and global environment, and many are limited to specialists in aluminum plating. For this reason, it is not easy to inline the alumite film treatment process, and the delivery time cannot be shortened. Further, even in the high-precision etching process of the conductor pattern, there is a problem that a difference in etching occurs due to the quality of the alumite film treated plate.

On the other hand, an aluminum-based printed wiring board using a thin aluminum plate cannot be dealt with by the above-described adhesion processing method, and is currently not in practical use. This is because when the thickness of the aluminum plate is 200 μm or less, the aluminum plate is drawn into a curl shape by mechanical treatment. In addition, since the aluminum plate does not have strength (waist) in the base treatment process, dents, bends, scratches, etc. are generated. Therefore, in the production of an aluminum-based printed wiring board, there is a problem that a series of adhesion processing steps from mechanical polishing to ground treatment cannot be used.
In addition, since the alumite film forms a porous anodic oxide film having a thickness of several μm to several tens of μm on the material surface in a sulfuric acid bath or a phosphoric acid bath, variations in etching in the circuit forming process hinder improvement in pattern accuracy.

  Currently, an aluminum core printed wiring board using an aluminum plate with a thickness of 0.5mm to 1.2mm for the core and a copper foil with a thickness of 70μm to 500μm for the conductor is used for machine tools, vending machines, etc. Used in high current circuits and automotive electrical components. In recent years, aluminum core printed wiring boards using copper plates with a thickness of 200 μm to 500 μm have been studied for hybrid cars, electric cars, fuel cell cars, etc. as a substitute for wiring harnesses for automobile interior wiring. However, as described above, it is difficult to put an aluminum-based printed wiring board using an aluminum thin plate into practical use.

  The problem to be solved is that an aluminum plate that can be inlined in the production of an aluminum-based printed wiring board and that can form a high-precision pattern cannot be obtained.

上式において、Ｒは、−ＮＲ¹Ｒ²で表され、Ｒ¹およびＲ²は、アルキル基または不飽和アルキル基を表し、Ｍは水素原子またはアルカリ金属を表す。
また、上記トリアジンジチオール誘導体は、Ｒが異なるトリアジンジチオール誘導体の混合物であり、特に２−ジブチルアミノ−１，３，５−トリアジン−２，４−ジチオールモノソジウム（以下、ＤＢＮと略称する）と２−ジイソオクチルアミノ−１，３，５−トリアジン−２，４−ジチオールモノソジウム（以下、iso-ＤＯＮと略称する）との混合物であることを特徴とする。
また、トリアジンジチオール誘導体の電解重合体が熱処理されてなることを特徴とする。 The present invention is an aluminum plate surface-treated with a triazine dithiol derivative layer for use in an aluminum-based printed wiring board, wherein the surface layer of the surface-treated aluminum plate is a triazine dithiol derivative layer, and the contact angle thereof is It is characterized by 40 to 75 degrees.
The triazine dithiol derivative layer is an electrolytic polymer of a triazine dithiol derivative represented by the following formula (1).

In the above formula, R is represented by —NR ¹ R ² , R ¹ and R ² represent an alkyl group or an unsaturated alkyl group, and M represents a hydrogen atom or an alkali metal.
The triazine dithiol derivative is a mixture of triazine dithiol derivatives having different Rs, particularly 2-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (hereinafter abbreviated as DBN). It is a mixture with 2-diisooctylamino-1,3,5-triazine-2,4-dithiol monosodium (hereinafter abbreviated as iso-DON).
Further, the electrolytic polymer of a triazine dithiol derivative is heat-treated.

The method for producing an aluminum plate of the present invention includes a polymerization step of forming a polymer film on the surface of the aluminum metal plate by electrolytic polymerization of the triazine dithiol derivative represented by the above formula (1), and a heat treatment step of subjecting the polymer film to a heat treatment In the manufacturing method provided with these, it has the adhesiveness improvement process process of a triazine dithiol derivative and an aluminum metal plate as pre-processing of a superposition | polymerization process, It is characterized by the above-mentioned.
In the polymerization step, a supporting electrolyte containing at least one compound of sodium hydroxide, sodium nitrite and sodium carbonate is used.

  The aluminum-based printed wiring board of the present invention is obtained by laminating and bonding the above-described aluminum plate to a prepreg, a thermosetting resin, or a thermoplastic resin.

In the aluminum plate of the present invention, the surface-treated surface layer is a triazine dithiol derivative layer, and the contact angle is 40 to 75 degrees. Excellent heat resistance.
Since the manufacturing method of the aluminum plate of this invention has an adhesive improvement process process as a pre-process of a superposition | polymerization process, it can be made in-line.
Since the aluminum-based printed wiring board of the present invention is obtained by laminating and bonding the above-described aluminum plates, it can be easily applied to an aluminum-based printed wiring board using an aluminum thin plate.

It was found that by using a triazine dithiol derivative, particularly a triazine dithiol derivative represented by the formula (1), the contact angle of the surface can be made 40 degrees to 75 degrees. The present invention is based on such knowledge.
Examples of the aluminum plate that can be used in the present invention include pure aluminum or an aluminum-based alloy material containing at least 60% by weight of aluminum formed into a plate shape.
In high-speed transmission of electrical signals, current flows through the surface conductor within 1 μm from the surface. Therefore, it is desirable that the aluminum metal plate has as many surface irregularities as possible and is close to a mirror surface. The aluminum plate of the present invention can be produced by the method of the present invention to obtain a smooth surface-treated aluminum plate. However, the aluminum plate serving as the substrate has a surface roughness (JIS Ra value) of 0.05 μm or less. preferable. By using an aluminum plate having an Ra value of 0.05 μm or less, the surface roughness of the surface-treated aluminum plate also becomes an Ra value of 0.05 μm or less, and an aluminum-based printed wiring board having optimal characteristics for high-speed transmission of electrical signals can be obtained.
The thickness of the aluminum metal plate that can be used in the present invention is 0.005 to 50 mm. In the present invention, the aluminum metal plate can be applied to a thin aluminum metal plate having a thickness of 0.005 to 0.5 mm.

The triazine dithiol derivative represented by the formula (1) that can be used in the present invention will be described.
R ¹ and R ² represent an alkyl group or an unsaturated alkyl group.
Specific examples of the alkyl group include —CH ₃ , —C ₂ H ₅ , —C ₄ H ₉ , —C ₆ H ₁₃ , —C ₈ H ₁₇ , —C ₁₀ H ₂₁ , —C ₁₂ H ₂₅ , —C _{18 H 37, -C 20 H 41} , -C 22 H 45, include -C ₂₄ H _49.
Examples of unsaturated alkyl _{groups, -CH 2 CH = CH 2,} - (CH 2) 8 CH = CH 2, - (CH 2) 9 CH = CH 2, -C 8 H 16 CH = CHC 8 H ₁₇ is mentioned.

R ¹ and R ² may be the same as or different from each other. In the present invention, a mixture of triazine dithiol derivatives having different R is preferable.
Examples of triazine dithiol derivatives suitable for the present invention are 2-dibutylamino-1,3,5-triazine-2,4-dithiol, 2-diisooctylamino-1,3,5-triazine-2,4. -Dithiols, and mono- or dialkali metal salts of the respective dithiols. A particularly preferred triazine dithiol derivative in the present invention is DBN or iso-DON, more preferably a mixture of DBN and iso-DON.
The mixing ratio of DBN and iso-DON is preferably a molar ratio of DBN: iso-DON = (3: 7) to (7: 3). By using these mixtures, the contact angle of the film formed on the surface of the aluminum metal plate can be made 40 ° to 75 °.
The triazine dithiol derivative can be obtained by a known method, for example, the method described in JP-A No. 11-71357.

Examples of the method for forming the triazine dithiol derivative coating layer on the surface of the metal plate include an electrolytic polymerization method, a vacuum deposition method, and a sputtering method.
In the present invention, an electropolymerization method that easily adjusts the contact angle of the formed film is preferable. The electrolytic polymerization method is, for example, a method in which an aluminum metal plate is immersed in an electrolytic solution composed of a triazine dithiol derivative and an electrolyte, and is electropolymerized using the aluminum metal plate as an anode, thereby generating a triazine dithiol derivative coating layer on the surface of the aluminum metal plate. is there.

  The layer thickness of the triazine dithiol derivative coating layer is preferably 50 to 2000 nm, particularly preferably 100 to 300 nm, and the processing conditions are set so that this coating layer thickness is obtained.

  The triazine dithiol derivative coating layer formed on the surface of the metal plate can be subjected to heat treatment. By the heat treatment, the degree of polymerization of the coating layer increases, or the crosslinking reaction of the unsaturated bond portion occurs, whereby the coating strength can be increased. As heat treatment conditions, the temperature is 100 to 350 ° C., preferably 150 to 200 ° C., and the treatment time is 5 to 600 minutes, preferably 10 to 120 minutes in an air atmosphere.

  The contact angle of the surface of the triazine dithiol derivative surface coating layer is 40 to 75 degrees, preferably 45 to 72 degrees. When the contact angle is within this range, the adhesiveness to the resin substrate is excellent, and the heat resistance after adhesion is excellent.

  The contact angle of the surface coating layer was measured by a droplet method using an Elmer optical contact angle measuring instrument G-1 as a contact angle with respect to pure water. The measurement was performed at 20 ° C, and the average value of 10 measurement points was defined as the contact angle.

A method for producing a surface-treated aluminum plate will be described with reference to FIG. FIG. 1 is a manufacturing process diagram.
An aluminum metal plate 1 is prepared (step 1). As the aluminum metal plate, a metal plate having a shape suitable for an aluminum conductor printed wiring board or an aluminum core printed wiring board is prepared. An aluminum metal plate having a surface roughness Ra value of 0.05 μm or less is prepared.

  When using an aluminum plate for an aluminum conductor printed wiring board, the pre-processing step 3 without performing drilling or the like, and when using an aluminum core printed wiring board after the drilling step (step 2) for performing a drilling process, It is sent to the pretreatment step 3.

Adhesion improvement treatment is performed as pretreatment on the aluminum metal plate before electrolytic polymerization (step 3). This pretreatment improves the adhesion of the triazine dithiol derivative layer to the aluminum metal plate. First, the surface is degreased with an organic solvent. Examples of the organic solvent include ketone solvents used for degreasing the metal surface, such as acetone. Degreasing can be performed in combination with ultrasonic treatment. Finally, it is thoroughly washed with pure water and methanol and dried.
Moreover, a reduction process can be used together as a pretreatment process. The reduction treatment is performed by immersing the degreased aluminum metal plate in an aqueous hydrazine solution. The concentration of hydrazine is preferably 1 to 10% by weight, the immersion time is preferably 0.1 to 5 minutes, and the immersion temperature is preferably 20 to 60 ° C. This pretreatment condition facilitates electrolytic polymerization on the surface of the aluminum metal plate, which is the next step. Finally, it is thoroughly washed with pure water and methanol and dried.

Next, as a polymerization step, an electrolytic polymerization film of a triazine dithiol derivative is formed on the surface of the pretreated aluminum metal plate (step 4).
The electrolytic solution is obtained by dissolving the triazine dithiol derivative and the supporting electrolyte in pure water.
The triazine dithiol derivative is preferably a mixed triazine dithiol derivative. For example, DBN and iso-DON are blended at a molar ratio of 1: 1. The mixed triazine dithiol derivative concentration in the aqueous solution is 0.001 to 5% by weight, preferably 0.01 to 1% by weight. When the mixed triazine dithiol derivative concentration is less than 0.001% by weight, it is difficult to form an electrolytic polymerized film. When the mixed triazine dithiol derivative concentration exceeds 5% by weight, the transfer rate of monomer ions is slowed and the polymerization degree is lowered.
As the supporting electrolyte, NaNO ₂ , NaOH, LiOH, KOH, Na ₂ CO ₃ , Na ₂ SO ₄ , K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ CO ₃ , KNO ₂ , KNO ₃ , NaClO ₄ , CH ₃ COONa, Na ₂ B ₂ O ₇ , NaBO ₃ , NaH ₂ PO ₂ , (NaPO ₃ ) ₆ , Na ₂ MnO ₄ , Na ₃ SiO _{3 and the} like can be mentioned.

In the present invention, it is preferable to use a supporting electrolyte containing at least one compound of sodium hydroxide (NaOH), sodium nitrite (NaNO ₂ ), and sodium carbonate (Na ₂ CO ₃ ). In particular, as shown in Examples described later, a supporting electrolyte containing sodium nitrite (NaNO ₂ ) as an essential component is preferable. That is, a mixed electrolyte of sodium nitrite and sodium hydroxide or a mixed electrolyte of sodium nitrite and sodium carbonate is preferable.

When aluminum is used as one electrode, two oxidation reactions of the aluminum oxidation reaction and the triazine dithiol derivative oxidation reaction compete on that electrode. The standard electrode potential of aluminum (Al ³⁺ + 3e ⁻ = Al) is −1.66 V (vs. saturated calomel electrode), and Al ³⁺ produced by oxidation combines with water as a solvent to finally form alumina (Al ₂ O ₃ ). On the other hand, the oxidation potential of triazine dithiol is estimated to be 0.4 V on the copper plate and 0.7 V on the iron plate, which is considered to be less than 1 V. On the aluminum electrode, alumina formation is more likely than the electropolymerization of the triazine dithiol derivative. It is likely to occur. However, when sodium nitrite (NaNO ₂ ) is used as the supporting electrolyte, the triazinedithiol derivative is easily electropolymerized on the aluminum electrode due to the radical polymerization promoting action of sodium nitrite. The formation of the triazine dithiol polymerized film can be confirmed by the presence of C = C and C = N stretching vibration peaks based on the triazine ring by FT-IR measurement. Appeared.

The concentration of the supporting electrolyte is preferably 0.05 to 0.3 M / l in terms of molar concentration. When the concentration of the supporting electrolyte is outside this range, the film thickness by electrolytic polymerization is not sufficient.
The mixing ratio in the case of using a mixed electrolyte of sodium nitrite and sodium hydroxide or a mixed electrolyte of sodium nitrite and sodium carbonate is preferably about 1: 1.

  Electrolysis at the time of electropolymerization includes constant current electrolysis with a constant current between the working electrode and the counter electrode, constant potential electrolysis with a constant potential between the working electrode and the counter electrode, and potential up to an arbitrary potential. Any one of a scanning potential electrolysis method in which electrolysis is performed by sweeping the current and a pulse electrolysis method in which a current is applied for a certain period of time or a certain period of time after applying a constant voltage can be employed. In the electropolymerization of mixed triazine dithiol derivatives on an aluminum metal plate, a constant-current electrolysis method in which a good-quality film is easily obtained because the electrode reaction proceeds constantly, or a constant potential that can control the type of reaction that occurs on the electrode The electrolytic method is preferred.

The electropolymerization temperature is preferably 10 to 40 ° C. When the electropolymerization temperature is out of this range, the film thickness is not sufficiently generated by the electropolymerization.
The polymerization time can be adjusted depending on the desired film thickness. However, if the polymerization time is too long, peeling of the film, corrosion of the aluminum metal plate, and the like are not preferable.
The current density is preferably 0.09 mA / cm ² or more. If it is less than this, the polymerization potential of the triazine dithiol derivative will not be reached. Further, if the current density is too high, the surface of the coating tends to be rough, and therefore it is preferably 1 mA / cm ² or less.

Next, as a heat treatment step, the polymer film obtained in the polymerization step is subjected to heat treatment (step 5).
The heat treatment is a process for increasing the film strength by increasing the degree of polymerization of the triazine dithiol derivative film. As heat treatment conditions, the temperature is 60 to 350 ° C., preferably 80 to 200 ° C., and the treatment time is 5 to 600 minutes, preferably 5 to 120 minutes in an air atmosphere. Simultaneously with the heat treatment, radiation treatment such as ultraviolet treatment can be used together.
If the polymerized film has uneven electrodeposition, it is preferable to carry out water washing and immersion treatment in an alcohol solution after electrolytic polymerization and before heat treatment. As the alcohol solution, alcohol alone or an alcohol solution in which an acrylic acid derivative or a maleic acid derivative is dissolved can be used. Specific examples of the alcohol solution include an ethanol solution in which 10% by weight of acrylic acid-n-hexyl is dissolved, an ethanol solution in which 10% by weight of maleic acid-n-butyl is dissolved, and the like.

  In the aluminum plate 6 of the present invention, a triazine dithiol derivative film having a thickness of 100 to 300 nm is formed on the surface having a surface roughness of 0.05 μm (Ra) or less. The surface contact angle of this aluminum plate shows a value of 40 to 75 degrees and shows a peel strength of 10 KN / m or more, so it is suitable for aluminum printed wiring boards such as aluminum conductor printed wiring boards or aluminum core printed wiring boards. Can be used.

A process for producing an aluminum conductor printed wiring board using the aluminum plate 6 subjected to the triazine dithiol derivative coating treatment will be described with reference to FIGS. FIG. 2 is a process diagram of an aluminum conductor printed wiring board, and FIG. 3 is a structural diagram for each process.
In the surface-treated aluminum plate 6 of the present invention, a triazine dithiol derivative coating 61 is formed on the surface of the untreated aluminum metal plate 1 (FIG. 3A).
An aluminum laminated plate 8 is formed by laminating an aluminum plate 6 and an insulating resin 81 such as a thermosetting resin or a thermoplastic resin and performing a laminating press step 7 (FIG. 3B).
The insulating resin 81 is preferably a thermosetting resin, and particularly preferably a prepreg. The prepreg can be used as long as the base material is impregnated with a thermosetting resin. Paper, glass cloth, glass nonwoven fabric, polyester nonwoven fabric, aromatic polyamide paper, or combinations thereof can be used. Examples of thermosetting resins include epoxy resins, phenol resins, polyimide resins, imide-modified epoxy resins, and aralkyls. Examples include ether resins, polyvinylphenol resins, bismaleimide / triazine resins, and the like.
In the laminating press step 7, the aluminum plate 6 is overlapped on both sides of the insulating resin 81 and set up using a laminating jig such as a release aluminum plate or a cushion plate, and inserted between the hot press hot plates and laminated and bonded. Press.

After drilling holes 92 for through-holes using the aluminum laminated plate 8, surface polishing, degreasing, zinc replacement treatment, etc. are performed, and finally, copper electroplating is performed to form an electro copper plating layer 91 on the surface. (Step 9, FIG. 3C).
Next, a conductor pattern is formed (step 10, FIG. 3 (d)). The conductor pattern can be formed by any method such as a method using a dry film or a method using pattern printing. For example, by performing dry film sticking, exposure / development, direct plating, electrolytic copper plating, etc., a conductor pattern is formed by the electrolytic copper plating 101 including the inner surface of the through hole 92. Reference numeral 102 denotes a plating resist.
Finally, by removing the plating resist 102 and etching the aluminum plate 6 (step 11), the aluminum conductor printed wiring board 12 is obtained (FIG. 3E).
Since the aluminum conductor printed wiring board 12 of the present invention uses the aluminum plate 6 subjected to the triazine dithiol derivative coating treatment, the adhesiveness between the insulating resin 81 and the aluminum plate 6 is excellent. For this reason, the aluminum conductor printed wiring board excellent in heat resistance, such as few peeling at the time of high temperature and withstanding heat cycle, can be obtained.

A process for producing an aluminum core printed wiring board using the perforated aluminum plate 6a subjected to the triazine dithiol derivative coating treatment will be described with reference to FIGS. FIG. 4 is a process diagram of an aluminum core printed wiring board, and FIG. 5 is a structural diagram for each process.
In the aluminum plate 6a of the present invention, after the drilling treatment, the triazine dithiol derivative coating 61 is formed on the surface of the untreated aluminum metal plate 1 (FIG. 5A).
In the same manner as the aluminum conductor printed wiring board, the lamination press step 7a is performed to form the aluminum core copper-clad plate 13 (step 13, FIG. 5B).
In the laminating press step 7a, an insulating resin 81 is placed on both sides of the aluminum plate 6a, and a copper foil 131 is placed on the outer side of the aluminum plate 6a, and set up using a laminating jig such as a release aluminum plate or a cushion plate. Is inserted between the hot plates and laminated adhesive press is performed.

After drilling the through hole 141 using the aluminum core copper-clad plate 13, a chemical copper plating process and an electrolytic copper plating process are performed to form an electrolytic copper plating layer 142 on the surface (step 14, FIG. 5 (c)).
Next, a conductor pattern is formed (step 15, FIG. 5 (d)). For the formation of the conductor pattern, a method using a dry film 151 is preferable.
Finally, an etching / dry film removal process (step 16) is performed to obtain an aluminum core printed wiring board 17 (FIG. 5E).
Since the aluminum core printed wiring board 17 of the present invention uses the aluminum plate 6a subjected to the triazine dithiol derivative coating treatment, the adhesiveness between the insulating resin 81 and the aluminum plate 6a is excellent. For this reason, the aluminum core printed wiring board excellent in heat resistance, such as few peeling at high temperature and withstanding heat cycle, can be obtained.

Examples 1 to 9
An aluminum metal plate having a thickness of 0.1 mm and a surface roughness of 50 nm (Ra) or less is prepared. The surface of this aluminum metal plate was degreased in acetone for 30 minutes under ultrasound and dried at room temperature. Using this degreased aluminum metal plate, surface treatment was performed under the electrolytic solution, electrolytic polymerization conditions and heat treatment conditions shown in Table 1 to obtain a surface-treated aluminum plate. The thickness of the triazine dithiol derivative coating was about 200 nm.

  The contact angle and peel strength with respect to pure water of the obtained surface-treated aluminum plate were measured. The peel strength was measured using a tensile tester (manufactured by Shimadzu Corporation, AGS-500A). The results are shown in Table 1. The treated surface state was judged visually, and the case where no uneven electrodeposition was observed was considered good. In addition, when the contact angle, the treated surface state and the peel strength were taken into consideration, the overall best case was evaluated as 、, the next best case as ○, and the worst case as ×. In addition, the comparative example 1 is the characteristic of the aluminum plate without surface treatment.

表１に示すように、各実施例は接触角が 40 度〜 75 度の範囲内であり、比較例１よりも優れたピール強度を有している。

As shown in Table 1, each example has a contact angle in the range of 40 degrees to 75 degrees, and has a peel strength superior to that of Comparative Example 1.

Examples 10 to 12
The surface-treated aluminum plate obtained in Example 4 and three types of glass epoxy prepregs were laminated under the conditions shown in Table 2, and the peel strength after heating was measured under the heating conditions shown in Table 2. As for the used glass epoxy prepreg, Example 10 is a prepreg ES-3305 manufactured by Risho Kogyo Co., Ltd., Example 11 is a prepreg P-6514 manufactured by Nikkan Kogyo, and Example 12 is a prepreg P-6524 manufactured by Nikkan Kogyo. is there. The results are shown in Table 2.

表２に示すように、各実施例はいずれも 150℃、96 時間加熱後であってもピール強度の低下は少なかった。

As shown in Table 2, in each example, the peel strength decreased little even after heating at 150 ° C. for 96 hours.

Example 13 to Example 15
A solder heat resistance test was performed using the samples laminated in the conditions of 180 ° C., 25 kgf / cm ² , and 100 min. The solder heat resistance test was conducted by flowing on a static solder at 260 ° C. The results are shown in Table 3. The case where no swelling or peeling occurs is indicated by OK.

表３に示すように、各実施例はいずれもハンダ耐熱試験に優れていた。

As shown in Table 3, each example was excellent in the solder heat resistance test.

  Since the aluminum plate of the present invention is excellent in adhesion to a resin base material and excellent in heat resistance after bonding, an aluminum conductor printed wiring board that requires excellent heat resistance and a high-precision pattern and It can be applied to aluminum-based printed wiring boards such as aluminum core printed wiring boards.

It is a manufacturing-process figure of the surface-treated aluminum plate. It is process drawing of an aluminum conductor printed wiring board. FIG. 3 is a structural diagram for each step of FIG. 2. It is process drawing of an aluminum core printed wiring board. FIG. 5 is a structural diagram for each step of FIG. 4. It is a manufacturing-process figure of an aluminum copper clad board.

Explanation of symbols

1 Aluminum metal plate 2 Process 2
3 Step 3
4 Process 4
5 Process 5
6 Surface-treated aluminum plate 12 Aluminum conductor printed wiring board 17 Aluminum core printed wiring board

Claims (8)

An aluminum plate surface-treated with a triazine dithiol derivative layer for use in an aluminum-based printed wiring board,
The aluminum plate, wherein the surface-treated aluminum plate has a contact angle of 40 degrees to 75 degrees. The aluminum plate according to claim 1, wherein the triazine dithiol derivative layer is an electrolytic polymer of a triazine dithiol derivative represented by the following formula (1).

(R is represented by —NR ¹ R ² , R ¹ and R ² represent an alkyl group or an unsaturated alkyl group, and M represents a hydrogen atom or an alkali metal)   The aluminum plate according to claim 2, wherein the triazine dithiol derivative is a mixture of triazine dithiol derivatives having different Rs.   The mixture of the triazine dithiol derivatives is 2-dibutylamino-1,3,5-triazine-2,4-dithiolmonosodium and 2-diisooctylamino-1,3,5-triazine-2,4-dithiolmono The aluminum plate according to claim 3, which is a mixture with sodium.   The aluminum plate according to any one of claims 1 to 4, wherein the electrolytic polymer is heat-treated. An aluminum-based printed wiring board comprising: a polymerization step of forming a polymer film on the surface of an aluminum metal plate by electrolytic polymerization of a triazine dithiol derivative represented by the following formula (1); and a heat treatment step of subjecting the polymer film to a heat treatment In the manufacturing method of the aluminum plate surface-treated with the triazine dithiol derivative used for
A method for producing an aluminum plate, comprising a step of improving the adhesion between a triazine dithiol derivative and an aluminum metal plate as a pretreatment for the polymerization step.

(R is represented by —NR ¹ R ² , R ¹ and R ² represent an alkyl group or an unsaturated alkyl group, and M represents a hydrogen atom or an alkali metal)   7. The method for producing an aluminum plate according to claim 6, wherein the polymerization step uses a supporting electrolyte containing at least one compound of sodium hydroxide, sodium nitrite and sodium carbonate. In an aluminum-based printed wiring board obtained by laminating and bonding an aluminum plate to a prepreg, a thermosetting resin or a thermoplastic resin,
An aluminum-based printed wiring board, wherein the aluminum plate is the aluminum plate according to any one of claims 1 to 5.

Images