JP2007186620A - Adhesive composite composition, method for adhesion thereof and method for producing laminated sheet using the same method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composite composition which is a low dielectric responsive to a high frequency of ≥1 GHz, to provide a method for adhesion thereof and to provide a method for producing a laminated sheet using the same method. <P>SOLUTION: The adhesive composite composition comprises a triallyl isocyanate and a peroxide as essential components in polyphenylene ether. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention is an adhesive composite composition that can be used in electronic devices and computer control products used in various applications, and is capable of supporting a frequency of 1 GHz or higher with a low dielectric material, an adhesion method thereof, and a laminate using the method. It is related with the manufacturing method.

  In recent years, it is necessary to increase the signal propagation speed with the increase in information processing speed. For this reason, it is known to use a polyphenylene ether (PPE) substrate as a material having a low relative dielectric constant (for example, Patent Document 1). 2). In the information communication field, the frequency band of radio waves has become higher and narrower due to the increase in wireless communication devices and the number of channels. Specifically, high frequency capable of high-speed processing of signals in the high frequency band of 1 GHz or higher. Development of high-density multilayer printed circuit boards using signal processing boards and built-up methods is required.

In order to manufacture such a high-frequency signal processing substrate having a high frequency characteristic of 1 GHz or more, it is important to bond a metal foil, which is a conductor having a smooth surface, to PPE. Up to now, as a method of bonding PPE and a metal foil as a conductor, for example, a copper foil, a method of thermocompression bonding a blackened copper foil to a PPE film is known, but the substrate obtained by this method is The adhesive strength between the copper foil and the PPE film is very low, and further practical adhesive strength is desired. Further, the surface of the copper foil becomes rough due to the blackening treatment, and such a roughened copper foil attenuates an electric signal having a high frequency, and it has been difficult to realize the intended high frequency characteristics.
JP 2005-082793 A JP 2005-008829 A

  Therefore, the present invention has been made from the background as described above, and is an adhesive composite composition capable of supporting a high frequency of 1 GHz or higher with a low dielectric material, an adhesion method thereof, and a laminate using the method. It is an object to provide a manufacturing method.

The present invention is characterized by the following in order to solve the above problems.
<1> An adhesive composite composition comprising polyphenylene ether containing triallyl isocyanate and a peroxide as essential components.
<2> The above-mentioned <1>, wherein 10 to 150 parts by mass of triallyl isocyanate and 0.1 to 20 parts by mass of peroxide are contained with respect to 100 parts by mass of polyphenylene ether. Item 2. The adhesive composite composition according to Item 1.
<3> The above <1>, wherein 10 to 150 parts by mass of triallyl isocyanate and 1 to 10 parts by mass of peroxide are contained per 100 parts by mass of polyphenylene ether. The adhesive composite composition as described in 1.
<4> Formula (I)

（式中、Ｍはアルカリ金属である。）
で表されるトリアジントリチオール化合物を含む溶液中に導体金属箔を浸漬してその表面に反応性皮膜を生成させた後、上記＜１＞から＜３＞のいずれかに記載の接着性複合体組成物と前記導体金属箔とを加熱圧着して接着性複合体組成物と導体金属箔とを接着することを特徴とする接着性複合体組成物の接着方法。
＜５＞ 前記式（Ｉ）で表されるトリアジントリチオール化合物において、式中のＭは、Ｌｉ，Ｎａ，ＫまたはＣｓであることを特徴とする上記＜４＞に記載の接着性複合体組成物の接着方法。
＜６＞ トリアジントリチオール化合物を含む溶液において、トリアジントリチオール化合物の濃度は０．１〜１０００ｍｇ／ｄｍ^３の範囲であることを特徴とする上記＜４＞または＜５＞に記載の接着性複合体組成物の接着方法。
＜７＞ トリアジントリチオール化合物を含む溶液において、トリアジントリチオール化合物の濃度は１〜１００ｍｇ／ｄｍ^３の範囲であることを特徴とする上記＜４＞または＜５＞に記載の接着性複合体組成物の接着方法。
＜８＞ トリアジントリチオール化合物を含む溶液に三級アミン類が添加されていることを特徴とする上記＜４＞から＜７＞のいずれかに記載の接着性複合体組成物の接着方法。
＜９＞ 三級アミン類は、トリエタノールアミンであることを特徴とする上記＜８＞に記載の接着性複合体組成物の接着方法。
＜１０＞ ８０℃〜２００℃の温度範囲で加熱圧着することを特徴とする上記＜４＞から＜９＞のいずれかに記載の接着性複合体組成物の接着方法。
＜１１＞ 上記＜４＞から＜１０＞のいずれかの方法で接着性複合体組成物の片面または両面に導体金属箔を積層配置することを特徴とする積層板の製造方法。
＜１２＞ 導体金属箔は、その表面の平均粗さ（Ｒａ）が１μｍ以下の表面粗度を有する平滑な導体金属箔であることを特徴とする上記＜１１＞に記載の積層板の製造方法。
＜１３＞ 上記＜１１＞または＜１２＞に記載の方法で得られた積層板の導体金属箔に導体パターンを作製してなることを特徴とするプリント配線板。
＜１４＞ １〜２０ＧＨｚの周波数帯域において、誘電率が２．４〜２．８の範囲の低誘電体特性を有していることを特徴とする上記＜１３＞に記載のプリント配線板。

(In the formula, M is an alkali metal.)
After immersing the conductor metal foil in a solution containing the triazine trithiol compound represented by formula (1) to form a reactive coating on the surface, the adhesive composite according to any one of <1> to <3> above A method for bonding an adhesive composite composition, comprising bonding the adhesive composite composition and the conductive metal foil by thermocompression bonding the composition and the conductive metal foil.
<5> In the triazine trithiol compound represented by the formula (I), M in the formula is Li, Na, K or Cs, wherein the adhesive composite composition according to the above <4> Bonding method of objects.
<6> The adhesive composite as described in <4> or <5> above, wherein in the solution containing the triazine trithiol compound, the concentration of the triazine trithiol compound is in the range of 0.1 to 1000 mg / dm ^3. Method for bonding body composition.
<7> In the solution containing a triazine trithiol compound, the concentration of the triazine trithiol compound is in the range of 1 to 100 mg / dm ³ , and the adhesive composite composition according to the above <4> or <5> Bonding method of objects.
<8> The method for adhering an adhesive composite composition according to any one of <4> to <7>, wherein a tertiary amine is added to the solution containing the triazine trithiol compound.
<9> The method for adhering an adhesive composite composition according to <8>, wherein the tertiary amine is triethanolamine.
<10> The method for adhering an adhesive composite composition according to any one of the above <4> to <9>, wherein thermocompression bonding is performed in a temperature range of 80 ° C to 200 ° C.
<11> A method for producing a laminated board, characterized in that a conductive metal foil is laminated on one or both sides of the adhesive composite composition by any one of the above <4> to <10>.
<12> The method for producing a laminated board according to <11>, wherein the conductor metal foil is a smooth conductor metal foil having a surface roughness of an average roughness (Ra) of 1 μm or less. .
<13> A printed wiring board comprising a conductor pattern formed on a conductor metal foil of a laminate obtained by the method according to <11> or <12>.
<14> In the frequency band of 1 to 20 GHz, the printed wiring board according to the above <13>, which has a low dielectric property having a dielectric constant of 2.4 to 2.8.

  According to the present invention as described above, a conductive metal foil having a smooth surface, more specifically, an adhesive that can be firmly bonded to a conductive metal foil having an average roughness (Ra) of the surface of 1 μm or less. A composite composition and an adhesion method thereof are provided. Furthermore, the laminate obtained by bonding the adhesive composite composition and the conductive metal foil by this bonding method is a high-frequency signal processing substrate capable of supporting a frequency of 1 GHz or higher with a low dielectric material or a high-performance by a built-up method. Densified multilayer printed circuit boards can be manufactured.

  The present invention has the features as described above, and an embodiment thereof will be described below.

  The adhesive composite composition of the present invention contains triallyl isocyanate (TAIC) and peroxide as essential components in polyphenylene ether (PPE).

  Examples of the polyphenylene ether in the present invention include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, and poly (2,6-dipropyl-1). , 4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, and the like. If it is generally used for a printed circuit board etc., it will not be restrict | limited in particular.

  Further, the peroxide is not particularly limited as long as it is used for three-dimensionalizing the polyphenylene ether with the triallyl isocyanate and generally used for PPE resins. For example, benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2 , 5-bis (t-butylperoxy) hexyne-3, α, α′-di (t-butylperoxy) diisopropylbenzene, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, etc. Can be mentioned.

  The above triallyl isocyanate and peroxide contain, for example, 10 to 150 parts by weight of triallyl isocyanate and 0.1 to 20 parts by weight of peroxide with respect to 100 parts by weight of polyphenylene ether. It is preferable. If the triallyl isocyanate is less than 10 parts by mass, the resulting resin may be inferior in heat resistance (hardness, strength, etc.), which is not preferred. If it exceeds 150 parts by mass, the resin component decreases. Therefore, it may become brittle and the film forming ability is lowered, which is not preferable. When the peroxide is less than 0.1 part by mass, the chloroform insolubilization rate is not sufficiently high when the adhesive composite composition is heated. When the peroxide exceeds 20 parts by mass, the adhesive composite This is not preferable because the surface may gel at the stage of preparation of a resin film obtained by heating the body composition to cause adhesion inhibition. More preferably, it is considered that the peroxide is in the range of 1 to 10 parts by mass. In this case, the chloroform insolubilization rate can be 90% or more by containing 1 part by mass or more. Thus, by containing a peroxide, the glass transition temperature of the PPE resin composition can be increased to about 180 ° C., and the substrate obtained from this PPE resin composition is made insoluble and infusible. , It can withstand a heat history of 5 minutes at 260 ° C.

  The adhesive composite composition of the present invention contains the above polyphenylene ether powder, triallyl isocyanate, and peroxide. For example, these polyphenylene ether powder, triallyl isocyanate, and peroxide are used as a kneader or a banbury. It puts into mixers, such as a mixer, mixes for 5 to 60 minutes at the temperature of about 20-80 degreeC, prepares a resin paste, forms a coating film on a ferrite plate using an applicator or a roll, then 130 degreeC A transparent resin film may be obtained by heating in an oven for 20 minutes. Of course, the heating condition is not limited to this. Moreover, it is considered that the film thickness of the obtained resin film is in the range of 20 to 1000 μm.

  In addition, the resin film further reinforced can be manufactured by impregnating cloth with resin paste and heating this at the time of resin film preparation. Examples of such cloth include glass woven cloth, polyester woven cloth, rayon woven cloth, nylon woven cloth, polyethylene woven cloth, cotton woven cloth, vinylon woven cloth, and carbon woven cloth.

  The method for adhering the adhesive composite composition of the present invention involves immersing a conductive metal foil in a solution containing the triazine trithiol compound represented by the formula (I) (hereinafter also referred to as triazine trithiol treatment). After forming a reactive film on the surface, the adhesive composite composition and the conductor metal foil are bonded by thermocompression bonding to the adhesive composite composition and the conductor metal foil.

  Here, M in the formula (I) can include Li, Na, K, Cs, and the like. In addition, the triazine trithiol compound is used by dissolving in water or an organic solvent such as alcohols, acetone, and toluene. Specifically, an aqueous triazine trithiol monoalkali salt solution is considered, and by immersing the conductive metal foil in this aqueous solution, the reactive film (adhesive layer) of amorphous triazine thiol metal salt (3CNSM) is converted into the conductive metal foil. Can be produced on the surface.

The solution containing the above triazine thiol compound preferably has, for example, a triazine thiol compound concentration in the range of 0.1 to 1000 mg / dm ³ . If it is less than 0.1 mg / dm ³ , it may take too much time to produce a sufficient film for adhesion, and if it is 1000 mg / dm ³ or more, the aromaphos triazine trithiol metal salt will not be formed on the surface, resulting in high density. This is not preferable because the film is formed and the adhesion is inhibited. More preferably, it is in the range of 1 to 100 mg / dm ^{3 in} consideration of the film formation time, the density of the film to be formed, and the like.

  To the solution containing the above triazine trithiol compound, a tertiary amine may be added for the purpose of ensuring the stability of the triazine trithiol compound or the formed reactive film. By adding such a tertiary amine, the conductor metal foil and the adhesive composite composition can be stably manufactured so as to have sufficient adhesive strength.

  Specific examples of the tertiary amines include trimethylamine, triethanolamine, dimethylaniline, N-ethylimidazole, etc., but triethanolamine is preferred in consideration of handling properties and availability. Used. It is considered that these tertiary amines are added in an amount of 0.01 to 10 mol, preferably 0.1 to 1 mol, relative to 1 mol of triazine trithiol monoalkali salt. By adding the tertiary amine in such a range, the effect can be sufficiently exhibited.

  The conductor metal foil in the present invention is not particularly limited as long as it is used for a normal printed wiring board and the like, and examples thereof include gold, copper, and aluminum. The thickness of the conductor metal foil For example, it may be in the range of 10 to 100 μm. If the thickness exceeds 100 μm, the printed board to be manufactured may be too heavy. If the thickness is less than 10 μm, for example, when used as a high-frequency signal processing board, there may be a problem in communication volume, which is preferable. Absent.

  Further, the average roughness (Ra) on the surface of the conductive metal foil is preferably 1 μm or less, and more preferably 0.5 μm or less. The attenuation factor of the electrical signal of the conductive metal foil is known as a skin effect related to the average surface roughness of the surface of the conductive metal foil. When a high frequency electrical signal of 1 GHz or higher is sent, the average surface roughness of at least 1 μm or less is required. It is said that it is necessary. The bonding method of the adhesive composite composition of the present invention can be firmly bonded even with a smooth conductive metal foil having an average roughness of 1 μm or less as described above. By adhering the foil, it is possible to obtain a laminate that can handle a frequency of 1 GHz or more.

  The above triazine trithiol treatment effectively produces an amorphous triazine trithiol metal salt (3CNSM) reactive film by immersing in the treatment solution at a temperature in the range of 0 to 100 ° C. for about 1 to 200 seconds. can do. A temperature lower than 0 ° C. is not preferable because the film formation rate is low and the productivity is poor. When the temperature exceeds 100 ° C., the tendency to form a crystalline high-density reactive film increases, which is not preferable. As a more suitable temperature, a range of 20 to 70 ° C. is considered, whereby a reactive film can be generated more effectively.

In the present invention, a reactive film is formed on the surface of the conductive metal foil as described above, and then the conductive metal foil and the resin film are heat-bonded. _{CH 2} CH = CH 2 groups interfacial bonding between -SM group reactive film formed on the (allyl group) and a conductive metal foil surface to produce. For this reason, it can be set as the laminated board to which the resin film and conductor metal foil were adhere | attached firmly. In addition, the conductor metal foil may be heat-pressed on one side or both sides of the resin film.

As the thermocompression bonding conditions, specifically, press heating is considered in a temperature range of 80 to 200 ° C. under a load of 1 to ²⁰ kg / cm ² . Under a load of less than 1 kg / cm ² , air may not be completely removed from between the resin film and the conductive metal foil, and may not be sufficiently bonded. Further, it is not preferable that the resin film cannot be held at a predetermined film thickness under a load exceeding 20 kg / cm ² . When the temperature is lower than 80 ° C., the interfacial reaction hardly occurs between the TAIC allyl group of the resin film and the -SM group of the reactive coating on the surface of the conductive metal foil, and when the temperature exceeds 200 ° C., the curing reaction of TAIC proceeds from the interface. Then, the interfacial reaction between the conductive metal foil and the resin film hardly occurs, which is not preferable.

  The thermocompression bonding time can generally be 1 minute or longer. Less than 1 minute is not preferable because the interface reaction between the conductive metal foil and the resin film does not occur sufficiently. The upper limit of the thermocompression bonding time is not particularly limited considering the time until the interface reaction between the conductive metal foil and the resin film is almost completed, but is generally about 200 minutes.

  The printed wiring board of this invention can obtain a printed wiring board by producing a conductor pattern by carrying out an etching process etc. on the conductor metal foil surface of said laminated board, and forming a circuit. The printed wiring board thus obtained is a low dielectric having a dielectric constant of 2.4 to 2.8, a dielectric loss tangent of 0.003 to 0.006, and a high dielectric of 1 to 20 GHz. It is possible to manufacture a high-frequency signal processing board that can cope with a frequency or a high-density multilayer printed board by a built-up method.

  Hereinafter, examples will be shown and described in more detail. Of course, the present invention is not limited by the following examples. Moreover, in the following Examples, although copper foil was used as conductor metal foil, it is not limited to this, Even if it is gold foil and aluminum foil, the same effect can be provided.

<Example 1><Comparative Examples 1-4>
PPE (polydimethylphenyl ether, Mitsubishi Engineering Plastics, YPX-100), TAIC (triallyl isocyanate, Nippon Kasei Co., Ltd.), DCP (dicumyl peroxide, reagent) with the compounding amounts shown in Table 1 are bench kneaders (Irie Shokai) And blended at 60 ° C. for 20 minutes. When 20 g of the obtained PPE paste is taken on a ferrite plate (chrome-plated steel plate), a film is drawn with an applicator, and heated at 130 ° C. for 20 minutes in a heat oven (Asahi Techno Glass Co., Ltd. electric constant temperature machine AFO-82). 82.2 μm PPE resin film, average surface roughness Ra: 0.19 to 0.21 (atomic force microscope, Nano Scope III manufactured by Digital Instruments, resolution: 1 nm). The dielectric constant of the PPE resin film was 2.65. The dielectric constant is obtained by depositing gold on the surface of the resin film, taking a terminal with a silver paste, and measuring the capacitance at a frequency of AC 500 mV, 1 kHz to 1 MHz using an impedance measuring instrument (Impedance Analyzer 4294A manufactured by Agilent Technology Co., Ltd.). And calculated.

Next, electrolytic copper foil (40 × 60 × 0.05 mm, manufactured by Fukuda Metal Foil Powder Co., Ltd., average roughness Ra on both sides: 0.19 to 0.21 μm) was washed with acetone (20 ° C., 5 sec), 1 After washing with a% -HCl aqueous solution (20 ° C., 5 sec) and 1% -NaOH aqueous solution (20 ° C., 5 sec), washing with water and ethanol were performed, followed by drying with a drier. Triazine trithiol monosodium 50 mg / dm ³ and triethanolamine 40 mg / dm ³ were dissolved in 1 dm ³ of deaerated ion-exchanged water to prepare a treatment solution. The electrolytic copper foil was immersed in a treatment solution at 50 ° C. for 30 seconds, washed with water and dried. Ra of the obtained treated electrolytic copper foil was 0.21 μm.

A PPE resin film (40 × 40 × 0.08 mm) was sandwiched between two treated electrolytic copper foils from both sides, applied with a load of ² kg / cm ² , and heated and pressed at 160 ° C. for 20 minutes. A 1 cm wide fillet was put into the obtained PPE-Cu adhesive, and a peel test (Shimadzu Autograph AGS-1kND) was performed at a tensile speed of 5 mm / min. Evaluation of the peel test is “◎” (adhesive strength is good) when the peel strength is 0.40 (kN / m) or higher, and 0.10 (kN / m) or higher and less than 0.40 (kN / m) “◯” (a level that causes no problem in practical use), 0.05 (kN / m) or more and less than 0.10 (kN / m) “Δ” (adhesive strength is weak, and there is a problem in practical use) Level), less than 0.05 (kN / m) was evaluated as “×” (not almost adhered or not adhered).

  In Comparative Examples 1 and 3, the PPE resin film was prepared by dissolving the resin and DCP in chloroform and stripping the solvent in a flat petri dish to create a PPE resin film.

  The results are shown in Table 1.

比較例１〜４ではＰＰＥ樹脂フィルムの必須成分を調べたものであるが、ＰＰＥの他にＴＡＩＣとＤＣＰの１成分がなくとも、ＰＰＥ樹脂フィルムはたとえ銅箔が処理されていても接着しないことが確認された。またＰＰＥ樹脂フィルムにＴＡＩＣとＤＣＰの２成分が含まれていても、銅箔が処理されていなければ、比較例４に示されるように接着しないことも確認された。したがって、ＰＰＥ樹脂フィルムと銅箔が接着するためにはＰＰＥ樹脂フィルムにＴＡＩＣとＤＣＰの２成分が含まれていることが重要である。そして、銅箔をトリアジントリチオールで処理することも重要である。

In Comparative Examples 1 to 4, the essential component of the PPE resin film was examined. Even if there is no TAIC and DCP component other than PPE, the PPE resin film should not adhere even if the copper foil is treated. Was confirmed. Moreover, even if two components of TAIC and DCP were contained in the PPE resin film, it was confirmed that the copper foil was not bonded as shown in Comparative Example 4 if the copper foil was not treated. Therefore, in order for the PPE resin film and the copper foil to adhere, it is important that the PPE resin film contains two components, TAIC and DCP. It is also important to treat the copper foil with triazine trithiol.

Although the dielectric constant of PPE is 2.45, it changes slightly when TAIC (dielectric constant: 2.50) and DCP are added, but it maintains a dielectric constant of 2.7 or lower and can be used in the high frequency era of 1 GHz or higher. It turns out that it is a composition. In addition, the average surface roughness of the copper foil needs to be at least 1 μm or less in order to send a high frequency electrical signal of 1 GHz or more. Although the copper foil used this time is mirror-polished, Ra can be sufficiently lowered to 0.2 μm or less, and even if it is treated with triazine trithiol, the variation in surface roughness is Ra: 0. It is 02 μm or less and can be used up to about 20 GHz in combination with the use of PPE resin.
<Examples 2 to 10>
A PPE resin film and a TTN (triazine trithiol) -treated copper foil were prepared in the same manner as in Example 1 with the formulation shown in Table 2, and the dielectric constant of the resin film and the surface roughness of the treated copper foil were measured. The treatment liquid was adjusted to a ratio of 1 mol of triethanolamine to 1 mol of monosodium salt of triazine trithiol.

  Next, these were adhered under the conditions shown in Table 2, and the peel strength was measured. These results are shown in Table 2.

ＴＡＩＣの量を変化させると、ＰＰＦ樹脂フィルムの強度は減少（実施例２：３５０ｋｇ／ｃｍ^２から実施例４：４０ｋｇ／ｃｍ^２）するが、ガラス転移温度Ｔｇは高く（実施例２：Ｔｇ＝１２０℃から実施例４：Ｔｇ＝１８０℃）なった。ＤＣＰの添加量を増量（実施例６）すると、極性成分が増加するため誘電率が増加する傾向にある。ＴＴＮの処理濃度と温度が高いと、被膜の充填密度が高くなりアリル基と反応しがたくなるため、接着強度が減少（実施例８）する傾向にある。接着温度が高くなると、界面層のアリル基の硬化反応が進行して界面層のアリル基濃度が減少するので、処理銅箔の−ＳＣｕとＰＰＥ樹脂フィルムの−ＣＨ_２ＣＨ＝ＣＨ_２基の界面反応量が減少し、結果として接着強度が減少（実施例１０）する。
＜実施例１１〜２３＞
ＴＡＩＣやＤＣＰの配合量、処理液におけるトリアジントリチオールモノナトリウム塩の濃度、接着時の加熱温度を変えて、実施例１と同様にしてＰＰＥ樹脂フィルムとＴＴＮ処理銅箔を作成し、これらを接着して剥離強度を測定した。なお、処理液はトリアジントリチオールのモノナトリウム塩１モルに対してトリエタノールアミン１モルの割合となるようにした。これらの結果を表３に示す。

When the amount of TAIC is changed, the strength of the PPF resin film decreases (Example 2: 350 kg / cm ² to Example 4: 40 kg / cm ² ), but the glass transition temperature Tg is high (Example 2: Tg = 120 ° C. and Example 4: Tg = 180 ° C.). Increasing the amount of DCP added (Example 6) tends to increase the dielectric constant because the polar component increases. When the treatment concentration and temperature of TTN are high, the filling density of the coating film becomes high and it becomes difficult to react with allyl groups, so that the adhesive strength tends to decrease (Example 8). As the adhesion temperature increases, the allyl group curing reaction of the interface layer proceeds and the allyl group concentration of the interface layer decreases, so the interface between the treated copper foil -SCu and the PPE resin film -CH ₂ CH = CH ₂ groups The amount of reaction decreases, resulting in a decrease in adhesive strength (Example 10).
<Examples 11 to 23>
Change the blending amount of TAIC and DCP, the concentration of triazine trithiol monosodium salt in the treatment liquid, and the heating temperature at the time of adhesion to create a PPE resin film and a TTN-treated copper foil in the same manner as in Example 1, and bond these The peel strength was measured. The treatment liquid was adjusted to a ratio of 1 mol of triethanolamine to 1 mol of monosodium salt of triazine trithiol. These results are shown in Table 3.

これらの結果から、十分な接着強度を確保するためには、ＰＰＥ樹脂１００質量部に対してＴＡＩＣ１０〜１５０部、ＤＣＰ０．１〜２０質量部なかでもＤＣＰ１〜１０質量部とすることが有効であることが確認された。また、処理液におけるトリアジントリチオールのモノナトリウムの濃度が０．１〜１０００ｍｇ／ｄｍ^３なかでも１〜１００ｍｇ／ｄｍ^３、あるいは接着時の加熱温度が８０〜２００℃の温度範囲で加熱することも有効であることが確認された。

From these results, in order to ensure sufficient adhesive strength, it is effective to make DCP 1 to 10 parts by mass among TAIC 10 to 150 parts and DCP 0.1 to 20 parts by mass with respect to 100 parts by mass of PPE resin. It was confirmed. In addition, the concentration of monosodium triazine trithiol in the treatment liquid may be 1 to 100 mg / dm ³ among 0.1 to 1000 mg / dm ³ , or the heating temperature at the time of adhesion may be 80 to 200 ° C. It was confirmed to be effective.

Claims (14)

  An adhesive composite composition comprising a polyphenylene ether containing triallyl isocyanate and a peroxide as essential components.   The adhesiveness according to claim 1, wherein 10 to 150 parts by mass of triallyl isocyanate and 0.1 to 20 parts by mass of peroxide are contained with respect to 100 parts by mass of polyphenylene ether. Composite composition.   The adhesive composite according to claim 1, wherein 10 to 150 parts by mass of triallyl isocyanate and 1 to 10 parts by mass of peroxide are contained with respect to 100 parts by mass of polyphenylene ether. Composition. Formula (I)

(In the formula, M is an alkali metal.)
The conductive composite foil is immersed in a solution containing a triazine trithiol compound represented by the following formula to generate a reactive film on the surface thereof, and then the adhesive composite composition according to any one of claims 1 to 3 and A method for bonding an adhesive composite composition, wherein the conductive composite foil and the conductive metal foil are bonded by thermocompression bonding with the conductive metal foil.   In the triazine trithiol compound represented by the formula (I), M in the formula is Li, Na, K, or Cs. . The method for adhering an adhesive composite composition according to claim 4 or 5, wherein in the solution containing the triazine trithiol compound, the concentration of the triazine trithiol compound is in the range of 0.1 to 1000 mg / dm ^3. . The method for adhering an adhesive composite composition according to claim 4 or 5, wherein in the solution containing the triazine trithiol compound, the concentration of the triazine trithiol compound is in the range of 1 to 100 mg / dm ³ .   The method for adhering an adhesive composite composition according to any one of claims 4 to 7, wherein a tertiary amine is added to the solution containing the triazine trithiol compound.   The method for bonding an adhesive composite composition according to claim 8, wherein the tertiary amine is triethanolamine.   The method for adhering an adhesive composite composition according to any one of claims 4 to 9, wherein thermocompression bonding is performed in a temperature range of 80 ° C to 200 ° C.   A method for producing a laminated board, characterized in that a conductive metal foil is laminated on one or both sides of an adhesive composite composition by any one of the methods according to claim 4.   The method for producing a laminated board according to claim 11, wherein the conductive metal foil is a smooth conductive metal foil having a surface roughness with an average surface roughness (Ra) of 1 µm or less.   A printed wiring board obtained by producing a conductor pattern on a conductor metal foil of a laminated board obtained by the method according to claim 11.   14. The printed wiring board according to claim 13, wherein the printed circuit board has a low dielectric property with a dielectric constant of 2.4 to 2.8 in a frequency band of 1 to 20 GHz.