JP2019172803A - Resin composition, copper foil with resin, printed circuit board, and treatment method of copper foil with resin - Google Patents

Abstract

To provide a resin composition having low dielectric loss tangent, high adhesiveness with a copper layer, and a heat resistance, and including a silica filler capable of suppressing deterioration progress of a continuously used melanism treatment liquid.SOLUTION: There is provided a resin composition containing an elastomer, a polyarylene ether compound, a phosphorous compound represented by the following formula (I): where n is 3 or 4, a silica particle, and a silane coupling agent, and having content of the silane coupling agent satisfying a relation of 0.0900≤x/S≤0.4000, wherein x is weight percentage of the silane coupling agent based on weight of the silica particle, and S (m/g) is BET specific area of the silica particle.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a resin-coated copper foil, a printed wiring board, and a method for treating a resin-coated copper foil.

  Printed wiring boards are widely used in electronic devices such as portable electronic devices. In particular, with higher functions of portable electronic devices and the like in recent years, the frequency of signals has been increased, and printed wiring boards suitable for such high-frequency applications have been demanded. The printed wiring board for high frequency is desired to have a low transmission loss in order to enable transmission without deteriorating the quality of the high frequency signal. A printed wiring board is provided with a copper foil processed into a wiring pattern and an insulating resin base material, but transmission loss is mainly due to conductor loss due to the copper foil and dielectric loss due to the insulating resin base material. It consists of. Therefore, in a copper foil with a resin layer applied to high frequency applications, it is desirable to suppress dielectric loss due to the resin layer. For this purpose, the resin layer is required to have excellent dielectric properties, particularly low dielectric loss tangent.

  On the other hand, various resin compositions having excellent dielectric properties and the like have been proposed for uses such as printed wiring boards. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-262191) discloses a flame retardant curable composition containing a polyfunctional vinyl aromatic copolymer, a phosphorus-nitrogen flame retardant, and an inorganic filler in a predetermined blending ratio. A resin composition is disclosed. Patent Document 2 (Japanese Patent Laid-Open No. 2011-6683) discloses a thermosetting resin composition containing a styrene-maleic anhydride copolymer resin, a cyanate compound, and a phosphorus flame retardant. . Patent Document 3 (International Publication No. 2013/061688) discloses a resin composition including an epoxy resin, a curing agent, and an inorganic filler surface-treated with a specific organic compound. In any of Patent Documents 1 to 3, it is described that silica is used as an inorganic filler.

JP 2007-262191 A JP 2011-6683 A International Publication No. 2013/061688

  By the way, the copper foil for printed wiring boards may be subjected to a blackening treatment for the purpose of improving adhesion to an insulating resin. This blackening treatment is performed, for example, by immersing a circuit board (for example, a laminate including a copper layer and an insulating resin layer) in a blackening treatment liquid containing hypochlorous acid and sodium hydroxide as main components. However, when blackening treatment is performed in a mass production process using a copper foil with resin filled with silica filler having a low dielectric loss tangent, it is within the range of the blackening treatment capacity (liquid load) specified in the product specification. Even so, the deterioration of the blackening treatment liquid progressed early, and the blackening treatment was easily inhibited. That is, as the blackening process is continuously carried out in the mass production process, the brightness of the blackened copper foil surface is greatly increased (that is, the degree of blackening is greatly reduced). there were. In fact, when a resin-coated copper foil was newly treated using a blackening treatment solution obtained by treating a large-area resin-coated copper foil, the target brightness value of the obtained resin-coated copper foil could not be achieved. . Furthermore, it is difficult to determine the change point of deterioration of the blackening treatment liquid. Therefore, in the mass production process in which the copper foil with resin containing silica filler is continuously blackened using the same blackening treatment liquid, it is desired to suppress the early deterioration of the blackening treatment liquid.

  The present inventors have recently developed a resin composition containing an elastomer, a polyarylene ether compound, a predetermined phosphorus-based compound, silica particles, and a predetermined amount of a silane coupling agent, having a low dielectric loss tangent and high adhesion to a copper layer. In addition, the present inventors have obtained the knowledge that, when subjected to a mass production process accompanied by a blackening treatment, the early deterioration of the blackening treatment solution used continuously can be effectively suppressed while having heat resistance.

  Therefore, the object of the present invention is to provide a blackening treatment that is continuously used when it is subjected to a mass production process involving a blackening treatment while having a low dielectric loss tangent, high adhesion with a copper layer, and heat resistance. An object of the present invention is to provide a silica-filled resin composition that can effectively suppress the early deterioration of the liquid.

（式中、ｎは３又は４である）で表されるリン系化合物と、
（ｄ）シリカ粒子と、
（ｅ）シランカップリング剤と、
を含み、前記シランカップリング剤の含有量が、前記シリカ粒子の重量に対する前記シランカップリング剤の重量百分率をｘとし、かつ、前記シリカ粒子のＢＥＴ比表面積をＳ（ｍ^２／ｇ）としたとき、０．０９００≦ｘ／Ｓ≦０．４０００の関係を満たす量である、樹脂組成物が提供される。 According to one aspect of the invention, (a) an elastomer,
(B) a polyarylene ether compound;
(C) Formula (I) below:

A phosphorus compound represented by the formula (wherein n is 3 or 4);
(D) silica particles;
(E) a silane coupling agent;
And the content of the silane coupling agent is x as the weight percentage of the silane coupling agent relative to the weight of the silica particles, and the BET specific surface area of the silica particles is S (m ² / g). When the resin composition is provided in an amount satisfying the relationship of 0.0900 ≦ x / S ≦ 0.4000.

  According to another aspect of the present invention, the resin layer includes a copper foil and a resin layer made of the resin composition provided on at least one surface of the copper foil, and the resin layer is cured. Copper foil is provided.

  According to the other one aspect | mode of this invention, it is a printed wiring board provided with the said resin-coated copper foil, Comprising: The printed wiring board with which the said copper foil has a blackening process part is provided.

  According to the other one aspect | mode of this invention, the processing method of copper foil with resin including the said copper foil with resin being immersed in a blackening process liquid and performing a blackening process is provided.

  Embodiments of the present invention will be described below. In the present specification, a numerical range expressed in the format of “X to Y” means “X or more and Y or less”.

Resin Composition The resin composition of the present invention comprises an elastomer, a polyarylene ether compound, a phosphorus compound represented by the above formula (I), silica particles, and a silane coupling agent. The content of the silane coupling agent is 0.1395 when the weight percentage of the silane coupling agent with respect to the weight of the silica particles is x and the BET specific surface area of the silica particles is S (m ² / g). ≦ x / S ≦ 0.6047 is an amount that satisfies the relationship. Thus, according to the resin composition including the elastomer, the polyarylene ether compound, the predetermined phosphorus compound, the silica particles, and the predetermined amount of the silane coupling agent, the low dielectric loss tangent and the copper layer are high. While having adhesiveness and heat resistance, when subjected to a mass production process involving blackening treatment, it is possible to effectively suppress early deterioration of the blackening treatment liquid used continuously. That is, by producing a resin-coated copper foil using the resin composition of the present invention, good characteristics as a substrate material such as low dielectric loss tangent, high adhesion between the resin and the copper layer, and heat resistance are ensured. However, it is possible to suppress early deterioration of the blackening treatment liquid. That is, the resin composition containing a silica filler for printed wiring boards as disclosed in Patent Documents 1 to 3 inherently has good characteristics as a substrate material such as a low dielectric loss tangent and high adhesion to a copper layer. However, when it is subjected to a mass production process involving blackening treatment, the blackening treatment solution that is continuously used is deteriorated at an early stage. Although the cause is not necessarily certain, it is guessed that the component of a silica filler (silica particle) elutes in a blackening process liquid, and covers the surface of copper foil. In this regard, according to the resin composition of the present invention, it is possible to effectively suppress the early deterioration of the blackening treatment liquid. The mechanism is not necessarily clear, but the presence of the silane coupling agent makes it difficult for the silica filler (silica particle) component to elute into the blackening treatment solution. As a result, the copper foil surface is covered with the silica filler-derived component. It is presumed that it may be difficult to break.

  As described above, the resin composition of the present invention has a low dielectric loss tangent. For example, the resin composition of the present invention has a dielectric loss tangent at 3 GHz after curing of preferably less than 0.0030, more preferably less than 0.0025, and even more preferably less than 0.0020. The lower limit value of the dielectric loss tangent is not particularly limited, but is typically 0.0001 or more.

(A) Elastomer Elastomer contributes to adhesion and the like. As the elastomer, various types of elastomers can be used, but a thermoplastic elastomer is preferable. Examples of thermoplastic elastomers include styrene elastomers (TPS), olefin elastomers (TPO), vinyl chloride elastomers (TPVC), urethane elastomers (TPU), ester elastomers (TPEE, TPC), amide elastomers ( TPAE, TPA), and combinations thereof, and styrene elastomers are preferable. The styrenic elastomer may be either hydrogenated or non-hydrogenated. That is, the styrene-based elastomer is a compound containing a site derived from styrene and may contain a site derived from a compound having a polymerizable unsaturated group such as olefin in addition to styrene. When a double bond is present at a site derived from a compound having a polymerizable unsaturated group in the styrene elastomer, the double bond portion may be hydrogenated or not hydrogenated. There may be. Particularly preferred elastomers include hydrogenated styrene-butadiene elastomers. Examples of styrene-based elastomers include TR manufactured by JSR Corporation, SIS manufactured by JSR Corporation, Toughtec (registered trademark) manufactured by Asahi Kasei Corporation, Septon (registered trademark) manufactured by Kuraray Co., Ltd., and Hibler (registered trademark) manufactured by Kuraray Co., Ltd. Is mentioned.

  The content of the elastomer in the resin composition is preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight, and still more preferably, with respect to 100 parts by weight of the total amount of the elastomer, polyarylene ether compound and phosphorus compound. It is 25 to 45 parts by weight, particularly preferably 30 to 40 parts by weight.

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立して水素原子又は炭素数１〜３の炭化水素基であり、ｎは繰り返し数であり、典型的には４〜１０００であり、より好ましくは５〜５０である）
で表される骨格を分子中に含む化合物であるのが好ましい。ポリフェニレンエーテル化合物の例としては、ポリフェニレンエーテルオリゴマーのスチレン誘導体、末端水酸基変性ポリフェニレンエーテルオリゴマー、末端メタクリル変性ポリフェニレンエーテルオリゴマー、末端グリシジルエーテル変性ポリフェニレンエーテルオリゴマー等が挙げられる。ポリフェニレンエーテルオリゴマーのスチレン誘導体の製品例としては、三菱ガス化学株式会社製ＯＰＥ−２Ｓｔ−１２００及びＯＰＥ−２Ｓｔ−２２００が挙げられる。末端水酸基変性ポリフェニレンエーテルオリゴマーの製品例としては、ＳＡＢＩＣ社製ＳＡ−９０及びＳＡ−１２０が挙げられる。末端メタクリル変性ポリフェニレンエーテルオリゴマーの製品例としては、ＳＡＢＩＣ社製ＳＡ−９０００が挙げられる。 (B) Polyarylene ether compound The polyarylene ether compound contributes to heat resistance and the like. The polyarylene ether compound is preferably a polyphenylene ether compound. The polyarylene ether compound or polyphenylene ether compound has the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, n is a repeating number, typically 4 to 1000) Yes, more preferably 5-50)
It is preferable that it is a compound which contains the frame | skeleton represented by these in a molecule | numerator. Examples of polyphenylene ether compounds include styrene derivatives of polyphenylene ether oligomers, terminal hydroxyl group-modified polyphenylene ether oligomers, terminal methacryl-modified polyphenylene ether oligomers, terminal glycidyl ether-modified polyphenylene ether oligomers, and the like. Examples of styrene derivatives of polyphenylene ether oligomers include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of products of the terminal hydroxyl group-modified polyphenylene ether oligomer include SA-90 and SA-120 manufactured by SABIC. As an example of a product of terminal methacryl-modified polyphenylene ether oligomer, SA-9000 manufactured by SABIC may be mentioned.

  The content of the polyarylene ether compound in the resin composition of the present invention is preferably 10 to 50 parts by weight, more preferably 20 to 45 parts per 100 parts by weight of the total amount of the elastomer, the polyarylene ether compound and the phosphorus compound. Part by weight, more preferably 30 to 40 parts by weight.

（式中、ｎは３〜４である）
で表される環状シアノフェノキシホスファゼン化合物であり、難燃性に寄与する。リン系化合物は、上記式におけるｎ＝３の化合物と、式（Ｉ）におけるｎ＝４の化合物との混合物であってもよい。式（Ｉ）におけるｎ＝３単独の化合物の製品例としては、株式会社伏見製薬所製ＦＰ−３００が挙げられ、式（Ｉ）におけるｎ＝３の化合物とｎ＝４の化合物の混合物の製品例としては、株式会社伏見製薬所製ＦＰ−３００Ｂが挙げられる。 (C) Phosphorus compound The phosphorus compound is represented by the following formula (I):

(Wherein n is 3-4)
Is a cyclic cyanophenoxyphosphazene compound represented by the formula, which contributes to flame retardancy. The phosphorus compound may be a mixture of the compound of n = 3 in the above formula and the compound of n = 4 in the formula (I). As an example of a product of a compound having n = 3 alone in formula (I), FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. may be mentioned, and a product of a mixture of a compound of n = 3 and n = 4 in formula (I) An example is FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

  The content of the phosphorus compound in the resin composition of the present invention is preferably 10 to 50 parts by weight, more preferably 20 to 100 parts by weight, with the total amount of the elastomer, polyarylene ether compound and phosphorus compound being 100 parts by weight. 40 parts by weight, more preferably 25 to 35 parts by weight.

(D) Silica particles Silica particles contribute to low dielectric loss tangent, fluidity and the like as fillers excellent in dispersibility and dielectric properties. The average particle diameter D50 of the silica particles is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm, and still more preferably 0.5 to 1.5 μm. By using silica particles (for example, spherical silica particles) having an average particle diameter D50 within the above range, a resin composition excellent in fluidity and workability can be provided. The silica particles may be in any form such as pulverized particles, spherical particles, core-shell particles, and hollow particles.

  The content of the silica particles in the resin composition of the present invention may be any amount and is not particularly limited. However, the addition amount of the coupling agent depending on the content of the silica particles, the ease of filler dispersion, the resin composition From the viewpoint of fluidity, etc., 20 to 300 parts by weight is preferable, more preferably 30 to 240 parts by weight, and still more preferably 40 to 40 parts by weight with respect to 100 parts by weight of the total amount of the elastomer, the polyarylene ether compound and the phosphorus compound. 180 parts by weight, particularly preferably 50 to 160 parts by weight. With such a content, the resin composition is excellent in dielectric loss tangent, but when the resin-coated copper foil is used, it is possible to avoid a decrease in peel strength between the resin composition and the copper foil.

(E) Silane coupling agent A silane coupling agent contributes to suppression of deterioration of the blackening treatment liquid accompanying use of a resin containing a silica filler. The content of the silane coupling agent in the resin composition of the present invention is determined by setting the weight percentage of the silane coupling agent to the weight of the silica particles as x (wt%) and the BET specific surface area of the silica particles (that is, measured by the BET method). The specific surface area) is S (m ² / g), the amount satisfying the relationship of 0.0900 ≦ x / S ≦ 0.4000, preferably 0.1100 ≦ x / S ≦ 0.2900, More preferably, the amount satisfies 0.1300 ≦ x / S ≦ 0.1800. Within such a range, early deterioration progress of the blackening treatment liquid can be effectively suppressed. Without being bound by theory, it is presumed that the silica particles are eluted from the resin composition into the blackening treatment solution to cover the surface of the copper foil and prevent the blackening treatment. As silane coupling agent, amino functional silane coupling agent, acrylic functional silane coupling agent, methacryl functional silane coupling agent, epoxy functional silane coupling agent, olefin functional silane coupling agent, mercapto functional silane Various silane coupling agents such as coupling agents and vinyl functional silane coupling agents can be used. In particular, a silane coupling agent composed of a silane compound having a total of three methoxy groups and / or ethoxy groups in the molecule is preferable, and specific examples of such silane coupling agents include 8-methacryloxyoctyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, p-styryltrimethoxysilane, 7-octenyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Examples include silane, 3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like.

Resin-coated copper foil The resin composition of the present invention is preferably provided in the form of a resin-coated copper foil. That is, according to the preferable aspect of this invention, the copper foil with resin containing copper foil and the resin layer which consists of a resin composition provided in the at least one surface of copper foil is provided. By adopting the resin layer containing the resin composition of the present invention, the resin layer has excellent dielectric properties (very low dielectric loss tangent) suitable for high frequency applications, and is a copper-clad laminate or printed wiring board. In this case, excellent interlayer adhesion and heat resistance can be exhibited. Such excellent adhesion and heat resistance between the copper foil and the resin layer, when used in the manufacture of copper-clad laminates or printed wiring boards, prevents defects such as circuit peeling from the substrate and product yield. Improvement can be realized. In addition, a low dielectric loss tangent contributes to a reduction in dielectric loss, and as a result, a reduction in transmission loss in high frequency applications can be realized. Therefore, the copper foil with resin of the present invention can be preferably applied as an insulating layer and a conductor layer of a printed wiring board for high frequencies. Examples include (i) base station servers, routers, (ii) corporate networks, (iii) high-speed mobile communication backbone systems, and the like.

  Specifically, the resin-coated copper foil of the present invention preferably has a dielectric loss tangent of less than 0.0030 at a frequency of 3 GHz, more preferably 0.0025 in a state where the resin layer is cured. Less than, more preferably less than 0.0020. The dielectric loss tangent typically has a value of 0.0001 or more. Moreover, the resin-coated copper foil of the present invention is measured in accordance with JIS C 6481-1996 in a state where the resin layer is cured (peel strength to be described later in Examples). Is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and still more preferably 0.6 kgf / cm or more. In general, the higher the peel strength, the better. However, the product typically has a value of 3 kgf / cm or less, more typically 1.5 kgf / cm or less.

  Although the thickness of a resin layer is not specifically limited, It is preferable that it is 0.1-150 micrometers, More preferably, it is 20-70 micrometers, More preferably, it is 25-65 micrometers. When the thickness is within these ranges, it is easy to form a resin layer by applying the resin composition, and it is easy to ensure sufficient adhesion with the copper foil.

The resin layer itself may constitute an insulating layer in a copper clad laminate or a printed wiring board. Further, the resin layer may be formed on the surface of the copper foil as a primer layer for bonding with a prepreg in a copper clad laminate or a printed wiring board. In this case, the resin layer of the resin-coated copper foil can improve the adhesion between the prepreg and the copper foil as a primer layer. Therefore, the resin-coated copper foil of the present invention may have a prepreg on the resin layer. In addition, this resin layer may be obtained by curing the above-described resin composition, or the above-described resin composition is provided as a resin composition layer in a semi-cured (B stage) state. As the step, it may be subjected to adhesive curing by hot pressing. This hot press employs a vacuum hot press method in which a vacuum is reached in advance and then cured under conditions of a temperature of 150 to 250 ° C., a temperature holding time of 30 to 300 minutes, and a pressure of 5 to 50 kgf / cm ^2. Is possible.

  The copper foil may be an electrolytic foil or a rolled metal foil (so-called raw foil), or may be in the form of a surface-treated foil having a surface treatment applied to at least one surface. Also good. The surface treatment is various surface treatments performed to improve or impart some property (for example, rust prevention, moisture resistance, chemical resistance, acid resistance, heat resistance, and adhesion to the substrate) on the surface of the metal foil. It can be. The surface treatment may be performed on at least one side of the metal foil, or may be performed on both sides of the metal foil. Examples of the surface treatment performed on the copper foil include rust prevention treatment, silane treatment, roughening treatment, barrier formation treatment and the like.

  The 10-point average roughness Rzjis measured in accordance with JIS B0601-2001 on the surface of the resin layer side of the copper foil is preferably 2.0 μm or less, more preferably 1.5 μm or less, and even more preferably 1 0.0 μm or less. Within such a range, transmission loss in high frequency applications can be desirably reduced. That is, it is possible to reduce the conductor loss due to the copper foil that can be increased by the skin effect of the copper foil that appears more prominently as the frequency becomes higher, thereby realizing further reduction in transmission loss. The lower limit of the ten-point average roughness Rzjis on the surface of the resin layer side of the copper foil is not particularly limited, but Rzjis is preferably 0.005 μm or more, more preferably 0.01 μm or more from the viewpoint of improving the adhesion with the resin layer. More preferably, it is 0.05 μm or more.

  Particulate protrusions are formed on the surface of the copper foil on the resin layer side in that the heat-resistant adhesion with the resin layer can be remarkably improved within the range where the numerical range of the ten-point average roughness Rzjis is maintained. preferable. The metal constituting the particulate protrusions is preferably copper in that the high-frequency transmission loss of the printed wiring board can be reduced.

  Although the thickness of copper foil is not specifically limited, It is preferable that it is 0.1-100 micrometers, More preferably, it is 0.15-40 micrometers, More preferably, it is 0.2-30 micrometers. If the thickness is within these ranges, methods such as MSAP (modified semi-additive), SAP (semi-additive), and subtractive methods, which are general pattern formation methods for wiring formation of printed wiring boards, can be used. It can be adopted. However, when the thickness of the copper foil is, for example, 10 μm or less, the resin-coated copper foil of the present invention has a resin layer on the copper foil surface of the carrier-attached copper foil provided with a release layer and a carrier for improving handling properties. May be formed.

  In the copper foil with resin of the present invention, the copper foil is preferably used for blackening treatment. That is, according to a preferred embodiment of the present invention, there is provided a method for treating a resin-coated copper foil, which comprises immersing the resin-coated copper foil in a blackening treatment solution and performing a blackening treatment. By making the copper foil black, it is possible to improve the adhesion to the insulating resin. And as mentioned above, according to the resin composition of the present invention, when subjected to a mass production process accompanied by a blackening treatment, the early deterioration progress of the blackening treatment liquid continuously used is effectively suppressed. be able to. The blackening treatment may be performed according to a known method. For example, a circuit board (for example, a laminate including a copper layer and an insulating resin layer) is immersed in a blackening treatment liquid mainly containing hypochlorous acid and sodium hydroxide. Is done.

Printed wiring board The resin composition or resin-coated copper foil of the present invention is preferably used for production of a printed wiring board. That is, according to the preferable aspect of this invention, the printed wiring board provided with the said resin-coated copper foil or the printed wiring board obtained using the said resin-coated copper foil is provided. In this case, the resin layer of the resin-coated copper foil is cured. The printed wiring board according to this aspect includes a layer configuration in which an insulating resin layer and a copper layer are laminated in this order. The insulating resin layer is as described above for the copper-clad laminate. And it is preferable that the copper foil thru | or a copper layer have a blackening process part, ie, it is blackened. By blackening the copper foil or the copper layer, it is possible to improve the adhesion with the insulating resin. In any case, a known layer structure can be adopted for the printed wiring board. Specific examples of the printed wiring board include a single-sided or double-sided printed wiring board in which a circuit is formed on a laminated body obtained by bonding and curing the resin-coated copper foil of the present invention on one or both sides of a prepreg, or a multilayer in which these are multilayered A printed wiring board etc. are mentioned. Other specific examples include flexible printed wiring boards, COF, TAB tape, build-up multilayer wiring boards, and semiconductor integrated circuits that form a circuit by forming the resin-coated copper foil of the present invention on a resin film. Direct build-up-on-wafer, etc., in which the laminated copper foil and circuit formation are repeated alternately. For example, the resin-coated copper foil of the present invention is preferably applicable as an insulating layer and a conductor layer of a printed wiring board for high frequencies. Examples include (i) base station servers, routers, (ii) corporate networks, (iii) high-speed mobile communication backbone systems, and the like.

  The present invention is more specifically described by the following examples.

Examples 1-10
A resin varnish comprising a resin composition was prepared, a resin-coated copper foil was produced using this resin varnish, and the evaluation was performed. Specifically, it is as follows.

(1) Preparation of resin varnish First, the following elastomers, polyarylene ether compounds, phosphorus compounds, silica particles, and silane coupling agents were prepared as resin varnish raw material components.
(A) Elastomer MP-10: Asahi Kasei Co., Ltd., hydrogenated styrene elastomer (b) Polyarylene ether compound OPE-2St-1200: Mitsubishi Gas Chemical Co., Ltd., bifunctional polyphenylene ether oligomer styrene derivative (number average molecular weight About 1200)
OPE-2St-2200: a styrene derivative of a bifunctional polyphenylene ether oligomer (manufactured by Mitsubishi Gas Chemical Company, Inc.) (number average molecular weight of about 2200)
(C) Phosphorus compound FP-300B: manufactured by Fushimi Pharmaceutical Co., Ltd., cyclic cyanophenoxyphosphazene compound (d) silica particles SO-C4: manufactured by Admatex Co., Ltd., spherical silica particles (measured by laser diffraction particle size distribution measurement Average particle diameter D50: 1.0 μm, BET specific surface area S: 4.3 m ² / g)
(E) Silane coupling agent KBM-5803: Shin-Etsu Chemical Co., Ltd., 8-methacryloxyoctyltrimethoxysilane KBM-4803: Shin-Etsu Chemical Co., Ltd., 8-glycidoxyoctyltrimethoxysilane KBM-6803: Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -8-aminooctyltrimethoxysilane KBM-1403: Shin-Etsu Chemical Co., Ltd., p-styryltrimethoxysilane KBM-1083: Shin-Etsu Chemical Co., Ltd. 7-octenyltrimethoxysilane KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane KBM-903: manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane KBM-5103: 3-acrylo manufactured by Shin-Etsu Chemical Co., Ltd. Trimethoxysilane KBM-573: manufactured by Shin-Etsu Chemical Co., Ltd., N- phenyl-3-aminopropyltrimethoxysilane

  Each raw material component shown in Table 1 is weighed at the solid content weight ratio shown in Table 1, an organic solvent is added so that the solid content concentration becomes 55%, and the dispersion is dissolved at 60 ° C. using a disperser. did. A resin solution (varnish) thus prepared was obtained.

(2) Production of resin-coated copper foil in semi-cured state (B-stage) The obtained resin solution was comma coated on the surface of electrolytic copper foil (MWG foil, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 18 μm). It applied so that the thickness of the resin layer after drying might be set to 50 micrometers using the machine. The obtained coating film was dried at 150 ° C. for 3 minutes, whereby the resin composition was semi-cured. Thus, a resin-coated copper foil provided with a resin layer in a semi-cured state (B-stage) was produced.

(3) Preparation of substrate provided with cured copper foil with resin (C-stage) The obtained copper foil with resin is laminated so that the resin layer comes into contact with the core material (manufactured by Mitsubishi Gas Chemical Co., Ltd., HL832NS). The substrate was laminated in the order of core material layer-resin layer-copper layer by performing hot vacuum press molding under the heating and pressing conditions of a press temperature of 200 ° C., a temperature holding time of 90 minutes, and a press pressure of 30 kgf / cm ^2. Was made.

(4) Production of single resin film Two resin-coated copper foils were bonded together so that the resin layers were in contact with each other, and hot vacuum press was performed at 200 ° C. for 90 minutes under a heating and pressing condition of 30 kgf / cm ^2. Molding was performed to prepare a double-sided copper-clad laminate. All the copper on both sides of the obtained copper-clad laminate was removed by etching to obtain a resin film as a simple substance.

(5) Various evaluations The following various evaluations were performed on the substrates, resin films, and double-sided copper-clad laminates obtained in (3) and (4) above.

<Dielectric properties>
With respect to the resin film obtained in (4) above, the dielectric loss tangent Df at 3 GHz was measured by the perturbation type cavity resonator method. The measurement was performed according to JIS R 1641 using a measuring device (resonator manufactured by KEYCOM Co., Ltd. and network analyzer manufactured by KEYSIGHT Co., Ltd.) after cutting the resin film alone in accordance with the sample size of the resonator. The results were as shown in Table 1.

<Peel strength>
A circuit was formed on the copper layer for the substrate obtained in (3) above. Specifically, a dry film was bonded to both surfaces of the substrate to form an etching resist layer. Then, a 10 mm width peel strength measurement test circuit was exposed and developed on the etching resist layers on both sides to form an etching pattern. Thereafter, circuit etching was performed with a copper etchant, and the etching resist was removed to obtain a circuit. The circuit thus formed was peeled from the resin layer, and the peel strength (kgf / cm) between the circuit and the resin layer was measured in accordance with JIS C 6481-1996. The average value of three measurements was taken as the measurement value. The results were as shown in Table 1.

<Solder heat resistance>
About the board | substrate obtained by said (3), solder heat resistance was evaluated based on JISC6481-1996. Specifically, after the substrate was floated once in a 260 ° C. solder bath for 10 minutes, the appearance change was visually observed to check for the occurrence of swelling. This evaluation was performed on four pieces of samples. The confirmation results were evaluated in three stages according to the following criteria. The results were as shown in Table 1.
-Evaluation A: No blistering occurred in all of the four specimens.
-Evaluation B: Swelling occurred in a part of the four pieces of samples.
-Evaluation C: Swelling occurred in all of the four specimens.

<Evaluation of blackening solution>
500 mL of blackening solution (PROBON ^™ 80 manufactured by Dow Electronic Materials) was built according to the manufacturer's specifications. A resin film and a double-sided copper-clad laminate are simultaneously immersed in the resulting blackening solution, and the following formula:
Liquid load factor (%) = {(actual blackening area) / (area where blackening liquid can be treated)} × 100
The blackening treatment was performed so that the liquid load ratio defined by the formula (66) reached 66% and then 93%. In addition, the “processable area of the blackening treatment liquid” in the above formula is based on the value of the liquid load described in the product specification of the blackening treatment liquid. The brightness of the blackened surface of the double-sided copper-clad laminate at each liquid load factor, specifically the brightness L in the L ^* a ^* b ^* color space (JIS Z 8781-4: 2013), is determined by TIME GROUP INC. Measurement was made using TCD100. The liquid deterioration rate at each liquid load factor is expressed by
Liquid deterioration rate (%) = {(lightness at each liquid load factor) / (lightness at initial stage)} × 100
And rated according to the following criteria. The results were as shown in Table 1.
-Evaluation A: Liquid deterioration rate at 93% liquid load rate is less than 200%-Evaluation B: Liquid deterioration rate at 93% liquid load rate is 200% or more and less than 400%-Evaluation C: Liquid deterioration rate at 93% liquid load rate Is over 400%

Example 11 (Comparison)
A resin composition and the like were prepared and evaluated in the same manner as in Example 1 except that the silane coupling agent was not used and the amount of silica particles added was 150.0 parts by weight. The results were as shown in Table 1.

Example 12 (Comparison)
Preparation and evaluation of a resin composition and the like were performed in the same manner as in Example 1 except that the addition amount of the silane coupling agent was 0.50 parts by weight and the addition amount of the silica particles was 150.8 parts by weight. went. The results were as shown in Table 1.

Claims (12)

(A) an elastomer;
(B) a polyarylene ether compound;
(C) Formula (I) below:

A phosphorus compound represented by the formula (wherein n is 3 or 4);
(D) silica particles;
(E) a silane coupling agent;
And the content of the silane coupling agent is x as the weight percentage of the silane coupling agent relative to the weight of the silica particles, and the BET specific surface area of the silica particles is S (m ² / g). When the resin composition is in an amount satisfying the relationship of 0.0900 ≦ x / S ≦ 0.4000.   The resin composition according to claim 1, wherein the elastomer comprises a hydrogenated styrene-butadiene elastomer.   The resin composition of Claim 1 or 2 whose average particle diameter D50 of the said silica particle is 0.1-5 micrometers. The polyarylene ether compound has the following formula:

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is the number of repetitions)
The resin composition as described in any one of Claims 1-3 which is a compound which contains the frame | skeleton represented by these in a molecule | numerator.   The resin composition according to any one of claims 1 to 4, wherein the silane coupling agent comprises a silane compound having a total of three methoxy groups and / or ethoxy groups in the molecule.   10 to 60 parts by weight of the elastomer, 10 to 50 parts by weight of the polyarylene ether compound, and 10 to 50 parts by weight, where the total amount of the elastomer, the polyarylene ether compound and the phosphorus compound is 100 parts by weight. The resin composition as described in any one of Claims 1-5 containing the said phosphorus-type compound and 20-300 weight part of said silica particles.   20 to 50 parts by weight of the elastomer, 20 to 45 parts by weight of the polyarylene ether compound, 20 to 40 parts by weight of the phosphorus compound, and 30 to 240 parts by weight of the silica particles. 7. The resin composition according to 6.   The resin composition according to any one of claims 1 to 7, wherein a dielectric loss tangent at a frequency of 3 GHz after curing is less than 0.0030.   A resin comprising a copper foil and a resin layer comprising the resin composition according to any one of claims 1 to 8 provided on at least one surface of the copper foil, wherein the resin layer is cured. Copper foil.   The copper foil with a resin according to claim 9, wherein the copper foil is used for blackening treatment.   It is a printed wiring board provided with the copper foil with resin of Claim 10, Comprising: The printed wiring board with which the said copper foil has a blackening process part.   The processing method of copper foil with a resin including immersing the copper foil with resin of Claim 10 in a blackening process liquid, and performing a blackening process.