JPWO2019021862A1 - Resin composition, insulating layer for wiring board and laminate - Google Patents

Abstract

Provided is a resin composition which is excellent in various properties such as flame retardancy, circuit embedding property, handling property (flexibility), and can bring about a significantly low dielectric loss tangent. This resin composition comprises a predetermined high-viscosity resin (A) having a viscosity at 120° C. of 8000 Pa·s or more, a predetermined low-viscosity resin (B) having a viscosity at 120° C. of less than 8000 Pa·s, and the following formula: A phosphorous compound (C) represented by the following formula (wherein n is 3 or 4) and a filler (D) which is an organic filler or an inorganic filler.

Description

  The present invention relates to a resin composition, a wiring board insulating layer, and a laminate.

  Printed wiring boards are widely used in electronic devices such as portable electronic devices. In particular, as the functions of portable electronic devices and the like have become higher in recent years, the frequency of signals has been increasing, and printed wiring boards suitable for such high frequency applications have been demanded. This high-frequency printed wiring board 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, and transmission loss is mainly a conductor loss caused by the copper foil and a dielectric loss caused by the insulating resin base material. Consists of. Therefore, in the 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.

  Materials for printed wiring boards are also required to have properties such as flame retardancy, heat resistance, and peel strength with copper foil, etc., and various resin compositions have been proposed to meet these requirements. In particular, since resins having a low dielectric loss tangent tend to have poor flame retardancy, it is desirable to add a flame retardant to the resin composition. Halogen compounds are known as such flame retardants, but they are environmentally unfavorable because they are harmful substances such as dioxins generated during incineration. Further, compounds of halogens (for example, bromine, etc.) other than fluorine have poor dielectric properties.

  Therefore, a resin composition containing a cyclophosphazene compound which is a halogen-free flame retardant has been proposed. For example, in Patent Document 1 (International Publication No. 2015/133292), (A) a polyphenylene ether (PPE) having a number average molecular weight of 500 to 5000, (B) a cyclophosphazene compound containing a vinyl group, (C). A resin composition containing a non-halogen epoxy resin, a (D) cyanate ester compound, and a (E) filler is disclosed. According to this resin composition, flame retardancy, thermal expansion coefficient, and moisture absorption are disclosed. It is said that it is possible to provide a printed wiring board having excellent heat resistance at the time.

  On the other hand, as a flame-retardant resin composition suitable as a solder resist for a flexible printed wiring board, a resin composition containing cyanophenoxy-modified phosphazene is known. For example, in Patent Document 2 (JP 2009-191252 A), (A) a carboxyl group- and ethylenically unsaturated group-containing urethane resin, (B) a phenoxyphosphazene compound, (C) a photopolymerization initiator, (D). A flame-retardant resin composition containing an ethylenically unsaturated group-containing compound, (E) flame-retardant component, (F) thermosetting component, and (G) thermosetting auxiliary agent is disclosed. In this document, the phenoxyphosphazene compound is merely positioned as a flame retardant having excellent compatibility with the urethane resin for the solder resist, and no study on dielectric loss tangent has been made.

International Publication No. 2015/133292 JP, 2009-191252, A

  In the production of a printed wiring board, an insulating layer is formed on a circuit by laminating a resin-coated copper foil on a substrate on which the circuit is formed and embedding the circuit with a resin layer as an insulating layer. However, since this work is performed in a semi-cured state (B-stage), if the fluidity (resin flow) of the resin is too high, it becomes impossible to secure the required insulating layer thickness due to the outflow of the resin. If the fluidity of the resin (resin flow) is too low, the insulating layer cures with undesired voids (voids). That is, if the resin flow is too high or too low, the circuit embedding property is deteriorated. Therefore, extremely careful compositional design in consideration of such characteristic changes is desired. On the other hand, the resin composition after curing (C-stage) is desired to have various properties such as low dielectric loss tangent, excellent heat resistance, flame retardancy, and handling property (flexibility). However, when a composition design that emphasizes circuit embeddability and handling (flexibility) is emphasized, various properties of the cured resin composition tend to deteriorate, especially flame retardancy and dielectric properties (low dielectric loss tangent). It becomes difficult to achieve both. That is, a resin composition which is excellent in circuit embedding property in a semi-cured state (B-stage) while improving various characteristics (dielectric property and flame retardancy) of the resin composition in a cured state (C-stage) is obtained. desired.

  The present inventor has recently found that a resin composition containing a predetermined high-viscosity resin (A), a predetermined low-viscosity resin (B), a predetermined phosphorus compound (C), and a predetermined filler (D) is difficult. It has been found that it has a significantly low dielectric loss tangent while being excellent in various properties such as flammability, circuit embedding property, and handling property (flexibility).

  Therefore, an object of the present invention is to provide a resin composition which is excellent in various properties such as flame retardancy, circuit embedding property, handling property (flexibility), and can bring about a significantly low dielectric loss tangent. is there.

（式中、ｎは３又は４である）
で表されるリン系化合物（Ｃ）と、
有機充填剤又は無機充填剤である充填剤（Ｄ）と、
を含む、樹脂組成物が提供される。According to one aspect of the invention,
Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrene elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds having a viscosity at 120° C. of 8000 Pa·s or more. And at least one high-viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism that does not generate a hydroxyl group,
Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrene elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds having a viscosity at 120° C. of less than 8000 Pa·s. At least one low-viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism that does not generate a hydroxyl group,
Formula (I) below:

(In the formula, n is 3 or 4)
A phosphorus compound (C) represented by
A filler (D) which is an organic filler or an inorganic filler,
A resin composition comprising:

  According to another aspect of the present invention, there is provided an insulating layer for a wiring board, which is obtained by curing the resin composition.

  According to another aspect of the present invention, there is provided a laminate having a resin layer formed by curing the resin composition on the surface of a metal layer.

Resin composition The resin composition of the present invention contains a high-viscosity resin (A), a low-viscosity resin (B), a phosphorus compound (C), and a filler (D). The high-viscosity resin (A) is a resin having a viscosity at 120° C. of 8000 Pa·s or more, and is a cyanate compound, a polyarylene ether compound, a cycloolefin compound, a hydrogenated or non-hydrogenated styrene elastomer, a polyimide compound, a siloxane compound. , A polyalkyl compound, and one or more compounds selected from the group consisting of compounds having a reaction mechanism that does not generate a hydroxyl group when reacting with an epoxy compound. The low-viscosity resin (B) has a viscosity of less than 8000 Pa·s at 120° C., and is a cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene elastomer, polyimide compound, siloxane compound, polyalkyl. One or more compounds selected from the group consisting of compounds and compounds having a reaction mechanism that does not generate a hydroxyl group when reacting with an epoxy compound. The phosphorus compound (C) is a cyclic cyanophenoxyphosphazene compound represented by the above formula (I). The filler (D) is an organic filler or an inorganic filler. Thus, according to the resin composition containing the predetermined high-viscosity resin (A), the predetermined low-viscosity resin (B), the predetermined phosphorus compound (C), and the predetermined filler (D), circuit embedding is performed. It is possible to bring about significantly low dielectric loss tangent and flame retardancy after curing while being excellent in various properties such as property and handling property (flexibility). For example, the resin composition of the present invention has a dielectric loss tangent at 10 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 of the dielectric loss tangent is not particularly limited, but is typically 0.0001 or more.

High viscosity resin (A) and low viscosity resin (B)
The high-viscosity resin (A) contained in the resin composition of the present invention has a viscosity at 120° C. of 8000 Pa·s or more, preferably 10,000 to 300,000 Pa·s, more preferably 50,000 to 200,000 Pa·s, and particularly preferably 70,000 to It is 150000 Pa·s. On the other hand, the low-viscosity resin (B) contained in the resin composition of the present invention has a viscosity at 120° C. of less than 8000 Pa·s, preferably 5000 Pa·s or less, more preferably 1000 Pa·s or less, and particularly preferably 0. It is 0.0001-10 Pa*s. By mixing two kinds of resins in this way, it is possible to realize a desired resin flow, improve the circuit embedding property at the time of circuit formation, and also improve the handling property (flexibility).

  In addition, the "viscosity at 120 degreeC" referred to in this specification uses a rheometer (dynamic viscoelasticity measuring device) (Thermo Scientific HAAKE MARS) for a semi-cured state (B-stage), and JIS. According to K 7117, it shall be measured by the following method. That is, when a resin sample having a diameter of 10 mm and a thickness of 100 μm was installed between a plate having a diameter of 10 mm and a flat plate of a torque measuring portion having a diameter of 10 mm, the temperature was raised at an angular velocity of 6.2832 rad/s and a heating rate of 2° C./min. The viscosity at 120° C. was measured. The viscosity was measured 3 times and the average value of 3 times was adopted.

  The high-viscosity resin (A) and the low-viscosity resin (B) are each independently a cyanate compound, polyarylene ether compound, cycloolefin compound, hydrogenated or non-hydrogenated styrene elastomer, polyimide compound, siloxane compound, polyalkyl. It is selected from the group consisting of a compound and a compound having a reaction mechanism that does not generate a hydroxyl group when reacting with an epoxy compound. Both of these compounds provide low dielectric properties (eg, 0.005 or less dielectric loss tangent at 10 Gz) either by themselves (in the case of a polymer) or when cured with a hardener (in the case of a monomer). It is a thing.

  According to a preferred embodiment of the present invention, the high viscosity resin (A) and/or the low viscosity resin (B) may contain a cyanate compound. Especially, it is more preferable that the low-viscosity resin (B) contains a cyanate compound. In any case, the cyanate compound can be any organic compound containing a cyanato group or a triazine skeleton, and is not particularly limited. The functional number of the compound containing a cyanate group may be monofunctional or polyfunctional and is not particularly limited, but from the viewpoint of cross-linking and curing, polyfunctionality is preferred because it is easy to use for resin-coated copper foil (RCC). Examples of the compound having a cyanate group include phenol novolac type cyanate, cresol novolac type cyanate, dicyclopentadiene novolac type cyanate, biphenyl novolac type cyanate, bisphenol A type dicyanate, bisphenol F type dicyanate, dicyclopentadiene dicyanate, biphenyl diphenylate. Cyanate and the like can be mentioned. These cyanate compounds may be used alone or in combination of two or more. On the other hand, in the case of a cyanate compound having a triazine skeleton, it is not particularly limited as long as it is a compound having a skeleton obtained by trimerizing one or more cyanate compounds having a cyanato group. The triazine skeleton may or may not contain a reactive functional group, but it is preferable that the triazine skeleton contains a reactive functional group because it is easy to use for a resin-coated copper foil (RCC) from the viewpoint of crosslinking and curing.

（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。低粘度樹脂（Ｂ）に用いる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。According to a preferred embodiment of the present invention, the high-viscosity resin (A) and/or the low-viscosity resin (B) can contain a polyarylene ether compound, preferably a polyphenylene ether compound. Especially, it is more preferable that the low-viscosity resin (B) contains a polyphenylene ether compound. In any case, 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 is there)
It is preferable that the compound has a skeleton represented by Examples of the polyphenylene ether compound used for the low-viscosity resin (B) include a styrene derivative of a polyphenylene ether oligomer, a terminal hydroxyl group-modified polyphenylene ether oligomer, a terminal methacryl modified polyphenylene ether oligomer, and a terminal glycidyl ether modified polyphenylene ether oligomer. Examples of products of styrene derivatives of polyphenylene ether oligomer include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Inc. Examples of the product of the terminal hydroxyl group-modified polyphenylene ether oligomer include SA-90 and SA-120 manufactured by SABIC. As an example of the product of the terminal methacryl-modified polyphenylene ether oligomer, SA-9000 manufactured by SABIC is mentioned.

（式中、ｎは１〜３０、ｍは１〜３０である）
で表される数平均分子量３０００未満のポリフェニレンエーテル樹脂を含むものであり、より好ましい数平均分子量は８００〜２８００である。かかる上記式を満たすポリフェニレンエーテル樹脂の製品例としては、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。なお、数平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）法によりポリスチレン換算で測定した値を用いてもよい。Particularly preferably, the polyphenylene ether compound used for the low-viscosity resin (B) has the following formula:

(In the formula, n is 1 to 30 and m is 1 to 30)
A polyphenylene ether resin having a number average molecular weight of less than 3,000 represented by is included, and a more preferable number average molecular weight is 800 to 2,800. Examples of products of the polyphenylene ether resin satisfying the above formula include OPE-2St-1200 and OPE-2St-2200 manufactured by Mitsubishi Gas Chemical Co., Inc. The number average molecular weight may be a value measured in terms of polystyrene by GPC (gel permeation chromatography) method.

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立して−Ｈ又は炭素数１〜５のアルキル基であり、ｎは１〜３０００である）
で表されるジシクロペンタジエン骨格を含む化合物、又は下記式：

（式中、Ｘは−ＣＨ_２−又は−Ｃ_２Ｈ_４−であり、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立して−Ｈ又は炭素数１〜５のアルキル基であり、ｎは０〜２、ｍは１〜１０００である）
で表されるノルボルネン骨格を含む化合物、又は下記式：

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立して−Ｈ又は炭素数１〜５のアルキル基であり、ｎは１〜３０００である）
で表されるインダン骨格を含む化合物のいずれかであるのが好ましい。シクロオレフィン化合物の例としては、（ｉ）ジシクロペンタジエン型エポキシ樹脂、（ｉｉ）ノルボルネンモノマー、（ｉｉｉ）上記ジシクロペンタジエン骨格、上記ノルボルネン骨格及び上記インダン骨格から選ばれる１種以上の骨格を含むシクロオレフィン系ポリマー等が挙げられる。シクロオレフィン系ポリマーの製品例としては、日本ゼオン株式会社製ＺＥＯＮＯＲ（登録商標）、Ｔｏｐａｓ Ａｄｖａｎｃｅｄ Ｐｏｌｙｍｅｒｓ ＧｍｂＨ製ＴＯＰＡＳ（登録商標）等が挙げられる。According to a preferred embodiment of the present invention, the high viscosity resin (A) and/or the low viscosity resin (B) may contain a cycloolefin compound. The cycloolefin compound has the following formula:

(In the formula, R _1, R _2, R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3000)
A compound containing a dicyclopentadiene skeleton represented by, or the following formula:

(In the formula, X is —CH ₂ — or —C ₂ H ₄ —, R _1, R _2, R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, (n is 0 to 2 and m is 1 to 1000)
A compound containing a norbornene skeleton represented by, or the following formula:

(In the formula, R _1, R _2, R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3000)
It is preferably any of the compounds containing an indane skeleton represented by Examples of the cycloolefin compound include (i) a dicyclopentadiene type epoxy resin, (ii) a norbornene monomer, (iii) one or more skeletons selected from the above dicyclopentadiene skeleton, the above norbornene skeleton and the above indane skeleton. Examples include cycloolefin-based polymers. Examples of products of the cycloolefin polymer include ZEONOR (registered trademark) manufactured by Nippon Zeon Co., Ltd. and TOPAS (registered trademark) manufactured by Topas Advanced Polymers GmbH.

  According to a preferred embodiment of the present invention, the high-viscosity resin (A) and/or the low-viscosity resin (B) may contain a styrene elastomer. In particular, it is more preferable that the high viscosity resin (A) contains a styrene elastomer. In any case, the styrene elastomer may be hydrogenated or non-hydrogenated. That is, the styrene-based elastomer is a compound containing a site derived from styrene, and may be a polymer containing a site derived from a compound having a polymerizable unsaturated group such as olefin other than styrene. When a double bond is present at the site derived from the compound having a polymerizable unsaturated group of the styrene-based elastomer, the double bond part may be hydrogenated or may not be hydrogenated. It may be. Examples of styrene elastomers include TR manufactured by JSR Corporation, SIS manufactured by JSR Corporation, Tuftec (registered trademark) manufactured by Asahi Kasei Corporation, Septon (registered trademark) manufactured by Kuraray Co., Ltd., and Hibler (registered trademark) manufactured by Kuraray Co., Ltd., etc. Is mentioned. In particular, it is preferable to use a hydrogenated styrene-butadiene elastomer as the high viscosity resin (A).

  According to a preferred embodiment of the present invention, the high viscosity resin (A) and/or the low viscosity resin (B) can contain a polyimide compound. The polyimide compound is a compound containing an imide skeleton, and the skeleton of the precursor acid anhydride and amine may be any skeleton.

（式中、Ｒ_１及びＲ_２はそれぞれ独立してアルキル基、フェニル基又は側鎖に枝分かれしたシロキサン骨格であり、ｎは１〜１００である）
で表されるシロキサン骨格を含む化合物であるのが典型的であるが、他の樹脂との相溶性や反応性という点でシロキサン以外の骨格ないし官能基を含むのが好ましい。シロキサン化合物の例としては、シリコーンオイル等が挙げられる。例えば、他成分との反応性や相溶性の観点から、信越化学工業株式会社製ＫＦ−８０１０、Ｘ−２２−１６１Ａ、Ｘ−２２−２４４５や東レダウコーニング株式会社製ＢＹ１６−８５３Ｕ、ＢＹ１６−８５５等の反応性官能基を有するシリコーンオイルを任意に変性させたものやプレポリマー化したものを用いてもよい。According to a preferred embodiment of the present invention, the high viscosity resin (A) and/or the low viscosity resin (B) may contain a siloxane compound. The siloxane compound has the following formula:

(In the formula, R ₁ and R ₂ are each independently an alkyl group, a phenyl group or a siloxane skeleton branched into a side chain, and n is 1 to 100)
A compound having a siloxane skeleton represented by is typically used, but it is preferable that the compound has a skeleton or a functional group other than siloxane from the viewpoint of compatibility and reactivity with other resins. Examples of the siloxane compound include silicone oil and the like. For example, from the viewpoint of reactivity and compatibility with other components, Shin-Etsu Chemical Co., Ltd. KF-8010, X-22-161A, X-22-2445 and Toray Dow Corning Co., Ltd. BY16-853U, BY16-855. A silicone oil having a reactive functional group such as the above may be optionally modified or prepolymerized.

（式中、ｎは２〜１０００００である）
で表されるアルキル骨格を含む化合物であるのが典型的であるが、アルキル骨格以外の骨格も任意に含むことができる。ポリアルキル化合物の例としては、ポリエチレン、ポリプロピレン、三井化学株式会社製ＡＰＥＬ^ＴＭ等のオレフィンコポリマー、長鎖アルキルエポキシ等が挙げられる。According to a preferred embodiment of the present invention, the high viscosity resin (A) and/or the low viscosity resin (B) may contain a polyalkyl compound. The polyalkyl compound has the following formula:

(In the formula, n is 2 to 100,000)
It is typically a compound containing an alkyl skeleton represented by, but it is possible to optionally include a skeleton other than the alkyl skeleton. Examples of polyalkyl compounds include polyethylene, polypropylene, olefin copolymers such as APEL ^™ manufactured by Mitsui Chemicals, Inc., long chain alkyl epoxies, and the like.

  According to a preferred embodiment of the present invention, the high-viscosity resin (A) and/or the low-viscosity resin (B) can contain a compound having a reaction mechanism that does not generate a hydroxyl group when reacting with an epoxy compound. In particular, it is more preferable that the low-viscosity resin (B) contains the above compound. In any case, examples of the above compound include imidazole, active ester, carbodiimide and the like, and carbodiimide is particularly preferable from the viewpoint of reactivity.

  As described above, as the high-viscosity resin (A) and the low-viscosity resin (B), the same or different resins can be used except for the viscosity, but as the high-viscosity resin (A), a hydrogenated or non-hydrogenated styrene elastomer is used. It is particularly preferable to select and a polyarylene ether compound as the low-viscosity resin (B). It is more preferable to select a polyphenylene ether compound as the polyarylene ether compound.

  The content ratio of various components of the resin composition of the present invention can be optimized by combining each component, and the content ratio is not particularly limited, but the content of the high-viscosity resin (A) is high. The total amount of the resin (A), the low viscosity resin (B) and the phosphorus compound (C) is 100 parts by weight, preferably 10 to 80 parts by weight, more preferably 15 to 75 parts by weight, further preferably 20 to 70 parts by weight, particularly preferably 25 to 65 parts by weight, most preferably 30 to 60 parts by weight. The content of the high-viscosity resin (A) described above is particularly preferable when the high-viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer and the low-viscosity resin (B) is a polyphenylene ether compound. apply.

  On the other hand, the content of the low viscosity resin (B) in the resin composition of the present invention is 10 with the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C) being 100 parts by weight. It is preferably from 50 to 50 parts by weight, more preferably from 15 to 45 parts by weight, further preferably from 15 to 40 parts by weight, particularly preferably from 20 to 40 parts by weight, most preferably from 20 to 35 parts by weight. The content of the low-viscosity resin (B) described above is particularly preferable when the high-viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer and the low-viscosity resin (B) is a polyphenylene ether compound. apply.

（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。例えば、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。 Phosphorus compound (C)
The phosphorus compound (C) contained in the resin composition of the present invention functions as a flame retardant and has the following formula (I):

(In the formula, n is 3 to 4)
It is a cyclic cyanophenoxyphosphazene compound represented by. 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). For example, as an example of the product of the compound of n=3 alone in the formula (I), FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. may be mentioned, and a mixture of the compound of n=3 and the compound of n=4 in the formula (I). As an example of the product, FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

  The content of the phosphorus compound (C) in the resin composition of the present invention is 10 to 50, with the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C) being 100 parts by weight. It is preferably 15 parts by weight, more preferably 15 to 45 parts by weight, further preferably 15 to 40 parts by weight, particularly preferably 18 to 38 parts by weight, and most preferably 20 to 35 parts by weight. The content of the phosphorus compound (C) described above is particularly preferable when the high-viscosity resin (A) is a hydrogenated or non-hydrogenated styrene-based elastomer and the low-viscosity resin (B) is a polyphenylene ether compound. apply.

Filler (D)
In the present specification, the "filler" refers to a filler which is not compatibilized in the resin composition and exists in the resin composition as a single phase of the filler. The filler may or may not have a surface treatment layer on the surface of the filler, and the surface treatment layer may or may not be compatibilized with the resin component in the resin composition. You don't have to. The filler (D) contained in the resin composition of the present invention is not particularly limited, and various fillers generally used for addition to the resin composition can be used. Therefore, the filler may be either an organic filler or an inorganic filler, but the inorganic filler is preferable from the viewpoint of electrical characteristics and flame retardancy. Examples of inorganic fillers include silica, talc, boron nitride (BN), and the like. The inorganic filler is not particularly limited as long as it can be dispersed in the resin composition, but silica is preferable from the viewpoint of dispersibility and dielectric properties. The organic filler is not particularly limited as long as it is incompatible with the high-viscosity resin (A) and the low-viscosity resin (B), but a fluorine-based organic filler is preferable from the viewpoint of dielectric properties and flame retardancy. ..

  The filler (D) is preferably an inorganic filler. The average particle diameter D50 of the inorganic filler is preferably 0.1 to 3 μm, more preferably 0.3 to 1.5 μm. By using silica particles having an average particle diameter D50 within the above range (for example, spherical silica particles), it is possible to provide a resin composition having excellent fluidity and processability. The filler (D) may be in any form such as crushed particles, spherical particles, core-shell particles and hollow particles.

  The content of the filler (D) in the resin composition of the present invention is 5 to 200 parts by weight, with the total amount of the high viscosity resin (A), the low viscosity resin (B) and the phosphorus compound (C) being 100 parts by weight. It is preferably 25 parts by weight, more preferably 25 parts by weight to 190 parts by weight, still more preferably 45 parts by weight to 180 parts by weight, particularly preferably 90 parts by weight to 170 parts by weight, most preferably 110 parts by weight to 160 parts by weight. The content of the filler (D) described above is particularly preferably applied when the high-viscosity resin (A) is a hydrogenated or non-hydrogenated styrene elastomer and the low-viscosity resin (B) is a polyphenylene ether compound. .

Applications The resin composition of the present invention is excellent in various properties such as circuit embedding property and handling property (flexibility) at the time of circuit formation, but exhibits low dielectric loss tangent and excellent flame retardancy after curing. It is particularly suitable as an insulating layer for printed wiring boards. That is, the resin composition of the present invention is preferably used for the insulating layer for wiring boards. Therefore, according to a preferred aspect of the present invention, there is provided an insulating layer for a wiring board, which is obtained by curing the resin composition. Further, according to another preferred embodiment of the present invention, there is provided a laminate including a resin layer formed by curing a resin composition on the surface of a metal layer.

  The present invention will be described more specifically by the following examples.

Examples 1-16
(1) Preparation of Raw Materials First, various raw materials shown in Table 1 were prepared. Details of each raw material are as follows.

<High viscosity resin (A)>
MP-10 (hydrogenated styrene elastomer, manufactured by Asahi Kasei Co., Ltd., viscosity at 120° C.: 75400 Pa·s)
HG-252 (SEEPS-OH: polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene, terminal hydroxyl group modification, manufactured by Kuraray Co., Ltd., viscosity at 120° C.: 10060 Pa·s)
<Low viscosity resin (B)>
V-03 (carbodiimide resin, manufactured by Nisshinbo Chemical Co., Ltd., viscosity at 120° C.: less than 8000 Pa·s)
OPE-2St-1200 (styrene derivative of bifunctional polyphenylene ether oligomer, manufactured by Mitsubishi Gas Chemical Co., Inc., number average molecular weight of about 1200, viscosity at 120°C: less than 8000 Pa·s)
OPE-2St-2200 (styrene derivative of bifunctional polyphenylene ether oligomer, manufactured by Mitsubishi Gas Chemical Co., Inc., number average molecular weight of about 2200, viscosity at 120° C.: less than 8000 Pa·s)
SA-90 (bifunctional polyphenylene ether oligomer, manufactured by SABIC, viscosity at 120°C: less than 8000 Pa·s)
<Phosphorus compound (C)>
FP-300B (cyclic cyanophenoxyphosphazene compound, manufactured by Fushimi Pharmaceutical Co., Ltd., compound in which n=3 to 4 in formula (I))
FP-110 (Cyclic phenoxyphosphazene compound, manufactured by Fushimi Pharmaceutical Co., Ltd., compound not satisfying formula (I))
SPH-100 (cyclic hydroxyphenoxyphosphazene compound, manufactured by Otsuka Chemical Co., Ltd., compound not satisfying formula (I))
<Filler (D)>
SC4050 (spherical silica particles, manufactured by Admatechs Co., Ltd., average particle diameter D50 measured by laser diffraction type particle size distribution measurement: 1.0 μm)

(2) Production of varnish High-viscosity resin, low-viscosity resin (excluding Example 15), phosphorus compound (excluding Example 14) and filler (excluding Example 16) having the raw material names and solid content weight ratios shown in Table 1 To the above), a toluene solvent was added so that the solid content concentration became 50%, and the mixture was dissolved and dispersed at 60° C. using a disperser. A resin solution (varnish) thus prepared was obtained.

(3) Manufacture of semi-cured (B-stage) resin-coated copper foil The obtained resin solution was used as an electrolytic copper foil (TQ-M4-VSP foil, manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 18 μm, ten-point average). It was applied to a surface having a roughness (Rzjis) of 0.4 μm using a comma coater so that the thickness of the dried resin layer was 130 μm. The coating film was dried at 150° C. for 3 minutes to semi-cure the resin composition. Thus, a resin-coated copper foil having a semi-cured (B-stage) resin layer was produced.

(4) Manufacture of a resin film alone Two resin-coated copper foils are stuck together such that their resin layers are in contact with each other, and hot vacuum pressing is performed at 200° C. for 90 minutes under a heating/pressurizing condition of 30 kgf/cm ^2. Molding was performed to produce a double-sided copper clad laminate. All of 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 resin film alone obtained in (4) above or the semi-cured resin-coated copper foil obtained in (3) above.

(5a) Dielectric Property The dielectric constant Dk and the dielectric loss tangent Df at 10 GHz of the resin film alone were measured by the perturbation type cavity resonator method. This measurement was performed in accordance with JIS R 1641 using a measuring device (a resonator made by KEYCOM and a network analyzer made by KEYSIGHT) after cutting the resin film alone according to the sample size of the resonator. The measured Df value was rated and evaluated according to the following criteria.
<Dielectric property evaluation criteria>
-Evaluation A: Df value at 10 GHz is less than 0.0020-Evaluation B: Df value at 10 GHz is 0.0020 to less than 0.0025-Evaluation C: Df value at 10 GHz is 0.0025 to less than 0.0030-Evaluation D : Df value at 10 GHz is 0.0030 or more

(5b) Glass transition temperature (Tg)
With respect to the resin film alone, the peak temperature of Tan δ was measured as the glass transition temperature (Tg) by dynamic viscoelasticity measurement (DMA: Dynamic Mechanical Analysis). This measurement was performed using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.) according to JIS C6481. The measured glass transition temperature (Tg) was rated and evaluated according to the following criteria.
<Glass transition temperature (Tg) evaluation criteria>
-Evaluation A: Tg is 170°C or higher-Evaluation B: Tg is 150°C or higher and lower than 170°C-Evaluation C: Tg is 130°C or higher and lower than 150°C-Evaluation D: Tg is lower than 130°C

(5c) Handling property The handling property of the resin film itself was evaluated by the following procedure. First, a single resin film having a size of 10 cm×30 cm and a thickness of 250 μm was prepared. One short side of this resin film alone was fixed to a horizontal clamp, the other short side was vertically hung up to a position as high as 15 cm from the clamp, and then the resin film alone was separated. The presence or absence of cracks in the resin film when the resin film was dropped and bent due to its own weight was visually checked, and the presence or absence of whitening when the sample was bent at an angle of 180° was visually checked, and the rating was evaluated according to the following criteria. .
<Handling evaluation criteria>
-Evaluation A: The resin film was not cracked and whitening did not occur.
-Evaluation B: The resin film was not cracked, but whitening occurred.
-Evaluation D: The resin film was cracked.
Here, "whitening" refers to the appearance of white turbidity due to the generation of minute cracks inside the resin film when stress is applied to it.

(5d) Resin flow Four sheet pieces with a size of 10 cm×10 cm were cut out from a resin-coated copper foil (resin layer thickness 130 μm) in a semi-cured state (B-stage). A sample was prepared by laminating these four sheet pieces so that the resin-copper foil layers were staggered. The obtained sample was hot-pressed at 170° C. for 10 minutes at a pressure of 14 kgf/cm ² using a hot-pressing machine. The resin flow was measured by dividing the weight of the resin protruding from the area of 10 cm×10 cm, which is the original size, by the original resin weight, and multiplying the obtained value by 100. The resin flow value measured was rated and evaluated according to the following criteria.
<Resin flow evaluation criteria>
-Evaluation A: Resin flow value is more than 1.0% and 5.0% or less-Evaluation B: Resin flow value is more than 0.0% and 1.0% or less, or more than 5.0% and 10.0% Below-Evaluation C: Resin flow value is more than 10.0% and 20.0% or less-Evaluation D: Resin flow value is 0.0% or more than 20.0%

(5e) Flame Retardancy A vertical burning test was carried out on the resin film alone in accordance with the UL94 standard, and the rating was evaluated according to the following criteria.
<Flame retardancy evaluation criteria>
-Evaluation A: V-0 evaluation in UL94 standard-Evaluation B: V-1 evaluation in UL94 standard-Evaluation C: V-2 evaluation in UL94 standard-Evaluation D: HB evaluation in UL94 standard

(5f) Circuit embedding property A resin-coated copper foil (resin layer thickness 130 μm) in a semi-cured state (B-stage) is laminated on a substrate on which a circuit pattern (circuit height 35 μm) is formed, and insulation consisting of the resin layer is formed. A laminate having a circuit pattern embedded in the layers was obtained. In the obtained laminated body, (i) whether or not there are voids, and (ii) whether or not the required insulating layer thickness (specifically within 95 μm±10% from the circuit top) is secured The rating was evaluated based on the following criteria.
<Embedding evaluation criteria>
-Evaluation A: The required insulating layer thickness can be secured and no void exists.
-Evaluation B: The void is not present but the required insulating layer thickness is not secured, or the insulating layer thickness is secured but the void is present.
-Evaluation D: The required insulating layer thickness is not secured, and voids are present.

(5g) Evaluation result The evaluation result was as shown in Tables 1 and 2.

Claims (15)

Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrene elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds having a viscosity at 120° C. of 8000 Pa·s or more. And at least one high-viscosity resin (A) selected from the group consisting of compounds having a reaction mechanism that does not generate a hydroxyl group,
Reacts with cyanate compounds, polyarylene ether compounds, cycloolefin compounds, hydrogenated or non-hydrogenated styrene elastomers, polyimide compounds, siloxane compounds, polyalkyl compounds, and epoxy compounds having a viscosity at 120° C. of less than 8000 Pa·s. At least one low-viscosity resin (B) selected from the group consisting of compounds having a reaction mechanism that does not generate a hydroxyl group,
Formula (I) below:

(In the formula, n is 3 or 4)
A phosphorus compound (C) represented by
A filler (D) which is an organic filler or an inorganic filler,
A resin composition comprising:   The resin composition according to claim 1, wherein the filler (D) is an inorganic filler.   The resin composition according to claim 2, wherein the inorganic filler is silica particles having an average particle diameter D50 of 0.1 to 3 µm. The high viscosity resin (A) and/or the low viscosity resin (B) contains a polyphenylene ether compound as the polyarylene ether compound, and the polyphenylene ether compound has the following formula:

(In the formula, 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 according to any one of claims 1 to 3, which is a compound containing a skeleton represented by.   The high viscosity resin (A) and/or the low viscosity resin (B) contains the cyanate compound, and the cyanate compound is an organic compound containing a cyanato group or a triazine skeleton. The resin composition according to item. The high viscosity resin (A) and/or the low viscosity resin (B) contains the cycloolefin compound, and the cycloolefin compound has the following formula:

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3000)
A compound containing a dicyclopentadiene skeleton represented by, or the following formula:

(In the formula, X is —CH ₂ — or —C ₂ H ₄ —, and R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, (n is 0 to 2 and m is 1 to 1000)
A compound containing a norbornene skeleton represented by, or the following formula:

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently —H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3000)
The resin composition according to any one of claims 1 to 5, which is a compound containing an indane skeleton.   The resin composition according to any one of claims 1 to 6, wherein the high viscosity resin (A) and/or the low viscosity resin (B) contains the styrene elastomer.   The resin composition according to any one of claims 1 to 7, wherein the high-viscosity resin (A) and/or the low-viscosity resin (B) contains the polyimide compound.   The resin composition according to any one of claims 1 to 8, wherein the high-viscosity resin (A) and/or the low-viscosity resin (B) contains the siloxane compound.   The high viscosity resin (A) is the styrene-based elastomer, and the low viscosity resin (B) is a polyphenylene ether compound as the polyarylene ether compound. Resin composition.   Assuming that the total amount of the high-viscosity resin (A), the low-viscosity resin (B) and the phosphorus compound (C) is 100 parts by weight, 10 to 80 parts by weight of the high-viscosity resin (A) and 10 to 50 parts by weight are used. Any of claims 1 to 10, comprising parts by weight of the low viscosity resin (B), 10 to 50 parts by weight of the phosphorus compound (C), and 5 to 200 parts by weight of the filler (D). The resin composition according to 1 above.   20 to 70 parts by weight of the high viscosity resin (A), 15 to 40 parts by weight of the low viscosity resin (B), 15 to 40 parts by weight of the phosphorus compound (C), and 45 to 180 parts by weight. The resin composition according to claim 11, which comprises the filler (D).   An insulating layer for a wiring board, which is obtained by curing the resin composition according to any one of claims 1 to 12.   The resin composition according to any one of claims 1 to 12, which has a dielectric loss tangent at 10 GHz after curing of less than 0.003. A laminate comprising a resin layer obtained by curing the resin composition according to any one of claims 1 to 12 and 14 on the surface of a metal layer.