WO2018225665A1 - 樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び金属張積層板の製造方法 - Google Patents

樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び金属張積層板の製造方法 Download PDF

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Publication number
WO2018225665A1
WO2018225665A1 PCT/JP2018/021300 JP2018021300W WO2018225665A1 WO 2018225665 A1 WO2018225665 A1 WO 2018225665A1 JP 2018021300 W JP2018021300 W JP 2018021300W WO 2018225665 A1 WO2018225665 A1 WO 2018225665A1
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WIPO (PCT)
Prior art keywords
resin composition
metal
insulating layer
cured product
clad laminate
Prior art date
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PCT/JP2018/021300
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English (en)
French (fr)
Inventor
陽介 石川
一輝 松村
岸野　光寿
Original Assignee
パナソニックＩｐマネジメント株式会社
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Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to US16/619,385 priority Critical patent/US20200157300A1/en
Priority to KR1020197035594A priority patent/KR102286704B1/ko
Publication of WO2018225665A1 publication Critical patent/WO2018225665A1/ja

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    • C08J2461/10—Phenol-formaldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/04—Epoxynovolacs

Definitions

  • the present invention relates to a resin composition, a prepreg, a metal-clad laminate, a printed wiring board, and a method for producing a metal-clad laminate, and more specifically, a resin composition containing an epoxy resin, a dried or semi-cured product of the resin composition
  • the present invention relates to a prepreg comprising a metal-clad laminate and a printed wiring board having an insulating layer containing a cured product of the resin composition, and a method for producing a metal-clad laminate using the resin composition.
  • An object of the present invention is to provide a resin composition that contains an epoxy resin and can become a cured product having heat resistance by curing, a prepreg provided with a dried or semi-cured product of the resin composition, and a cured product of the resin composition. It is providing the manufacturing method of the metal-clad laminated board using the metal-clad laminated board provided with the insulating layer containing, a printed wiring board, and a resin composition.
  • the resin composition according to one embodiment of the present invention contains an epoxy resin (A), a phenol compound (B), and an imidazole compound (C) having a triazine skeleton.
  • the cured product of the resin composition has a glass transition temperature of 260 ° C. or higher.
  • the prepreg according to an aspect of the present invention includes a fiber base material and a dried or semi-cured product of the resin composition impregnated in the fiber base material.
  • the metal-clad laminate according to one embodiment of the present invention includes an insulating layer and a metal layer that overlaps the insulating layer.
  • the insulating layer includes a cured product of the resin composition.
  • the printed wiring board according to one aspect of the present invention includes an insulating layer and a conductor wiring overlapping the insulating layer, and the insulating layer includes a cured product of the resin composition.
  • a method for producing a metal-clad laminate according to one aspect of the present invention includes a method of stacking a metal foil on a prepreg comprising a fiber base and a dried or semi-cured product of the resin composition impregnated in the fiber base. Then, by hot pressing, an insulating layer including the fiber base material and a cured product of the resin composition and a metal layer made of the metal foil are produced.
  • the resin composition contains an epoxy resin (A), a phenol compound (B), and an imidazole compound (C) having a triazine skeleton.
  • the maximum heating temperature during the hot pressing is 280 ° C. or higher.
  • the resin composition contains an epoxy resin (A), a phenol compound (B), and an imidazole compound (C) having a triazine skeleton.
  • the cured product of the resin composition has a glass transition temperature of 260 ° C. or higher.
  • cured material is as explaining in the following Example.
  • a resin composition that can be cured by heat to become a cured product, a cured product having heat resistance, a prepreg provided with a dried or semi-cured product of the resin composition, and a cured product of the resin composition
  • a metal-clad laminate and a printed wiring board having an insulating layer containing the metal-clad laminate and a method for producing a metal-clad laminate using a resin composition can be provided.
  • the cured product is produced by heating a resin composition, a dried resin composition or a semi-cured resin composition.
  • the heating conditions are conditions that allow the resin composition to be sufficiently cured.
  • the resin composition may be a cured product having a glass transition temperature of 260 ° C. by being heated under at least one condition.
  • the conditions for heating the resin composition, the dried resin composition or the semi-cured resin composition are, for example, within the range of the maximum heating temperature of 260 to 400 ° C., the rate of temperature increase from the start of heating to the time of reaching the maximum heating temperature. Is in the range of 2 to 8 ° C./sec, and the heating time is in the range of 1.5 to 6 minutes.
  • the pressing pressure is in the range of 0.5 to 5 MPa, for example. It is preferable that the hardened
  • An insulating layer in a metal-clad laminate and a printed wiring board can be produced from the resin composition.
  • the resin composition can improve the heat resistance of the insulating layer.
  • imidazole compounds having a triazine skeleton are known.
  • International Publication WO2010 / 035452 also discloses 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′) as an example of an imidazole curing accelerator. Ethyl-s-triazine and the like are described.
  • the inventor has made a dramatic idea of using a resin composition containing an imidazole compound having a triazine skeleton in order to produce an insulating layer in a metal-clad laminate and a printed wiring board. Obtained. Furthermore, the inventor has found that a cured product of such a resin composition can have a high glass transition temperature, and an insulating layer having high heat resistance can be produced by using such a resin composition. The present invention has been found and the present invention has been completed.
  • the epoxy resin (A) is, for example, naphthalene type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, aralkyl.
  • Type epoxy resin, biphenol type epoxy resin, dicyclopentadiene type epoxy resin, epoxidized product of condensation product of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate and alicyclic epoxy resin Can contain at least one compound.
  • the epoxy resin (A) particularly preferably contains a phenol novolac type epoxy resin.
  • the resin composition contains a phenol novolac type epoxy resin together with the imidazole compound (C) having a triazine skeleton, the cured product of the resin composition can have a particularly high glass transition temperature.
  • the epoxy equivalent of the epoxy resin (A) is preferably 200 or more.
  • the cured product can have particularly excellent thermal stability.
  • the phenol compound (B) is a curing agent for the epoxy resin (A).
  • examples of the phenol compound (B) include tetrakisphenol resin, novolak type phenol resin, naphthalene type phenol resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, cresol aralkyl.
  • Resin naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, amino Triazine modified phenolic resin, biphenol, glyoxal tetraphenol resin, bisphenol A Novo It can contain at least one compound selected from the group consisting of click resin and bisphenol F novolac resin.
  • the phenol compound (B) particularly preferably contains a tetrakisphenol resin.
  • the resin composition contains the phenol compound (B) containing a tetrakisphenol resin together with the imidazole compound (C) having a triazine skeleton, the cured product of the resin composition can have a particularly high glass transition temperature. It is particularly preferred if the epoxy resin (A) contains a phenol novolac type epoxy resin and the phenol compound (B) contains a tetrakisphenol resin.
  • the hydroxyl equivalent of the phenol compound (B) is preferably 150 or more.
  • the cured product can have particularly excellent thermal stability.
  • the equivalent ratio of the epoxy resin (A) and the phenol compound (B) is preferably in the range of 0.8: 1.2 to 1.2: 0.8.
  • the resin composition contains an imidazole compound (C) having a triazine skeleton.
  • cured material of a resin composition can have a high glass transition temperature, and can also have a glass transition temperature of 260 degreeC or more.
  • cured material of a resin composition can have high heat resistance.
  • the insulating layer containing the cured product of the resin composition can have high adhesion to the metal layer.
  • the imidazole compound (C) can contain, for example, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine.
  • the imidazole compound (C) particularly preferably contains 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')] ethyl-s-triazine.
  • the cured product of the resin composition can have a particularly high glass transition temperature, and the insulating layer containing the cured product can have particularly high heat resistance.
  • the ratio of the imidazole compound (C) to the total of the epoxy resin (A) and the phenol compound (B) in the resin composition is preferably in the range of 0.02 to 1% by mass.
  • this ratio is 0.02% by mass or more, the cured product can have a particularly high glass transition temperature.
  • this ratio is 1% by mass or less, even when the resin composition is stored when the solvent is contained, the components of the resin composition are hardly aggregated, that is, the resin composition has good varnish storage stability.
  • the insulating layer can have good solder heat resistance.
  • varnish storage stability can be evaluated by the method shown in the following Example.
  • the resin composition may contain an inorganic filler.
  • the inorganic filler include silica, barium sulfate, silicon oxide powder, crushed silica, calcined talc, barium titanate, titanium oxide, clay, alumina, mica, boehmite, zinc borate and zinc stannate, and various other metals. It can contain at least one component selected from the group consisting of oxides and metal hydrates.
  • the coefficient of linear expansion of the insulating layer containing the cured product of the resin composition can be reduced. For this reason, deformation
  • the content of the inorganic filler is preferably 80% by mass or less with respect to the total amount of the resin composition, and particularly preferably in the range of 10 to 80% by mass.
  • the resin composition may contain a solvent.
  • the solvent can contain at least one component selected from the group consisting of ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, aromatic solvents such as toluene and xylene, and nitrogen-containing solvents such as dimethylformamide.
  • the resin composition may contain components other than those described above.
  • the resin composition may contain a light stabilizer, a viscosity modifier, a flame retardant, and the like.
  • the prepreg includes a fiber base material and a dried or semi-cured product of the resin composition impregnated in the fiber base material.
  • the fiber base material is, for example, a woven fabric of inorganic fibers such as glass, a non-woven fabric of inorganic fibers, an aramid cloth, a polyester cloth, or paper.
  • the fiber substrate is preferably a glass woven fabric, that is, a glass cloth.
  • a fiber base material is impregnated with a resin composition by a known method such as a dipping method or a coating method.
  • the resin composition is heated to be dried or semi-cured.
  • the heating conditions are, for example, within the range of heating temperature 120 to 190 ° C. and within the range of heating time 3 to 15 minutes, but are not limited thereto. Thereby, a prepreg is manufactured.
  • the metal-clad laminate will be described.
  • the metal-clad laminate includes an insulating layer and a metal layer that overlaps the insulating layer.
  • the insulating layer includes a cured product of the resin composition described above.
  • the metal-clad laminate may include two metal layers, and the two metal layers may overlap one surface of the insulating layer and the surface on the opposite side.
  • the metal-clad laminate may include only one metal layer, and this one metal layer may overlap one surface of the insulating layer.
  • the cured product of the resin composition can have a high glass transition temperature, and thus the metal-clad laminate can have high heat resistance. Furthermore, in the metal-clad laminate, a high peeling strength of the metal layer relative to the insulating layer can be achieved.
  • the cured product is produced, for example, by heating a resin composition, a dried resin composition, or a semi-cured resin composition.
  • the maximum heating temperature when heating the resin composition is preferably 260 ° C. or higher. In this case, a particularly high glass transition temperature and a particularly high peel strength can be achieved.
  • the maximum heating temperature is more preferably in the range of 260 to 400 ° C., and further preferably in the range of 280 to 320 ° C.
  • the rate of temperature increase from the start of heating when the resin composition is heated to the time when the maximum heating temperature is reached is 2 ° C./sec or more.
  • the cured product can have a particularly high glass transition temperature.
  • the rate of temperature rise is more preferably in the range of 2 to 8 ° C./sec, and further preferably in the range of 3 to 5 ° C./sec.
  • a metal foil is stacked on the prepreg described above or a laminate in which a plurality of prepregs are laminated to produce a laminate.
  • the metal-clad laminate includes two metal layers, the two metal foils are stacked on one surface of the prepreg or laminate and the opposite surface, respectively, to produce a laminate.
  • the metal-clad laminate includes only one metal layer, a metal foil is stacked on one surface of the prepreg or laminate to produce a laminate.
  • the cured product contained in the insulating layer in this metal-clad laminate can have a high glass transition temperature, and can also have a glass transition temperature of 260 ° C. or higher. For this reason, the metal-clad laminate can have high heat resistance.
  • a high peeling strength of the metal layer relative to the insulating layer can be achieved, and a peeling strength of 4 N / cm or more can also be achieved.
  • the method for measuring the peel strength is as described in the following examples.
  • the conditions for hot pressing the laminate include, for example, the maximum heating temperature, pressing pressure, and heating time.
  • the maximum heating temperature is preferably 260 ° C. or higher, more preferably in the range of 260 to 400 ° C., and even more preferably in the range of 280 to 320 ° C.
  • the rate of temperature increase from the start of heating during hot pressing to the time when the maximum heating temperature is reached is preferably 2 ° C./sec or more, more preferably in the range of 2 to 8 ° C./sec, as described above. More preferably, it is in the range of 3 to 5 ° C./sec.
  • the press pressure is, for example, in the range of 0.5 to 5 MPa. In this case, a particularly high glass transition temperature and a particularly high peel strength can be achieved.
  • the press pressure is preferably in the range of 0.5 to 5 MPa, more preferably in the range of 2 to 4 MPa.
  • the heating time is, for example, in the range of 1.5 to 6 minutes, and preferably in the range of 2.4 to 4 minutes.
  • the heating time is less than 1.5 minutes, the curing reaction is not completed, which may lead to deterioration of the properties of the cured product, and it is particularly difficult to obtain a cured product having a glass transition point of 260 ° C. Become.
  • it processes for 6 minutes at the heating temperature of 260 degreeC there exists a possibility that the characteristic of hardened
  • the conditions under which the laminate is hot-pressed affect the glass transition temperature of the insulating layer and the peel strength of the metal layer with respect to the insulating layer. Therefore, in this embodiment, the conditions for hot pressing the laminate specify the structure or characteristics of the laminate. However, even when the inventor analyzed the insulating layer produced by hot pressing the laminate under different conditions, no significant difference was found. Therefore, although the insulating layer has a structure or characteristics derived from conditions for hot pressing the laminate, the structure or characteristics cannot be specified in terms of words.
  • the printed wiring board will be described.
  • the printed wiring board includes an insulating layer and a conductor wiring that overlaps the insulating layer.
  • the insulating layer includes a cured product of the resin composition described above.
  • the printed wiring board may include two conductor wirings, which may overlap one surface of the insulating layer and the surface on the opposite side.
  • the printed wiring board may include only one conductor wiring, which may overlap one surface of the insulating layer.
  • the cured product of the resin composition can have a high glass transition temperature, and thus the printed wiring board can have high heat resistance.
  • the printed wiring board it is possible to achieve a high peeling strength of the conductor wiring with respect to the insulating layer.
  • a printed wiring board can be manufactured, for example, by producing a conductor wiring by patterning a metal layer in the metal-clad laminate described above by a photolithography method or the like.
  • the printed wiring board may be a multilayer printed wiring board having a plurality of insulating layers and a plurality of conductor wirings.
  • at least one of the plurality of insulating layers may contain a cured product of the resin composition described above.
  • a glass cloth (thickness 95 ⁇ m, manufactured by Nitto Boseki Co., Ltd., product number 2116) was impregnated with this resin composition, and then heated at 130 ° C. for 3 minutes to prepare a prepreg.
  • a laminate was prepared by stacking copper foil (thickness 18 ⁇ m, manufactured by Mitsui Mining & Smelting Co., Ltd., product number 3EC-VLP) on one surface of this prepreg and the other surface.
  • the laminate was hot pressed to produce a metal-clad laminate.
  • the rate of temperature increase, the maximum heating temperature, the pressing pressure, and the heating time from the start of heating to the time when the maximum temperature is reached when the laminate is hot-pressed are as shown in the column “Hot press conditions” in Table 1.
  • 2-ethyl-4-methylimidazole 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine 2E4MZ-A manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • Spherical silica SC-2050MTX, manufactured by Admatechs Co., Ltd.
  • Solvent methyl ethyl ketone.
  • peel strength The peel strength of the metal foil (copper foil) with respect to the insulating layer in the metal-clad laminate was measured. The measurement was performed according to JIS C6481.
  • the glass transition temperature of the cured product contained in the insulating layer of the metal-clad laminate was measured by dynamic viscoelasticity measurement. Using a viscoelastic spectrometer (DMS100) manufactured by Seiko Instruments Inc. as a measuring device, tan ⁇ is measured with a bending module under the conditions of a frequency of 10 Hz, a heating rate of 5 ° C./min, and a temperature range of room temperature to 340 ° C. The temperature showing the maximum was taken as the glass transition temperature.
  • DMS100 viscoelastic spectrometer
  • the resin composition according to the first aspect includes an epoxy resin (A), a phenol compound (B), and an imidazole compound (C) having a triazine skeleton, and a resin composition.
  • the cured product has a glass transition temperature of 260 ° C. or higher.
  • a resin composition that can become a cured product having heat resistance can be obtained by curing.
  • the ratio of the imidazole compound (C) to the total of the epoxy resin (A) and the phenol compound (B) is 0.02 to 1% by mass.
  • the cured product can have a particularly high glass transition temperature, and the resin composition can have good varnish storage stability.
  • an insulating layer contains hardened
  • cured material which concerns on a 3rd aspect is obtained by hardening
  • a cured product having heat resistance is obtained.
  • the prepreg according to the fourth aspect includes a fiber base and a dried or semi-cured product of the resin composition according to the first or second aspect impregnated in the fiber base.
  • a prepreg that can be an insulating layer having heat resistance is obtained.
  • the metal-clad laminate according to the fifth aspect includes an insulating layer and a metal layer overlapping the insulating layer, and the insulating layer includes a cured product of the resin composition according to the first or second aspect, or The hardened
  • the insulating layer in the metal-clad laminate can have heat resistance and adhesion to the metal layer.
  • the cured product has a maximum heating temperature of the resin composition according to the first or second aspect, the dried product, or the semi-cured product thereof. It is produced by heating at 260 ° C. or higher.
  • the insulating layer can have particularly high heat resistance and adhesion with a particularly high metal layer.
  • the rate of temperature increase from the start of heating to the time when the maximum heating temperature is reached is 2 ° C./sec or more.
  • the insulating layer can have particularly high heat resistance.
  • the peel strength of the metal layer with respect to the insulating layer is 4 N / cm or more.
  • the insulating layer can have particularly high adhesion to the metal layer.
  • the printed wiring board according to the ninth aspect includes an insulating layer and a conductor wiring overlapping the insulating layer, and the insulating layer includes a cured product of the resin composition according to the first or second aspect, or third The hardened
  • the insulating layer in the printed wiring board can have heat resistance and adhesion to the conductor wiring.
  • a metal foil is stacked on a prepreg comprising a fiber base material and a dried or semi-cured product of the resin composition impregnated in the fiber base material, It includes producing a laminated body and heat-pressing the laminated body to produce an insulating layer containing a fiber base material and a cured product of the resin composition, and a metal layer made of a metal foil.
  • the resin composition contains an epoxy resin (A), a phenol compound (B), and an imidazole compound (C) having a triazine skeleton.
  • the maximum heating temperature when the laminate is hot-pressed is 280 ° C. or higher.
  • the insulating layer in the metal-clad laminate can have heat resistance and adhesion to the metal layer.
  • the rate of temperature increase from the start of heating when the laminate is hot-pressed until the maximum heating temperature is reached is 2 ° C./sec or more.
  • the insulating layer can have particularly high heat resistance.

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Abstract

エポキシ樹脂を含有し、硬化することで耐熱性を有する硬化物になりうる樹脂組成物を提供する。樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。樹脂組成物の硬化物が２６０℃以上のガラス転移温度を有する。

Description

樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び金属張積層板の製造方法
　本発明は、樹脂組成物、プリプレグ、金属張積層板、プリント配線板、及び金属張積層板の製造方法に関し、詳しくはエポキシ樹脂を含有する樹脂組成物、樹脂組成物の乾燥物又は半硬化物を備えるプリプレグ、樹脂組成物の硬化物を含む絶縁層を備える金属張積層板及びプリント配線板、並びに樹脂組成物を用いる金属張積層板の製造方法に関する。
　金属張積層板及びプリント配線板における絶縁層の材料の一つとして、エポキシ樹脂、硬化剤、硬化促進剤等を含有する樹脂組成物がある（特許文献１参照）。
　近年、車載用途などのプリント配線板には、高い耐熱性が要求されている。
国際公開ＷＯ２０１０／０３５４５２
　本発明の課題は、エポキシ樹脂を含有し、硬化することで耐熱性を有する硬化物になりうる樹脂組成物、樹脂組成物の乾燥物又は半硬化物を備えるプリプレグ、樹脂組成物の硬化物を含む絶縁層を備える金属張積層板及びプリント配線板、並びに樹脂組成物を用いる金属張積層板の製造方法を提供することである。
　本発明の一態様に係る樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。前記樹脂組成物の硬化物が２６０℃以上のガラス転移温度を有する。
　本発明の一態様に係るプリプレグは、繊維基材と、前記繊維基材に含浸している前記樹脂組成物の乾燥物又は半硬化物とを備える。
　本発明の一態様に係る金属張積層板は、絶縁層と、前記絶縁層に重なる金属層とを備える。前記絶縁層は、前記樹脂組成物の硬化物を含む。
　本発明の一態様に係るプリント配線板は、絶縁層と、前記絶縁層に重なる導体配線とを備え、前記絶縁層は、前記樹脂組成物の硬化物を含む。
　本発明の一態様に係る金属張積層板の製造方法は、繊維基材と、前記繊維基材に含浸している樹脂組成物の乾燥物又は半硬化物とを備えるプリプレグに、金属箔を重ねて、熱プレスすることにより、前記繊維基材と前記樹脂組成物の硬化物とを含む絶縁層と、前記金属箔からなる金属層とを作製することを含む。前記樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。前記熱プレス時の最高加熱温度は２８０℃以上である。
　以下、本発明の一実施形態に係る樹脂組成物、プリプレグ、硬化物、金属張積層板、プリント配線板、及び金属張積層板の製造方法について、説明する。
　樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。樹脂組成物の硬化物は、２６０℃以上のガラス転移温度を有する。なお、硬化物のガラス転移温度の測定方法は、下記実施例で説明する通りである。
　本実施形態には、硬化することで耐熱性を有する硬化物になりうる樹脂組成物、耐熱性を有する硬化物、樹脂組成物の乾燥物又は半硬化物を備えるプリプレグ、樹脂組成物の硬化物を含む絶縁層を備える金属張積層板及びプリント配線板、並びに樹脂組成物を用いる金属張積層板の製造方法を、提供できるという利点がある。
　硬化物は、樹脂組成物、樹脂組成物の乾燥物又は樹脂組成物の半硬化物を加熱することで、作製される。加熱の条件は、樹脂組成物が十分に硬化できる条件である。樹脂組成物は、少なくとも一つの条件で加熱されることで、２６０℃のガラス転移温度を有する硬化物になればよい。樹脂組成物、樹脂組成物の乾燥物又は樹脂組成物の半硬化物を加熱する条件は、例えば最高加熱温度２６０～４００℃の範囲内、加熱開始時から最高加熱温度到達時までの昇温速度は、２～８℃／ｓｅｃの範囲内、加熱時間は１．５～６分の範囲内である。熱プレスにより加熱する場合には、プレス圧は例えば０．５～５ＭＰａの範囲内である。これらの範囲内にあるいずれかの条件で樹脂組成物が加熱されることで得られる硬化物が、２６０℃以上のガラス転移温度を有することが好ましい。
　樹脂組成物から、金属張積層板及びプリント配線板における絶縁層を作製することができ、この場合、樹脂組成物は絶縁層の耐熱性を向上できる。
　なお、トリアジン骨格を有するイミダゾール化合物は公知であり、例えば国際公開ＷＯ２０１０／０３５４５２にも、イミダゾール硬化促進剤の例として、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］エチル－ｓ－トリアジン等が記載されている。
　しかし、金属張積層板等の絶縁層を作製するためのエポキシ樹脂組成物に、実際にトリアジン骨格を有するイミダゾール化合物を配合した例は存在しない。その理由は、イミダゾール化合物はエポキシ樹脂の硬化を促進する作用を有するものの、トリアジン骨格を有するイミダゾール化合物においてはその作用が弱く、そのため実用に適さないとみなされていたからである。そのため、トリアジン骨格を有するイミダゾール化合物を含有する樹脂組成物を実際に利用しようという着想を得ることは、困難であった。
　発明者は、このような状況の下、金属張積層板及びプリント配線板における絶縁層を作製するために、トリアジン骨格を有するイミダゾール化合物を含有する樹脂組成物を利用するという、飛躍的な着想を得た。さらに、発明者は、このような樹脂組成物の硬化物は高いガラス転移温度を有することができ、このような樹脂組成物を利用することで、耐熱性の高い絶縁層を作製できるという、顕著な利点を見いだし、本発明の完成に至った。
　エポキシ樹脂（Ａ）は、例えばナフタレン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、アルキルフェノールノボラック型エポキシ樹脂、アラルキル型エポキシ樹脂、ビフェノール型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物、トリグリシジルイソシアヌレート及び脂環式エポキシ樹脂からなる群から選択される少なくとも一種の化合物を含有できる。
　エポキシ樹脂（Ａ）は、特にフェノールノボラック型エポキシ樹脂を含有することが好ましい。樹脂組成物がフェノールノボラック型エポキシ樹脂を、トリアジン骨格を有するイミダゾール化合物（Ｃ）とともに含有すると、樹脂組成物の硬化物は、特に高いガラス転移温度を有することができる。
　エポキシ樹脂（Ａ）のエポキシ当量は２００以上であることが好ましい。この場合、硬化物は特に優れた熱安定性を有することができる。
　フェノール化合物（Ｂ）は、エポキシ樹脂（Ａ）の硬化剤である。フェノール化合物（Ｂ）は、例えばテトラキスフェノール樹脂、ノボラック型フェノール樹脂、ナフタレン型フェノール樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂、クレゾールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニル変性フェノールアラルキル樹脂、フェノールトリメチロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮ノボラック樹脂、ナフトール－クレゾール共縮ノボラック樹脂、ビフェニル変性フェノール樹脂、アミノトリアジン変性フェノール樹脂、ビフェノール、グリオキザールテトラフェノール樹脂、ビスフェノールＡノボラック樹脂及びビスフェノールＦノボラック樹脂からなる群から選択される少なくとも一種の化合物を含有できる。
　フェノール化合物（Ｂ）は、特にテトラキスフェノール樹脂を含有することが好ましい。樹脂組成物がテトラキスフェノール樹脂を含有するフェノール化合物（Ｂ）を、トリアジン骨格を有するイミダゾール化合物（Ｃ）とともに含有すると、樹脂組成物の硬化物は、特に高いガラス転移温度を有することができる。エポキシ樹脂（Ａ）がフェノールノボラック型エポキシ樹脂を含有し、かつフェノール化合物（Ｂ）がテトラキスフェノール樹脂を含有すれば、特に好ましい。
　フェノール化合物（Ｂ）の水酸基当量は１５０以上であることが好ましい。この場合、硬化物は特に優れた熱安定性を有することができる。
　エポキシ樹脂（Ａ）とフェノール化合物（Ｂ）との当量比は、０．８：１．２～１．２：０．８の範囲内であることが好ましい。
　上記の通り、樹脂組成物は、トリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。このため、樹脂組成物の硬化物は高いガラス転移温度を有することができ、２６０℃以上のガラス転移温度を有することも可能となる。このため、樹脂組成物の硬化物を含む絶縁層は、高い耐熱性を有することができる。さらに、樹脂組成物の硬化物を含む絶縁層は、金属層との高い密着性を有することができる。
　イミダゾール化合物（Ｃ）は、例えば２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］エチル－ｓ－トリアジンを含有できる。イミダゾール化合物（Ｃ）は、特に２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］エチル－ｓ－トリアジンを含有することが好ましい。この場合、樹脂組成物の硬化物は特に高いガラス転移温度を有することができ、この硬化物を含む絶縁層は特に高い耐熱性を有することができる。
　樹脂組成物中における、エポキシ樹脂（Ａ）とフェノール化合物（Ｂ）との合計に対する、イミダゾール化合物（Ｃ）の割合は、０．０２～１質量％の範囲内であることが好ましい。この割合が０．０２質量％以上であると、硬化物は特に高いガラス転移温度を有することができる。また、この割合が１質量％以下であると、溶剤を含有する場合に樹脂組成物を保存しても樹脂組成物の成分の凝集が生じにくく、すなわち樹脂組成物は良好なワニス保存安定性を有することができ、また絶縁層は良好なはんだ耐熱性を有することができる。なお、ワニス保存安定性は、下記実施例に示す方法で評価できる。
　樹脂組成物は、無機充填材を含有してもよい。無機充填材は、例えばシリカ、硫酸バリウム、酸化ケイ素粉、破砕シリカ、焼成タルク、チタン酸バリウム、酸化チタン、クレー、アルミナ、マイカ、ベーマイト、ホウ酸亜鉛及びスズ酸亜鉛、並びに前記以外の各種金属酸化物及び金属水和物からなる群から選択される少なくとも一種の成分を含有できる。
　樹脂組成物が無機充填材を含有すると、樹脂組成物の硬化物を含む絶縁層の低線膨張係数化が可能である。このため、絶縁層を備える積層板及びプリント配線板の反りなどの変形が抑制される。無機充填材の含有量は、樹脂組成物全量に対して８０質量％以下であることが好ましく、１０～８０質量％の範囲内であれば特に好ましい。
　樹脂組成物は、溶剤を含有してもよい。溶剤は、例えばアセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレン等の芳香族系溶剤、及びジメチルホルムアミド等の窒素含有溶剤からなる群から選択される少なくとも一種の成分を含有できる。
　樹脂組成物は上記以外の成分を含有していてもよい。例えば樹脂組成物は光安定剤、粘度調整剤、難燃剤等を含有していてもよい。
　プリプレグについて説明する。
　プリプレグは、繊維基材と、繊維基材に含浸している樹脂組成物の乾燥物又は半硬化物とを備える。
　繊維基材は、例えばガラス等の無機質繊維の織布、無機質繊維の不織布、アラミドクロス、ポリエステルクロス、又は紙である。繊維基材は、ガラスの織布、すなわちガラスクロスであることが好ましい。
　プリプレグを製造する場合、例えばまず繊維基材に樹脂組成物を、浸漬法、塗布法といった公知の方法で含浸させる。
　続いて、樹脂組成物を加熱することで、乾燥させ又は半硬化させる。加熱の条件は、例えば加熱温度１２０～１９０℃の範囲内、加熱時間３～１５分間の範囲内であるが、これに限られない。これにより、プリプレグが製造される。
　金属張積層板について説明する。
　金属張積層板は、絶縁層と、絶縁層に重なる金属層とを備える。絶縁層は、上記で説明した樹脂組成物の硬化物を含む。
　金属張積層板は、金属層を二つ備え、この二つの金属層が、絶縁層における一つの面と、その反対側にある面とに、それぞれ重なっていてもよい。金属張積層板は、金属層を一つのみ備え、この一つの金属層が絶縁層における一つの面に重なっていてもよい。
　樹脂組成物の硬化物は高いガラス転移温度を有することができ、このため金属張積層板は高い耐熱性を有することができる。さらに、金属張積層板においては、絶縁層に対する金属層の高い引き剥がし強度を達成することもできる。
　硬化物は、例えば樹脂組成物、樹脂組成物の乾燥物又は樹脂組成物の半硬化物を加熱することで、作製される。
　樹脂組成物を加熱するときの最高加熱温度は２６０℃以上であることが好ましい。この場合、特に高いガラス転移温度と特に高い引き剥がし強度とを達成できる。この最高加熱温度は、２６０～４００℃の範囲内であることがより好ましく、２８０～３２０℃の範囲内であれば更に好ましい。
　樹脂組成物を加熱するときの加熱開始時から最高加熱温度到達時までの昇温速度は、２℃／ｓｅｃ以上であることが好ましい。この場合、硬化物は特に高いガラス転移温度を有することができる。この昇温速度は、２～８℃／ｓｅｃの範囲内であることがより好ましく、３～５℃／ｓｅｃの範囲内であれば更に好ましい。
　金属張積層板の製造方法の一例について説明する。
　上記で説明したプリプレグ、又はプリプレグを複数枚積層した積層物に、金属箔を重ねて、積層体を作製する。金属張積層板が金属層を二つ備える場合には、二つの金属箔を、プリプレグ又は積層物の一つの面と、その反対側の面とに、それぞれ重ねて、積層体を作製する。金属張積層板が金属層を一つのみ備える場合には、金属箔を、プリプレグ又は積層物の一つの面に重ねて、積層体を作製する。積層体を熱プレスすることにより、繊維基材と樹脂組成物の硬化物とを含む絶縁層と、金属箔からなる金属層とを作製できる。これにより、金属張積層板を製造できる。
　この金属張積層板における絶縁層に含まれる硬化物は、高いガラス転移温度を有することができ、２６０℃以上のガラス転移温度を有することもできる。このため、金属張積層板は高い耐熱性を有することができる。
　この金属張積層板においては、絶縁層に対する金属層の高い引き剥がし強度を達成することもでき、４Ｎ／ｃｍ以上の引き剥がし強度を達成することもできる。引き剥がし強度の測定方法は、下記実施例で説明する通りである。
　積層体を熱プレスする条件は、例えば最高加熱温度、プレス圧及び加熱時間を含む。
　最高加熱温度は、上記と同様、２６０℃以上であることが好ましく、２６０～４００℃の範囲内であることがより好ましく、２８０～３２０℃の範囲内であれば更に好ましい。熱プレス時の加熱開始時から最高加熱温度到達時までの昇温速度は、上記と同様、２℃／ｓｅｃ以上であることが好ましく、２～８℃／ｓｅｃの範囲内であることがより好ましく、３～５℃／ｓｅｃの範囲内であれば更に好ましい。
　プレス圧は、例えば０．５～５ＭＰａの範囲内である。この場合、特に高いガラス転移温度と特に高い引き剥がし強度とを達成できる。プレス圧は、０．５～５ＭＰａの範囲内であれば好ましく、２～４ＭＰａの範囲内であればより好ましい。
　加熱時間は、例えば１．５～６分の範囲内であり、２．４～４分の範囲内であれば好ましい。加熱時間が１．５分未満である場合には硬化反応が完了しないために、硬化物の特性低下に繋がる可能性があり、特にガラス転移点が２６０℃である硬化物を得ることが困難となる。また、加熱温度２６０℃で６分を超えて処理した場合には、分解反応の進行により、硬化物の特性が低下する恐れがある。
　なお、積層体を熱プレスする条件は、絶縁層のガラス転移温度及び絶縁層に対する金属層の引き剥がし強度に影響を与える。そのため、本実施形態では、積層体を熱プレスする条件は、積層板の構造又は特性を特定する。しかし、発明者が異なる条件で積層体を熱プレスすることで作製された絶縁層を分析しても、有意な相違は見いだせなかった。したがって、絶縁層は、積層体を熱プレスする条件に由来する構造又は特性を有するものの、その構造又は特性を文言上特定することはできない。
　プリント配線板について説明する。
　プリント配線板は、絶縁層と、絶縁層に重なる導体配線とを備える。絶縁層は、上記で説明した樹脂組成物の硬化物を含む。
　プリント配線板は、導体配線を二つ備え、これらが、絶縁層における一つの面と、その反対側にある面とに、それぞれ重なっていてもよい。プリント配線板は、導体配線を一つのみ備え、これが絶縁層における一つの面に重なっていてもよい。
　樹脂組成物の硬化物は高いガラス転移温度を有することができ、このためプリント配線板は高い耐熱性を有することができる。
　さらに、プリント配線板においては、絶縁層に対する導体配線の高い引き剥がし強度を達成することもできる。
　プリント配線板は、例えば上記で説明した金属張積層板における金属層を、フォトリソグラフィ法などでパターニングすることで、導体配線を作製することによって、製造できる。
　プリント配線板は、複数の絶縁層と複数の導体配線とを備える多層プリント配線板であってもよい。この場合、複数の絶縁層のうち少なくとも一つが、上記で説明した樹脂組成物の硬化物を含有すればよい。
　１．樹脂組成物の調製及び金属張積層板の製造
　表１の「組成」の欄に示す成分を混合することで、樹脂組成物を調製した。
　この樹脂組成物をガラスクロス（厚み９５μｍ、日東紡績株式会社製、品番２１１６）に含浸させてから、１３０℃、３分間の条件で加熱することで、プリプレグを作製した。
　このプリプレグの一つの面と、その反対側の面とに、それぞれ銅箔（厚み１８μｍ、三井金属鉱業株式会社製、品番３ＥＣ－ＶＬＰ）を重ねて、積層体を作製した。この積層体を熱プレスすることにより、金属張積層板を製造した。積層体を熱プレスするときの加熱開始時から最高温度到達時までの昇温速度、最高加熱温度、プレス圧、及び加熱時間は、表１の「熱プレス条件」の欄に示す通りである。
　なお、表１に示す成分の詳細は、次の通りである。
・フェノールノボラック型エポキシ樹脂：日本化薬株式会社製、ＥＰＰＮ－５０２Ｈ。
・ビスフェノールＡ型エポキシ樹脂：日本化薬株式会社製、ＲＥ－３１０Ｓ。
・フェノール樹脂１：ビフェニルアラルキル型フェノール樹脂、明和化成株式会社製、ＭＥＨ７８５１－４Ｈ。
・フェノール樹脂２：テトラキスフェノール樹脂、明和化成株式会社製、ＭＥＨ７６００－４Ｈ。
・１－シアノエチル－２－メチルイミダゾール：四国化成工業株式会社製、２ＭＺ－ＣＮ。
・２－エチル－４－メチルイミダゾール：四国化成工業株式会社製、２Ｅ４ＭＺ。
・２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン：四国化成工業株式会社製、２Ｅ４ＭＺ－Ａ。
・球状シリカ：株式会社アドマテックス製、ＳＣ－２０５０ＭＴＸ。
・溶剤：メチルエチルケトン。
　２．評価試験
　金属張積層板に対して、次の評価試験を行った。その結果を表１に示す。
　（１）引き剥がし強度
　金属張積層板における絶縁層に対する金属箔（銅箔）の引き剥がし強度を測定した。測定は、ＪＩＳ　Ｃ６４８１に準拠して行った。
　（２）ガラス転移温度
　金属張積層板の絶縁層に含まれる硬化物のガラス転移温度を、動的粘弾性測定により測定した。測定装置としてセイコーインスツルメンツ株式会社製の粘弾性スペクトロメータ（ＤＭＳ１００）を用い、曲げモジュールで、周波数１０Ｈｚ、昇温速度５℃／分、温度範囲室温～３４０℃の条件でｔａｎδを測定し、ｔａｎδが極大を示す温度をガラス転移温度とした。
　（３）ワニス保存安定性
　樹脂組成物を室温で３０日間放置してから、樹脂組成物の透明性を目視で確認した。樹脂組成物が透明であると確認できれば「Ａ」と評価し、樹脂組成物に濁りが確認できれば「Ｂ」と評価した。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
　上述の実施形態から明らかなように、第１の態様に係る樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有し、樹脂組成物の硬化物が２６０℃以上のガラス転移温度を有する。第１の態様では、硬化することで耐熱性を有する硬化物になりうる樹脂組成物が得られる。
　第２の態様に係る樹脂組成物では、第１の態様において、エポキシ樹脂（Ａ）とフェノール化合物（Ｂ）との合計に対する、イミダゾール化合物（Ｃ）の割合は、０．０２～１質量％の範囲内である。第２の態様では、硬化物は特に高いガラス転移温度を有することができ、かつ樹脂組成物は良好なワニス保存安定性を有することができる。また絶縁層が硬化物を含有する場合、絶縁層は良好なはんだ耐熱性を有することができる。
　第３の態様に係る硬化物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する樹脂組成物を硬化して得られ、２６０℃以上のガラス転移温度を有する。第３の態様では、耐熱性を有する硬化物が得られる。
　第４の態様に係るプリプレグは、繊維基材と、繊維基材に含浸している第１又は第２の態様に係る樹脂組成物の乾燥物又は半硬化物とを備える。第４の態様では、耐熱性を有する絶縁層になりうるプリプレグが得られる。
　第５の態様に係る金属張積層板は、絶縁層と、絶縁層に重なる金属層とを備え、絶縁層は、第１又は第２の態様に係る樹脂組成物の硬化物を含み、又は第３の態様に係る硬化物を含む。第５の態様では、金属張積層板における絶縁層は、耐熱性と、金属層との密着性とを有することができる。
　第６の態様に係る金属張積層板では、第５の態様において、硬化物は、第１又は第２の態様に係る樹脂組成物、その乾燥物、又はその半硬化物を、最高加熱温度が２６０℃以上で加熱することで作製される。第６の態様では、絶縁層は特に耐熱性と特に高い金属層との密着性を有することができる。
　第７の態様に係る金属張積層板では、第６の態様において、樹脂組成物、乾燥物、又は半硬化物を加熱するときの、加熱開始時から最高加熱温度到達時までの昇温速度は、２℃／ｓｅｃ以上である。第７の態様では、絶縁層は特に高い耐熱性を有することができる。
　第８の態様に係る金属張積層板では、第５から第７のいずれか一の態様において、絶縁層に対する金属層の引き剥がし強度は、４Ｎ／ｃｍ以上である。第８の態様では、絶縁層は特に高い金属層との密着性を有することができる。
　第９の態様に係るプリント配線板は、絶縁層と、絶縁層に重なる導体配線とを備え、絶縁層は、第１又は第２の態様に係る樹脂組成物の硬化物を含み、又は第３の態様に係る硬化物を含む。第９の態様では、プリント配線板における絶縁層は、耐熱性と、導体配線との密着性とを有することができる。
　第１０の態様に係る金属張積層板の製造方法は、繊維基材と、繊維基材に含浸している樹脂組成物の乾燥物又は半硬化物とを備えるプリプレグに、金属箔を重ねて、積層体を作製し、積層体を熱プレスすることにより、繊維基材と樹脂組成物の硬化物とを含む絶縁層と、金属箔からなる金属層とを作製することを含む。樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有する。積層体を熱プレスするときの最高加熱温度は２８０℃以上である。第１０の態様では、金属張積層板における絶縁層は、耐熱性と、金属層との密着性とを有することができる。
　第１１の態様に係る金属張積層板の製造方法では、積層体を熱プレスするときの加熱開始時から最高加熱温度到達時までの昇温速度は、２℃／ｓｅｃ以上である。第１１の態様では、絶縁層は特に高い耐熱性を有することができる。

Claims (10)

  1. エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有し、
    その硬化物が２６０℃以上のガラス転移温度を有する、
    樹脂組成物。
  2. 前記エポキシ樹脂（Ａ）と前記フェノール化合物（Ｂ）との合計に対する、前記イミダゾール化合物（Ｃ）の割合は、０．０２～１質量％の範囲内である、
    請求項１に記載の樹脂組成物。
  3. 繊維基材と、前記繊維基材に含浸している請求項１又は２に記載の樹脂組成物の乾燥物又は半硬化物とを備える、
    プリプレグ。
  4. 絶縁層と、前記絶縁層に重なる金属層とを備え、
    前記絶縁層は、請求項１又は２に記載の樹脂組成物の硬化物を含む、
    金属張積層板。
  5. 前記硬化物は、請求項１又は２に記載の樹脂組成物、その乾燥物、又はその半硬化物を、最高加熱温度が２６０℃以上で加熱することで作製される、
    請求項４に記載の金属張積層板。
  6. 前記樹脂組成物、前記乾燥物、又は前記半硬化物を加熱するときの、加熱開始時から最高加熱温度到達時までの昇温速度は、２℃／ｓｅｃ以上である、
    請求項５に記載の金属張積層板。
  7. 前記絶縁層に対する前記金属層の引き剥がし強度は、４Ｎ／ｃｍ以上である、
    請求項４から６のいずれか一項に記載の金属張積層板。
  8. 絶縁層と、前記絶縁層に重なる導体配線とを備え、
    前記絶縁層は、請求項１又は２に記載の樹脂組成物の硬化物を含む、
    プリント配線板。
  9. 繊維基材と、前記繊維基材に含浸している樹脂組成物の乾燥物又は半硬化物とを備えるプリプレグに、金属箔を重ねて、積層体を作製し、前記積層体を熱プレスすることにより、前記繊維基材と前記樹脂組成物の硬化物とを含む絶縁層と、前記金属箔からなる金属層とを作製することを含み、
    前記樹脂組成物は、エポキシ樹脂（Ａ）、フェノール化合物（Ｂ）、及びトリアジン骨格を有するイミダゾール化合物（Ｃ）を含有し、
    前記積層体を熱プレスするときの最高加熱温度は２８０℃以上である、
    金属張積層板の製造方法。
  10. 前記積層体を熱プレスするときの、加熱開始時から最高加熱温度到達時までの昇温速度は、２℃／ｓｅｃ以上である、
    請求項９に記載の金属張積層板の製造方法。
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