WO2021215382A1 - Organic resin film - Google Patents

Organic resin film Download PDF

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Publication number
WO2021215382A1
WO2021215382A1 PCT/JP2021/015809 JP2021015809W WO2021215382A1 WO 2021215382 A1 WO2021215382 A1 WO 2021215382A1 JP 2021015809 W JP2021015809 W JP 2021015809W WO 2021215382 A1 WO2021215382 A1 WO 2021215382A1
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Prior art keywords
solvent
organic resin
resin film
sample
film according
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PCT/JP2021/015809
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French (fr)
Japanese (ja)
Inventor
梶田　智
長澤　忠
智恵 主税
智士 芦浦
晃次 藤川
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京セラ株式会社
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Priority to JP2022517028A priority Critical patent/JPWO2021215382A1/ja
Publication of WO2021215382A1 publication Critical patent/WO2021215382A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits

Definitions

  • This disclosure relates to an organic resin film.
  • Patent Document 1 When a resin film formed of a conventional cyclic olefin copolymer as described in Patent Document 1 is used, for example, as an insulating layer of a wiring board, it tends to change to a state in which it is difficult to laminate and crimp in the manufacturing process of the wiring board. There is a problem.
  • the organic resin film according to the present disclosure contains a resin containing a cyclic olefin copolymer as a main component, a first solvent, and a second solvent having a boiling point lower than that of the first solvent.
  • the first solvent is at least one solvent selected from the group consisting of toluene, xylene, naphtha, octane, decalin, glycol ethers, decane and tridecane.
  • the second solvent is at least one solvent selected from the group consisting of cyclohexane, benzene, hexane, chloroform and dichloroethane.
  • the organic resin film according to the present disclosure contains a resin containing a cyclic olefin copolymer as a main component, a first solvent, and a second solvent having a boiling point lower than that of the first solvent. Therefore, the organic resin film according to the present disclosure has an effect of being easily laminated and pressure-bonded in the manufacturing process of the wiring board.
  • the cyclic olefin copolymer contained in the organic resin film according to the embodiment of the present disclosure is a polyolefin-based copolymer having a cyclic structure.
  • the cyclic olefin copolymer is obtained by polymerizing the cyclic olefin with another monomer copolymerizable with the cyclic olefin.
  • the ratio of the cyclic olefin to other monomers is not particularly limited. For example, other monomers are used in a ratio of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cyclic olefin.
  • the cyclic olefin copolymer preferably contains a crosslinkable functional group in the molecule.
  • a crosslinkable functional group it is preferable that the crosslinking reaction proceeds with a peroxide having a benzene ring.
  • Peroxides having a benzene ring include di-t-butyl peroxide (perbutyl D), di- (t-butylperoxy) diisopyrbenzene (perbutyl P, t-butylcumyl peroxide (perbutyl C)) and dik. Examples thereof include mil peroxide (park mill D).
  • Examples of the cyclic olefin include a norbornene-based monomer, a cyclic diene-based monomer, and a vinyl alicyclic hydrocarbon-based monomer.
  • examples of the cyclic olefin include norbornene, vinylnorbornene, phenylnorbornene, dicyclopentadiene, tetracyclododecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene, cyclooctadiene and the like. These cyclic olefins may be used alone or in combination of two or more.
  • Examples of other monomers copolymerizable with the cyclic olefin include chain olefins, acrylate acrylates, acrylates, methacrylic acids, aromatic vinyl compounds, unsaturated nitriles, and aliphatic conjugated dienes.
  • such monomers include ethylene, propylene, butene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, and propyl acrylate.
  • Isopropyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene and the like can be mentioned.
  • These other monomers may be used alone or in combination of two or more.
  • the "resin containing a cyclic olefin copolymer as a main component” means a resin containing 50% by mass or more of the above-mentioned cyclic olefin copolymer, excluding the additives described later. That is, the "resin containing the cyclic olefin copolymer as a main component” may be a resin composed only of the cyclic olefin copolymer (100% by mass of the cyclic olefin copolymer), and the cyclic olefin copolymer and the resin other than the cyclic olefin copolymer may be used. It may be a resin containing.
  • resins other than the cyclic olefin copolymer include acrylic resin, epoxy resin, phenol resin, melamine resin, urea resin, polyamide, and polyimide. These resins may be used alone or in combination of two or more, for example, in consideration of compatibility with the cyclic olefin copolymer.
  • the first solvent contained in the organic resin film is at least one solvent selected from the group consisting of toluene, xylene, octane, decahydronaphthalene, glycol ether (ethylene glycol dimethyl ether), decane, and tridecane.
  • the first solvent is a solvent having a relatively high boiling point. Among these first solvents, toluene or xylene is preferably used.
  • the second solvent contained in the organic resin film according to the first embodiment is a solvent having a boiling point lower than that of the first solvent.
  • the second solvent is at least one solvent selected from the group consisting of cyclohexane, benzene, hexane, chloroform, and dichloroethane. Among these second solvents, cyclohexane is preferably used.
  • the organic resin film contains the first solvent and the second solvent, the suppleness of the organic resin film is increased, and the organic resin films are easily adhered to each other.
  • the contents of the first solvent and the second solvent for example, the content of the second solvent may be larger than the content of the first solvent.
  • the content of the second solvent is preferably 3.4 times or more and 7.2 times or less, particularly 4.1 times or more and 7.2 times or less the content of the first solvent.
  • the solvent of the obtained organic resin film tends to volatilize in the process of evacuation during laminating and pressure bonding. The organic resin film thus obtained is less likely to cause delamination and blistering.
  • cyclohexane easily dissolves the cyclic olefin copolymer.
  • Cyclohexane has a hydrophilic lipophilic balance (HLB) of about 15. Cyclohexane tends to generate static electricity. Therefore, a solvent having a lower HLB value than cyclohexane is mixed. The generation of static electricity can be suppressed by mixing a solvent having a HLB value lower than that of cyclohexane.
  • examples of such a solvent include the above-mentioned first solvent (toluene).
  • the HLB value of toluene is 11.3.
  • the content of the first solvent and the second solvent contained in the organic resin film is such that the total amount of the first solvent and the second solvent is 0.2% by mass or more and 1.1% by mass or less. good. When these are expressed in units of ppm as a mass ratio, they are 2000 ppm or more and 11000 ppm or less. When the total amount of the first solvent and the second solvent contained in the organic resin film is 0.2% by mass or more and 1.1% by mass or less, an organic resin film that is difficult to peel off is obtained in the laminated pressure bonding test and the solder heat resistance test. be able to. The contents of the first solvent and the second solvent contained in the organic resin film are measured by performing gas chromatography analysis on a sample piece cut out from the produced organic resin film.
  • the content of the second solvent is the content of the first solvent in the organic resin film according to the first embodiment from the viewpoint that peeling can be suppressed in the laminated pressure bonding test and the solder heat resistance test on the laminate obtained after the pressure heat treatment. Better than more.
  • the organic resin film according to one embodiment may contain additives such as an antioxidant, an ultraviolet absorber, a colorant, a stress relaxant, an inorganic filler, and a flame retardant.
  • the content of the additive is not limited as long as it does not interfere with the effect of the organic resin film of the present disclosure.
  • the organic resin film according to one embodiment may contain, for example, an additive in a proportion of 1% by mass or more and 50% by mass or less.
  • examples of the inorganic filler include silica, talc, mica, clay, calcium carbonate, titanium oxide, barium titanate, carbon black, glass beads, and glass hollow spheres.
  • examples of silica include crushed silica and molten silica. Only one kind of inorganic filler may be used, or two or more kinds may be used in combination.
  • the average particle size of the inorganic filler is not particularly limited, and may be, for example, 0.01 ⁇ m or more and 10 ⁇ m or less, and 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the content of the inorganic filler may be 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer.
  • flame-retardant agents include melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonic acid ester, phosphinic acid ester, phosphine oxide, phosphazene, and melamine.
  • flame retardants include cyanolate, ethylene bispentabromobenzene, and ethylene bistetrabromophthalimide. These flame retardants may be used alone or in combination of two or more.
  • a bromine-based flame retardant (ethylenebispentabromobenzene, ethylenebistetrabromophthalimide, etc.) is used because the dielectric loss tangent of the laminated cured sheet obtained by curing the laminated uncured sheet can be lowered. May be good.
  • the average particle size of the flame retardant is not particularly limited, and may be, for example, 0.01 ⁇ m or more and 10 ⁇ m or less, and 0.5 ⁇ m or more and 3 ⁇ m or less.
  • the content of the flame retardant may be 15 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer.
  • the method for producing the organic resin film of the present disclosure is not particularly limited.
  • a resin containing a cyclic olefin copolymer as a main component is dissolved or dispersed in a mixed solvent containing a first solvent and a second solvent, and if necessary, an additive is added to obtain a resin varnish.
  • an additive a necessary additive may be selected and used from the above-mentioned plurality of types.
  • a film-shaped molded product is produced from the obtained resin varnish.
  • the resin varnish is formed into a film by a bar coater method, a doctor blade method, a die coater method, an extrusion method, an injection molding method, etc., and then dried at about 120 to 150 ° C. for about 1 to 10 minutes.
  • a film-shaped molded product is obtained.
  • This film-shaped molded product is subjected to pressure heat treatment to obtain an organic resin film in which the first solvent and the second solvent remain.
  • the conditions for the pressure heat treatment are, for example, a temperature of about 160 to 230 ° C. and a pressure of about 1 to 10 MPa.
  • the organic resin film thus obtained has a thickness of, for example, about 0.01 to 1 mm.
  • the metal-clad laminate of the present disclosure includes a metal foil on at least one surface of the organic resin film of the present disclosure.
  • the metal-clad laminate of the present disclosure is obtained, for example, by superimposing the above-mentioned organic resin film and a metal foil and heating (curing) pressure molding.
  • the metal foil is not particularly limited, and examples thereof include a copper foil such as an electrolytic copper foil and a rolled copper foil, an aluminum foil, and a composite foil obtained by superimposing these metal foils. Among these metal foils, for example, copper foil is used.
  • the thickness of the metal foil is not particularly limited, and is, for example, about 5 to 105 ⁇ m.
  • the metal-clad laminate of the present disclosure can also be obtained by laminating a desired number of the above-mentioned organic resin films and metal foils and heat-pressing molding.
  • the metal-clad laminate of the present disclosure is used for, for example, a printed wiring board.
  • the wiring board of the present disclosure includes a plurality of insulating layers and a conductor layer arranged between the insulating layers, and the insulating layer is formed of the organic resin film of the present disclosure.
  • Heat-resistant cyclic olefin copolymer (heat-resistant COC (including radically polymerizable functional group), manufactured by Mitsui Chemicals Co., Ltd.) 100 parts by mass, 30 parts by mass of SAYTEX8010 as a flame retardant, peroxide having a benzene ring in the molecule
  • As a substance 1.8 parts by mass of dit-butyl peroxide (Perbutyl D, manufactured by Nichiyu Co., Ltd.) and 20 parts by mass of silica were added. 40% by mass of the obtained mixture and 60% by mass of the solvent were mixed to obtain a resin varnish.
  • Toluene (boiling point 110 ° C.) was used as the first solvent.
  • Cyclohexane (boiling point 81 ° C.) was used as the second solvent.
  • Sample No. Reference numeral 1 denotes a sample prepared from an organic resin film obtained using only a second solvent (cyclohexane).
  • Sample No. Reference numeral 2 denotes a sample prepared from an organic resin film obtained by using only the first solvent (toluene).
  • Sample No. 3 to 8 are samples prepared from an organic resin film obtained by using a mixed solvent.
  • Example No. 1 The residual amount of cyclohexane (second solvent) in the organic resin film of No. 1 is shown in Table 1.
  • Example Nos. 2 to 8 The drying temperature and the drying time were variously changed to obtain organic resin films having a thickness of 15 ⁇ m in which the residual amount of the solvent was different (Sample Nos. 2 to 8).
  • Sample No. Table 1 shows the residual amounts of toluene (first solvent) and cyclohexane (second solvent) in the organic resin films 2 to 8.
  • Sample No. The drying conditions of 2 to 8 are as follows. The conditions are, in order, the maximum temperature and the holding time. Sample No. 2 is 140 ° C. and 4 minutes, sample No. 3 is 140 ° C. and 1 minute, sample No. 4 is 140 ° C. and 0.5 minutes, sample No. 5 is 130 ° C. and 2 minutes, sample No. 6 is 130 ° C. and 1 minute, sample No. 7 is 120 ° C. and 10 minutes, sample No. 8 is 110 ° C. and 10 minutes.
  • the contents of the first solvent and the second solvent contained in the produced organic resin film were measured by gas chromatography analysis.
  • the sample used for the gas chromatography analysis a sample piece cut out from the prepared organic resin film was used.
  • the laminated crimping test was carried out according to the following procedure. First, the obtained organic resin film was cut into a size of 500 mm ⁇ 500 mm. Next, 20 sheets of the cut organic resin film were laminated using a vacuum laminating hot press machine (manufactured by Meiki Seisakusho Co., Ltd.). The pressure at the time of stacking was 1 MPa, the temperature was 110 ° C. (maximum temperature), and the holding time at the maximum temperature was 1 minute. If there was even one peeled portion after laminating, it was evaluated as NG, and if there was no peeled portion, it was evaluated as OK. The results are shown in Table 1.
  • solder heat resistance test A solder heat resistance test A
  • the obtained organic resin film was cut into a size of 300 mm ⁇ 300 mm.
  • four obtained organic resin films were laminated to prepare a laminate.
  • copper foils were placed on both sides of the laminate and subjected to pressure heat treatment using a laminate press to prepare a copper-clad laminate.
  • the conditions for the pressure heat treatment were the maximum temperature: 180 ° C., the holding time at the maximum temperature: 2 hours, and the pressure: 3 MPa.
  • solder heat resistance test A solder heat resistance test A and solder heat resistance test B in Table 1
  • solder heat resistance test B solder heat resistance test B
  • the conditions of the solder heat resistance test A are that the maximum temperature is 288 ° C. and the holding time is 10 seconds.
  • the conditions of the solder heat resistance test B were the same as the maximum temperature and the holding time was 60 seconds.
  • Solder heat resistance tests A and B were carried out by a method in which the sample was floated in a solder bath. After the test, if there was even one peeled part, it was evaluated as NG, and if there was no peeled part, it was evaluated as OK. The results are shown in Table 1.
  • the amount of solvent contained in the organic resin film is expressed in ppm.
  • the samples prepared using the mixed solvent all contained the first solvent and the second solvent. Its content was 2735 ppm or more and 57600 ppm or less.
  • the sample No. prepared using the mixed solvent In 3 to 8, the content of the second solvent was higher than the content of the first solvent.
  • sample No. In Nos. 1 and 2 peeled portions were observed in the laminated crimping test. Further, in the solder heat resistance test (solder heat resistance test A and solder heat resistance test B), a peeled portion was observed in the sample after the test. Sample No. Sample Nos. 3 to 8 are No. Compared with 1 and 2, the adhesion between the organic resin films was excellent.
  • sample No. 9 shows the residual amounts of xylene (first solvent) and cyclohexane (second solvent) in the organic resin films 9 to 12.
  • Sample No. The drying conditions of 9 to 12 are as follows. The conditions are, in order, the maximum temperature and the holding time. Sample No. 9 is 140 ° C. and 1 minute, sample No. 10 is 140 ° C. and 0.5 minutes, sample No. No. 11 was sample No. 11 at 130 ° C. and 1 minute. 12 is 120 ° C. and 10 minutes.
  • solder heat resistance test A and solder heat resistance test B were performed in the same procedure as in 3 to 8. The results are shown in Table 2.
  • the amount of solvent contained in the organic resin film is expressed in ppm.
  • the samples prepared using the mixed solvent all contained the first solvent and the second solvent. Its content was 450 ppm or more and 39830 ppm or less.
  • the sample No. prepared using the mixed solvent In 9 to 12, the content of the second solvent was higher than the content of the first solvent.
  • sample Nos. 9 to 12 As shown in Table 2, in the samples (Sample Nos. 9 to 12) prepared using the organic resin film according to the present disclosure, no peeled portion was observed in the laminated pressure bonding test. Sample No. In Nos. 9 to 12, no peeled portion was observed under the conditions of the solder heat resistance test A and the conditions of the solder heat resistance test B, and no slight blister was observed on the copper foil on the surface. Furthermore, the sample No. 9 to 12 are the above-mentioned sample Nos. Compared with 1 and 2, the adhesion between the organic resin films was excellent.

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Abstract

An organic resin film according to the present disclosure contains a resin that is mainly composed of a cyclic olefin copolymer, a first solvent, and a second solvent that has a lower boiling point than the first solvent. The first solvent is composed of at least one solvent that is selected from the group consisting of toluene, xylene, naphtha, octane, decalin, glycol ethers, decane and tridecane. The second solvent is composed of at least one solvent that is selected from the group consisting of cyclohexane, benzene, hexane, chloroform and dichloroethane.

Description

有機樹脂フィルムOrganic resin film
　本開示は、有機樹脂フィルムに関する。 This disclosure relates to an organic resin film.
　特許文献１に記載のような従来の環状オレフィン共重合体で形成された樹脂フィルムは、例えば、配線基板の絶縁層として使用する場合、配線基板の製造工程において積層圧着しにくい状態に変化しやすいという問題がある。 When a resin film formed of a conventional cyclic olefin copolymer as described in Patent Document 1 is used, for example, as an insulating layer of a wiring board, it tends to change to a state in which it is difficult to laminate and crimp in the manufacturing process of the wiring board. There is a problem.
特開２０１０－１００８４３号公報Japanese Unexamined Patent Publication No. 2010-100843
　本開示に係る有機樹脂フィルムは、環状オレフィンコポリマーを主成分とする樹脂、第１溶媒、および該第１溶媒よりも低い沸点を有する第２溶媒を含む。第１溶媒は、トルエン、キシレン、ナフサ、オクタン、デカリン、グリコールエーテル、デカンおよびトリデカンからなる群より選択される少なくとも１種の溶媒である。第２溶媒は、シクロヘキサン、ベンゼン、ヘキサン、クロロホルムおよびジクロロエタンからなる群より選択される少なくとも１種の溶媒である。 The organic resin film according to the present disclosure contains a resin containing a cyclic olefin copolymer as a main component, a first solvent, and a second solvent having a boiling point lower than that of the first solvent. The first solvent is at least one solvent selected from the group consisting of toluene, xylene, naphtha, octane, decalin, glycol ethers, decane and tridecane. The second solvent is at least one solvent selected from the group consisting of cyclohexane, benzene, hexane, chloroform and dichloroethane.
　本開示に係る有機樹脂フィルムは、環状オレフィンコポリマーを主成分とする樹脂、第１溶媒、および該第１溶媒よりも沸点の低い第２溶媒を含む。そのため、本開示に係る有機樹脂フィルムは、配線基板の製造工程において積層圧着しやすいという効果が発揮される。 The organic resin film according to the present disclosure contains a resin containing a cyclic olefin copolymer as a main component, a first solvent, and a second solvent having a boiling point lower than that of the first solvent. Therefore, the organic resin film according to the present disclosure has an effect of being easily laminated and pressure-bonded in the manufacturing process of the wiring board.
　本開示の一実施形態に係る有機樹脂フィルムに含まれる環状オレフィンコポリマーは、環状構造を有しているポリオレフィン系共重合体である。環状オレフィンコポリマーは、環状オレフィンとこの環状オレフィンと共重合可能な他のモノマーとを重合させることによって得られる。環状オレフィンと他のモノマーとの割合は特に限定されない。例えば、環状オレフィン１００質量部に対して、他のモノマーが１質量部以上１００質量部以下の割合で使用される。 The cyclic olefin copolymer contained in the organic resin film according to the embodiment of the present disclosure is a polyolefin-based copolymer having a cyclic structure. The cyclic olefin copolymer is obtained by polymerizing the cyclic olefin with another monomer copolymerizable with the cyclic olefin. The ratio of the cyclic olefin to other monomers is not particularly limited. For example, other monomers are used in a ratio of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cyclic olefin.
　環状オレフィンコポリマーとしては、分子内に架橋可能な官能基を含んでいるものがよい。このような架橋可能な官能基としては、ベンゼン環を有する過酸化物によって架橋反応が進行するものがよい。例えば、ビニル基、アリル基、アクリル基およびメタクリル基などが挙げられる。ベンゼン環を有する過酸化物としては、ジ－ｔ－ブチルパーオキサイド（パーブチルＤ）、ジ－(ｔ－ブチルペルオキシ)ジイソピルベンゼン(パーブチルP、ｔ－ブチルクミルパーオキサイド（パーブチルＣ）およびジクミルパーオキサイド（パークミルＤ）などが挙げられる。 The cyclic olefin copolymer preferably contains a crosslinkable functional group in the molecule. As such a crosslinkable functional group, it is preferable that the crosslinking reaction proceeds with a peroxide having a benzene ring. For example, vinyl group, allyl group, acrylic group, methacrylic group and the like can be mentioned. Peroxides having a benzene ring include di-t-butyl peroxide (perbutyl D), di- (t-butylperoxy) diisopyrbenzene (perbutyl P, t-butylcumyl peroxide (perbutyl C)) and dik. Examples thereof include mil peroxide (park mill D).
　環状オレフィンとしては、例えば、ノルボルネン系モノマー、環状ジエン系モノマー、ビニル脂環式炭化水素系モノマーなどが挙げられる。具体的には、環状オレフィンとしては、ノルボルネン、ビニルノルボルネン、フェニルノルボルネン、ジシクロペンタジエン、テトラシクロドデセン、シクロプロペン、シクロブテン、シクロペンテン、シクロヘキセン、シクロヘキサジエン、シクロオクタジエンなどが挙げられる。これらの環状オレフィンは、単独で用いてもよく、２種以上が併用されていてもよい。 Examples of the cyclic olefin include a norbornene-based monomer, a cyclic diene-based monomer, and a vinyl alicyclic hydrocarbon-based monomer. Specifically, examples of the cyclic olefin include norbornene, vinylnorbornene, phenylnorbornene, dicyclopentadiene, tetracyclododecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclohexadiene, cyclooctadiene and the like. These cyclic olefins may be used alone or in combination of two or more.
　環状オレフィンと共重合可能な他のモノマーとしては、例えば、鎖状オレフィン、アクリル酸メタクリル酸、アクリル酸エステル、メタクリル酸エステル、芳香族ビニル化合物、不飽和ニトリル、脂肪族共役ジエンなどが挙げられる。具体的には、このようなモノマーとしては、エチレン、プロピレン、ブテン、アクリル酸、メタクリル酸、フマル酸、無水フマル酸、マレイン酸、無水マレイン酸、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、スチレン、ビニルトルエン、アクリロニトリル、メタクリロニトリル、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエンなどが挙げられる。これらの他のモノマーは、単独で用いてもよく、２種以上を併用してもよい。 Examples of other monomers copolymerizable with the cyclic olefin include chain olefins, acrylate acrylates, acrylates, methacrylic acids, aromatic vinyl compounds, unsaturated nitriles, and aliphatic conjugated dienes. Specifically, such monomers include ethylene, propylene, butene, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, maleic acid, maleic anhydride, methyl acrylate, ethyl acrylate, and propyl acrylate. Isopropyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, styrene, vinyltoluene, acrylonitrile, methacrylonitrile, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene and the like can be mentioned. These other monomers may be used alone or in combination of two or more.
　本開示において「環状オレフィンコポリマーを主成分とする樹脂」とは、後述する添加剤分を除いて、上述の環状オレフィンコポリマーを５０質量％以上含有する樹脂を意味する。すなわち、「環状オレフィンコポリマーを主成分とする樹脂」とは、環状オレフィンコポリマーのみからなる樹脂（環状オレフィンコポリマーが１００質量％）であってもよく、環状オレフィンコポリマーと環状オレフィンコポリマー以外の樹脂とを含む樹脂であってもよい。 In the present disclosure, the "resin containing a cyclic olefin copolymer as a main component" means a resin containing 50% by mass or more of the above-mentioned cyclic olefin copolymer, excluding the additives described later. That is, the "resin containing the cyclic olefin copolymer as a main component" may be a resin composed only of the cyclic olefin copolymer (100% by mass of the cyclic olefin copolymer), and the cyclic olefin copolymer and the resin other than the cyclic olefin copolymer may be used. It may be a resin containing.
　環状オレフィンコポリマー以外の樹脂としては、例えば、アクリル樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂、ポリアミド、ポリイミドなどが挙げられる。これらの樹脂は、例えば、環状オレフィンコポリマーとの相溶性などを考慮して、単独で使用してもよく、２種以上を併用してもよい。 Examples of resins other than the cyclic olefin copolymer include acrylic resin, epoxy resin, phenol resin, melamine resin, urea resin, polyamide, and polyimide. These resins may be used alone or in combination of two or more, for example, in consideration of compatibility with the cyclic olefin copolymer.
　一実施形態に係る有機樹脂フィルムに含まれる第１溶媒は、トルエン、キシレン、オクタン、デカヒドロナフタレン、グリコールエーテル（エチレングリコールジメチルエーテル）、デカン、およびトリデカンからなる群より選択される少なくとも１種の溶媒である。第１溶媒は比較的高い沸点を有する溶媒である。これらの第１溶媒の中でも、トルエンまたはキシレンを使用するのがよい。 The first solvent contained in the organic resin film according to one embodiment is at least one solvent selected from the group consisting of toluene, xylene, octane, decahydronaphthalene, glycol ether (ethylene glycol dimethyl ether), decane, and tridecane. Is. The first solvent is a solvent having a relatively high boiling point. Among these first solvents, toluene or xylene is preferably used.
　一実施形態に係る有機樹脂フィルムに含まれる第２溶媒は、第１溶媒よりも沸点の低い溶媒である。第２溶媒は、シクロヘキサン、ベンゼン、ヘキサン、クロロホルム、およびジクロロエタンからなる群より選択される少なくとも１種の溶媒である。これらの第２溶媒の中でも、シクロヘキサンを使用するのがよい。 The second solvent contained in the organic resin film according to the first embodiment is a solvent having a boiling point lower than that of the first solvent. The second solvent is at least one solvent selected from the group consisting of cyclohexane, benzene, hexane, chloroform, and dichloroethane. Among these second solvents, cyclohexane is preferably used.
　有機樹脂フィルムが第１溶媒および第２溶媒を含んでいることにより、有機樹脂フィルムはしなやかさが増し、有機樹脂フィルム同士が密着しやすくなる。第１溶媒および第２溶媒の含有量としては、例えば、第１溶媒の含有量よりも第２溶媒の含有量を多くするのがよい。具体的には、第２溶媒の含有量が、第１溶媒の含有量の３．４倍以上７．２倍以下、特に、４．１倍以上７．２倍以下であるのがよい。第１溶媒の含有量よりも第２溶媒の含有量を多くすると、得られる有機樹脂フィルムは、積層圧着時の真空引きの過程で溶媒が揮発しやすくなる。これにより得られる有機樹脂フィルムは、デラミやフクレが発生し難くなる。 Since the organic resin film contains the first solvent and the second solvent, the suppleness of the organic resin film is increased, and the organic resin films are easily adhered to each other. As the contents of the first solvent and the second solvent, for example, the content of the second solvent may be larger than the content of the first solvent. Specifically, the content of the second solvent is preferably 3.4 times or more and 7.2 times or less, particularly 4.1 times or more and 7.2 times or less the content of the first solvent. When the content of the second solvent is larger than the content of the first solvent, the solvent of the obtained organic resin film tends to volatilize in the process of evacuation during laminating and pressure bonding. The organic resin film thus obtained is less likely to cause delamination and blistering.
　上述の第２溶媒の中で、シクロヘキサンは環状オレフィンコポリマーを溶解しやすい。シクロヘキサンは、親水親油バランス（ＨＬＢ）は約１５である。シクロヘキサンは、静電気を発生しやすい。そこで、シクロヘキサンよりもＨＬＢ値の低い溶媒を混合する。シクロヘキサンよりもＨＬＢ値に低い溶媒を混合することで静電気の発生を抑えることができる。そのような溶媒として、上記した第１溶媒（トルエン）を挙げることができる。トルエンのＨＬＢ値は１１．３である。 Among the above-mentioned second solvents, cyclohexane easily dissolves the cyclic olefin copolymer. Cyclohexane has a hydrophilic lipophilic balance (HLB) of about 15. Cyclohexane tends to generate static electricity. Therefore, a solvent having a lower HLB value than cyclohexane is mixed. The generation of static electricity can be suppressed by mixing a solvent having a HLB value lower than that of cyclohexane. Examples of such a solvent include the above-mentioned first solvent (toluene). The HLB value of toluene is 11.3.
　一実施形態に係る有機樹脂フィルムに含まれる第１溶媒および第２溶媒の含有量は、第１溶媒および第２溶媒の合計量が０．２質量％以上１．１質量％以下であってもよい。これらを質量割合としてｐｐｍの単位で表すと、２０００ｐｐｍ以上１１０００ｐｐｍ以下である。有機樹脂フィルムに含まれる第１溶媒および第２溶媒の合計量が０．２質量％以上１．１質量％以下であると、積層圧着試験および半田耐熱試験において、剥離しにくい有機樹脂フィルムを得ることができる。有機樹脂フィルムに含まれる第１溶媒および第２溶媒の含有量は、作製した有機樹脂フィルムから切り出した試料片をガスクロマトグラフィー分析にかけて測定する。 The content of the first solvent and the second solvent contained in the organic resin film according to one embodiment is such that the total amount of the first solvent and the second solvent is 0.2% by mass or more and 1.1% by mass or less. good. When these are expressed in units of ppm as a mass ratio, they are 2000 ppm or more and 11000 ppm or less. When the total amount of the first solvent and the second solvent contained in the organic resin film is 0.2% by mass or more and 1.1% by mass or less, an organic resin film that is difficult to peel off is obtained in the laminated pressure bonding test and the solder heat resistance test. be able to. The contents of the first solvent and the second solvent contained in the organic resin film are measured by performing gas chromatography analysis on a sample piece cut out from the produced organic resin film.
一実施形態に係る有機樹脂フィルムは、加圧加熱処理後に得られる積層体に対する積層圧着試験、半田耐熱試験において、剥離を抑制できるという点から、第２溶媒の含有量が第１溶媒の含有量よりも多い方がよい。 The content of the second solvent is the content of the first solvent in the organic resin film according to the first embodiment from the viewpoint that peeling can be suppressed in the laminated pressure bonding test and the solder heat resistance test on the laminate obtained after the pressure heat treatment. Better than more.
　一実施形態に係る有機樹脂フィルムには、例えば、酸化防止剤、紫外線吸収剤、着色剤、応力緩和剤、無機フィラー、難燃剤などの添加剤が含まれていてもよい。添加剤の含有量は、本開示の有機樹脂フィルムが奏する効果を阻害しない範囲であれば限定されない。一実施形態に係る有機樹脂フィルムには、例えば、添加剤は１質量％以上５０質量％以下の割合で含まれていてもよい。 The organic resin film according to one embodiment may contain additives such as an antioxidant, an ultraviolet absorber, a colorant, a stress relaxant, an inorganic filler, and a flame retardant. The content of the additive is not limited as long as it does not interfere with the effect of the organic resin film of the present disclosure. The organic resin film according to one embodiment may contain, for example, an additive in a proportion of 1% by mass or more and 50% by mass or less.
　無機フィラーとしては、例えば、シリカ、タルク、マイカ、クレー、炭酸カルシウム、酸化チタン、チタン酸バリウム、カーボンブラック、ガラスビーズ、ガラス中空球などが挙げられる。例えばシリカとしては、粉砕シリカ、溶融シリカなどが挙げられる。無機フィラーは１種のみを用いてもよく、２種以上を併用してもよい。無機フィラーの平均粒子径は特に限定されず、例えば、０．０１μｍ以上１０μｍ以下であり、０．５μｍ以上３μｍ以下であってもよい。無機フィラーの含有量としては、環状オレフィンコポリマー１００質量部に対して５質量部以上４０質量部以下の割合で含まれていてもよい。 Examples of the inorganic filler include silica, talc, mica, clay, calcium carbonate, titanium oxide, barium titanate, carbon black, glass beads, and glass hollow spheres. For example, examples of silica include crushed silica and molten silica. Only one kind of inorganic filler may be used, or two or more kinds may be used in combination. The average particle size of the inorganic filler is not particularly limited, and may be, for example, 0.01 μm or more and 10 μm or less, and 0.5 μm or more and 3 μm or less. The content of the inorganic filler may be 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer.
　難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラム、ポリリン酸メレム、ピロリン酸メラミン、ポリリン酸アンモニウム、赤燐、芳香族リン酸エステル、ホスホン酸エステル、ホスフィン酸エステル、ホスフィンオキサイド、ホスファゼン、メラミンシアノレート、エチレンビスペンタブロモベンゼン、エチレンビステトラブロモフタルイミドなどが挙げられる。これらの難燃剤は、単独で用いてもよく、２種以上を併用してもよい。 Examples of flame-retardant agents include melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonic acid ester, phosphinic acid ester, phosphine oxide, phosphazene, and melamine. Examples thereof include cyanolate, ethylene bispentabromobenzene, and ethylene bistetrabromophthalimide. These flame retardants may be used alone or in combination of two or more.
　この場合、積層未硬化シートを硬化して得られる積層硬化シートの誘電正接を低くすることができるという点から臭素系の難燃剤（エチレンビスペンタブロモベンゼン、エチレンビステトラブロモフタルイミドなど）を用いてもよい。難燃剤の平均粒子径は特に限定されず、例えば、０．０１μｍ以上１０μｍ以下であり、０．５μｍ以上３μｍ以下であってもよい。難燃剤の含有量としては、環状オレフィンコポリマー１００質量部に対して１５質量部以上４５質量部以下の割合で含まれていてもよい。 In this case, a bromine-based flame retardant (ethylenebispentabromobenzene, ethylenebistetrabromophthalimide, etc.) is used because the dielectric loss tangent of the laminated cured sheet obtained by curing the laminated uncured sheet can be lowered. May be good. The average particle size of the flame retardant is not particularly limited, and may be, for example, 0.01 μm or more and 10 μm or less, and 0.5 μm or more and 3 μm or less. The content of the flame retardant may be 15 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the cyclic olefin copolymer.
　本開示の有機樹脂フィルムを製造する方法は特に限定されない。例えば、環状オレフィンコポリマーを主成分とする樹脂を、第１溶媒および第２溶媒を含む混合溶媒に溶解または分散させ、必要に応じて、添加剤を添加して樹脂ワニスを得る。添加剤については、上述の複数種の中で必要なものを選択して用いる場合がある。 The method for producing the organic resin film of the present disclosure is not particularly limited. For example, a resin containing a cyclic olefin copolymer as a main component is dissolved or dispersed in a mixed solvent containing a first solvent and a second solvent, and if necessary, an additive is added to obtain a resin varnish. As the additive, a necessary additive may be selected and used from the above-mentioned plurality of types.
　次いで、得られた樹脂ワニスからフィルム状成形体を作製する。具体的には、バーコーター法、ドクターブレード法、ダイコーター法、押出法、射出成形法などによって、樹脂ワニスをフィルム状に成形し、その後１２０～１５０℃程度で１～１０分程度乾燥し、フィルム状成形体が得られる。このフィルム状成形体を加圧加熱処理に供して、第１溶媒および第２溶媒が残存する有機樹脂フィルムが得られる。加圧加熱処理条件としては、例えば、温度が１６０～２３０℃程度で圧力が１～１０ＭＰａ程度である。このようにして得られた有機樹脂フィルムは、例えば、０．０１～１ｍｍ程度の厚みを有している。 Next, a film-shaped molded product is produced from the obtained resin varnish. Specifically, the resin varnish is formed into a film by a bar coater method, a doctor blade method, a die coater method, an extrusion method, an injection molding method, etc., and then dried at about 120 to 150 ° C. for about 1 to 10 minutes. A film-shaped molded product is obtained. This film-shaped molded product is subjected to pressure heat treatment to obtain an organic resin film in which the first solvent and the second solvent remain. The conditions for the pressure heat treatment are, for example, a temperature of about 160 to 230 ° C. and a pressure of about 1 to 10 MPa. The organic resin film thus obtained has a thickness of, for example, about 0.01 to 1 mm.
　次に、本開示の金属張積層板について説明する。本開示の金属張積層板は、本開示の有機樹脂フィルムの少なくとも一方の面に金属箔を備えている。本開示の金属張積層板は、例えば、上述の有機樹脂フィルムと金属箔とを重ね合わせ加熱（硬化）加圧成形して得られる。金属箔としては特に限定されず、例えば、電解銅箔、圧延銅箔などの銅箔、アルミニウム箔、これらの金属箔を重ね合わせた複合箔などが挙げられる。これらの金属箔の中でも、例えば銅箔が用いられる。金属箔の厚みは特に限定されず、例えば５～１０５μｍ程度である。本開示の金属張積層板は、上述の有機樹脂フィルムと金属箔とをそれぞれ所望の枚数重ね合わせ、加熱加圧成形しても得られる。本開示の金属張積層板は、例えばプリント配線基板などに用いられる。 Next, the metal-clad laminate of the present disclosure will be described. The metal-clad laminate of the present disclosure includes a metal foil on at least one surface of the organic resin film of the present disclosure. The metal-clad laminate of the present disclosure is obtained, for example, by superimposing the above-mentioned organic resin film and a metal foil and heating (curing) pressure molding. The metal foil is not particularly limited, and examples thereof include a copper foil such as an electrolytic copper foil and a rolled copper foil, an aluminum foil, and a composite foil obtained by superimposing these metal foils. Among these metal foils, for example, copper foil is used. The thickness of the metal foil is not particularly limited, and is, for example, about 5 to 105 μm. The metal-clad laminate of the present disclosure can also be obtained by laminating a desired number of the above-mentioned organic resin films and metal foils and heat-pressing molding. The metal-clad laminate of the present disclosure is used for, for example, a printed wiring board.
　次に、本開示の配線基板について説明する。本開示の配線基板は、複数の絶縁層と該絶縁層間に配置された導体層とを具備しており、絶縁層が本開示の有機樹脂フィルムで形成されている。本開示の配線基板は、例えば、本開示の金属張積層板に回路およびスルーホールが形成された内層板とプリプレグとを重ね合わせ、プリプレグの表面に金属箔を積層させた後、加熱（硬化）加圧成形して得られる。さらに、表面の金属箔に回路およびスルーホールを形成して、多層プリント配線基板としてもよい。 Next, the wiring board of the present disclosure will be described. The wiring board of the present disclosure includes a plurality of insulating layers and a conductor layer arranged between the insulating layers, and the insulating layer is formed of the organic resin film of the present disclosure. In the wiring board of the present disclosure, for example, an inner layer plate in which a circuit and a through hole are formed on the metal-clad laminate of the present disclosure and a prepreg are superposed, a metal foil is laminated on the surface of the prepreg, and then heating (curing) is performed. Obtained by pressure molding. Further, a circuit and a through hole may be formed in the metal foil on the surface to form a multilayer printed wiring board.
　以下、実施例を挙げて本開示の実施形態を具体的に説明するが、本開示の実施形態はこれらの実施例に限定されるものではない。 Hereinafter, embodiments of the present disclosure will be specifically described with reference to examples, but the embodiments of the present disclosure are not limited to these examples.
　耐熱環状オレフィンコポリマー（耐熱ＣＯＣ（ラジカル重合可能な官能基を含む）、三井化学（株）製）１００質量部に対して、難燃剤としてＳＡＹＴＥＸ８０１０を３０質量部、分子内にベンゼン環を有する過酸化物として、ジ－ｔ－ブチルパーオキサイド（パーブチルＤ、日油（株）製）を１．８質量部、およびシリカを２０質量部の割合で添加した。得られた混合物４０質量％と溶媒６０質量％とを混合して、樹脂ワニスを得た。溶媒としては、第１溶媒としてトルエン（沸点１１０℃）を用いた。第２溶媒としてシクロヘキサン（沸点８１℃）を用いた。第１溶媒（トルエン）と第２溶媒（シクロヘキサン）とを１：１の質量比で混合したものを混合溶媒として用いた。 Heat-resistant cyclic olefin copolymer (heat-resistant COC (including radically polymerizable functional group), manufactured by Mitsui Chemicals Co., Ltd.) 100 parts by mass, 30 parts by mass of SAYTEX8010 as a flame retardant, peroxide having a benzene ring in the molecule As a substance, 1.8 parts by mass of dit-butyl peroxide (Perbutyl D, manufactured by Nichiyu Co., Ltd.) and 20 parts by mass of silica were added. 40% by mass of the obtained mixture and 60% by mass of the solvent were mixed to obtain a resin varnish. As the solvent, toluene (boiling point 110 ° C.) was used as the first solvent. Cyclohexane (boiling point 81 ° C.) was used as the second solvent. A mixture of the first solvent (toluene) and the second solvent (cyclohexane) at a mass ratio of 1: 1 was used as the mixed solvent.
　試料Ｎｏ．１は、第２溶媒（シクロヘキサン）のみを用いて得られた有機樹脂フィルムから作製した試料である。試料Ｎｏ．２は、第１溶媒（トルエン）のみを用いて得られた有機樹脂フィルムから作製した試料である。試料Ｎｏ．３～８は、混合溶媒を用いて得られた有機樹脂フィルムから作製した試料である。 Sample No. Reference numeral 1 denotes a sample prepared from an organic resin film obtained using only a second solvent (cyclohexane). Sample No. Reference numeral 2 denotes a sample prepared from an organic resin film obtained by using only the first solvent (toluene). Sample No. 3 to 8 are samples prepared from an organic resin film obtained by using a mixed solvent.
　次いで、バーコーターを用いて、得られた樹脂ワニスをシート状に成形し、３０℃で４８時間乾燥させて、１５μｍの厚みを有する有機樹脂フィルムを得た（試料Ｎｏ．１）。試料Ｎｏ．１の有機樹脂フィルムにおけるシクロヘキサン（第２溶媒）の残存量を、表１に示す。 Next, using a bar coater, the obtained resin varnish was formed into a sheet and dried at 30 ° C. for 48 hours to obtain an organic resin film having a thickness of 15 μm (Sample No. 1). Sample No. The residual amount of cyclohexane (second solvent) in the organic resin film of No. 1 is shown in Table 1.
　乾燥温度および乾燥時間を種々変更して、溶媒の残存量が異なる１５μｍの厚みを有する有機樹脂フィルムを得た（試料Ｎｏ．２～８）。試料Ｎｏ．２～８の有機樹脂フィルムにおけるトルエン（第１溶媒）およびシクロヘキサン（第２溶媒）の残存量を、表１に示す。 The drying temperature and the drying time were variously changed to obtain organic resin films having a thickness of 15 μm in which the residual amount of the solvent was different (Sample Nos. 2 to 8). Sample No. Table 1 shows the residual amounts of toluene (first solvent) and cyclohexane (second solvent) in the organic resin films 2 to 8.
　試料Ｎｏ．２～８の乾燥条件は、以下の通りである。条件は、順に、最高温度および保持時間である。試料Ｎｏ．２は１４０℃および４分、試料Ｎｏ．３は１４０℃および１分、試料Ｎｏ．４は１４０℃および０．５分、試料Ｎｏ．５は１３０℃および２分、試料Ｎｏ．６は１３０℃および１分、試料Ｎｏ．７は１２０℃および１０分、試料Ｎｏ．８は１１０℃および１０分である。 Sample No. The drying conditions of 2 to 8 are as follows. The conditions are, in order, the maximum temperature and the holding time. Sample No. 2 is 140 ° C. and 4 minutes, sample No. 3 is 140 ° C. and 1 minute, sample No. 4 is 140 ° C. and 0.5 minutes, sample No. 5 is 130 ° C. and 2 minutes, sample No. 6 is 130 ° C. and 1 minute, sample No. 7 is 120 ° C. and 10 minutes, sample No. 8 is 110 ° C. and 10 minutes.
　まず、作製した有機樹脂フィルムに含まれる第１溶媒および第２溶媒の含有量をガスクロマトグラフィー分析により測定した。ガスクロマトグラフィー分析に用いる試料には、作製した有機樹脂フィルムから切り出した試料片を用いた。 First, the contents of the first solvent and the second solvent contained in the produced organic resin film were measured by gas chromatography analysis. As the sample used for the gas chromatography analysis, a sample piece cut out from the prepared organic resin film was used.
　次いで、試料Ｎｏ．１～８の有機樹脂フィルムについて、積層圧着試験および半田耐熱試験を行った。積層圧着試験は、次の手順で行った。まず、得られた有機樹脂フィルムを５００ｍｍ×５００ｍｍのサイズに切断した。次いで、切断した有機樹脂フィルムを真空積層ホットプレス機（（株）名機製作所製）を用いて、２０枚積層した。積層時の圧力は１ＭＰａであり、温度は１１０℃（最高温度）で、最高温度での保持時間は１分であった。積層後に剥離部分が１か所でも存在すればＮＧと評価し、剥離部分が存在しなければＯＫと評価した。結果を表１に示す。 Next, sample No. Laminated pressure bonding tests and solder heat resistance tests were performed on the organic resin films 1 to 8. The laminated crimping test was carried out according to the following procedure. First, the obtained organic resin film was cut into a size of 500 mm × 500 mm. Next, 20 sheets of the cut organic resin film were laminated using a vacuum laminating hot press machine (manufactured by Meiki Seisakusho Co., Ltd.). The pressure at the time of stacking was 1 MPa, the temperature was 110 ° C. (maximum temperature), and the holding time at the maximum temperature was 1 minute. If there was even one peeled portion after laminating, it was evaluated as NG, and if there was no peeled portion, it was evaluated as OK. The results are shown in Table 1.
　半田耐熱試験（半田耐熱試験Ａ）は、次の手順にて試料を作製し、評価した。まず、得られた有機樹脂フィルムを３００ｍｍ×３００ｍｍのサイズに切断した。次に、得られた有機樹脂フィルムを４枚重ねて積層体を作製した。次いで、積層体の両面に銅箔を置き、積層プレス機を用いて加圧加熱処理を行い、銅張積層板を作製した。加圧加熱処理時の条件は、最高温度：１８０℃、最高温度での保持時間：２時間、圧力：３ＭＰａの条件とした。 In the solder heat resistance test (solder heat resistance test A), a sample was prepared and evaluated according to the following procedure. First, the obtained organic resin film was cut into a size of 300 mm × 300 mm. Next, four obtained organic resin films were laminated to prepare a laminate. Next, copper foils were placed on both sides of the laminate and subjected to pressure heat treatment using a laminate press to prepare a copper-clad laminate. The conditions for the pressure heat treatment were the maximum temperature: 180 ° C., the holding time at the maximum temperature: 2 hours, and the pressure: 3 MPa.
　次に、作製した銅張積層板から半田耐熱試験に用いる試料を作製した。まず、銅張積層板を３０ｍｍ×３０ｍｍのサイズに切断して、半田耐熱試験用の試料を作製した。次に、半田耐熱試験用の試料に対して、下記の条件の半田耐熱試験（表１における半田耐熱試験Ａおよび半田耐熱試験Ｂ）を行った。半田耐熱試験Ａの条件は、最高温度が２８８℃、保持時間が１０秒である。半田耐熱試験Ｂの条件は、最高温度は同じで、保持時間を６０秒とした。半田耐熱試験ＡおよびＢは試料を半田槽に浮かせる方法で行った。試験後に剥離部分が１か所でも存在すればＮＧと評価し、剥離部分が存在しなければＯＫと評価した。結果を表１に示す。 Next, a sample used for the solder heat resistance test was prepared from the prepared copper-clad laminate. First, a copper-clad laminate was cut into a size of 30 mm × 30 mm to prepare a sample for a solder heat resistance test. Next, a solder heat resistance test under the following conditions (solder heat resistance test A and solder heat resistance test B in Table 1) was performed on the sample for the solder heat resistance test. The conditions of the solder heat resistance test A are that the maximum temperature is 288 ° C. and the holding time is 10 seconds. The conditions of the solder heat resistance test B were the same as the maximum temperature and the holding time was 60 seconds. Solder heat resistance tests A and B were carried out by a method in which the sample was floated in a solder bath. After the test, if there was even one peeled part, it was evaluated as NG, and if there was no peeled part, it was evaluated as OK. The results are shown in Table 1.
　表１では、有機樹脂フィルムに含まれている溶媒量をｐｐｍ表記で表した。混合溶媒を用いて作製した試料は、いずれも第１溶媒および第２溶媒を含んだものであった。その含有量は２７３５ｐｐｍ以上５７６００ｐｐｍ以下であった。また、混合溶媒を用いて作製した試料Ｎｏ．３～８は、第２溶媒の含有量が第１溶媒の含有量よりも多いものであった。 In Table 1, the amount of solvent contained in the organic resin film is expressed in ppm. The samples prepared using the mixed solvent all contained the first solvent and the second solvent. Its content was 2735 ppm or more and 57600 ppm or less. In addition, the sample No. prepared using the mixed solvent. In 3 to 8, the content of the second solvent was higher than the content of the first solvent.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本開示に係る有機樹脂フィルムを用いて作製した試料（試料Ｎｏ．３～８）は、積層圧着試験において剥離部分が認められなかった。試料Ｎｏ．３～７は、半田耐熱試験Ａの条件において剥離部分が認められず、試料Ｎｏ．３～６については、表面の銅箔にわずかなフクレも観察されなかった。試料Ｎｏ．３～６は、半田耐熱試験Ｂの条件においても剥離部分が認められず、試料Ｎｏ．３～６については、表面の銅箔にわずかなフクレも観察されなかった。このように、第２溶媒の含有量が、第１溶媒の含有量の３．４倍以上７．２倍以下であれば、剥離部分もわずかなフクレも観察されないことがわかる。 As shown in Table 1, in the samples (Sample Nos. 3 to 8) prepared using the organic resin film according to the present disclosure, no peeled portion was observed in the laminated pressure bonding test. Sample No. In Nos. 3 to 7, no peeled portion was observed under the conditions of the solder heat resistance test A, and the sample No. For 3 to 6, no slight blisters were observed on the copper foil on the surface. Sample No. In Nos. 3 to 6, no peeled portion was observed even under the condition of the solder heat resistance test B, and the sample No. For 3 to 6, no slight blisters were observed on the copper foil on the surface. As described above, when the content of the second solvent is 3.4 times or more and 7.2 times or less the content of the first solvent, it can be seen that neither the peeled portion nor a slight blistering is observed.
　一方、試料Ｎｏ．１および２は、積層圧着試験において剥離部分が認められた。また、半田耐熱試験（半田耐熱試験Ａおよび半田耐熱試験Ｂ）において、試験後の試料に剥離部分が認められた。試料Ｎｏ．３～８は、試料Ｎｏ．１および２に比べて、有機樹脂フィルム同士の密着性に優れていた。 On the other hand, sample No. In Nos. 1 and 2, peeled portions were observed in the laminated crimping test. Further, in the solder heat resistance test (solder heat resistance test A and solder heat resistance test B), a peeled portion was observed in the sample after the test. Sample No. Sample Nos. 3 to 8 are No. Compared with 1 and 2, the adhesion between the organic resin films was excellent.
　次に、第１溶媒としてキシレンを使用し、下記の乾燥条件で乾燥した以外は、上記の試料Ｎｏ．３～８と同様の手順で、溶媒の残存量が異なる１５μｍの厚みを有する有機樹脂フィルムを得た（試料Ｎｏ．９～１２）。試料Ｎｏ．９～１２の有機樹脂フィルムにおけるキシレン（第１溶媒）およびシクロヘキサン（第２溶媒）の残存量を、表２に示す。 Next, except that xylene was used as the first solvent and dried under the following drying conditions, the above sample No. By the same procedure as in 3 to 8, organic resin films having a thickness of 15 μm with different residual amounts of solvent were obtained (Sample Nos. 9 to 12). Sample No. Table 2 shows the residual amounts of xylene (first solvent) and cyclohexane (second solvent) in the organic resin films 9 to 12.
　試料Ｎｏ．９～１２の乾燥条件は、以下の通りである。条件は、順に、最高温度および保持時間である。試料Ｎｏ．９は１４０℃および１分、試料Ｎｏ．１０は１４０℃および０．５分、試料Ｎｏ．１１は１３０℃および１分、試料Ｎｏ．１２は１２０℃および１０分である。 Sample No. The drying conditions of 9 to 12 are as follows. The conditions are, in order, the maximum temperature and the holding time. Sample No. 9 is 140 ° C. and 1 minute, sample No. 10 is 140 ° C. and 0.5 minutes, sample No. No. 11 was sample No. 11 at 130 ° C. and 1 minute. 12 is 120 ° C. and 10 minutes.
　　次いで、上記の試料Ｎｏ．３～８と同様の手順で、積層圧着試験および半田耐熱試験（半田耐熱試験Ａおよび半田耐熱試験Ｂ）を行った。結果を表２に示す。 Next, the above sample No. The laminated crimping test and the solder heat resistance test (solder heat resistance test A and solder heat resistance test B) were performed in the same procedure as in 3 to 8. The results are shown in Table 2.
　表２では、有機樹脂フィルムに含まれている溶媒量をｐｐｍ表記で表した。混合溶媒を用いて作製した試料は、いずれも第１溶媒および第２溶媒を含んだものであった。その含有量は４５０ｐｐｍ以上３９８３０ｐｐｍ以下であった。また、混合溶媒を用いて作製した試料Ｎｏ．９～１２は、第２溶媒の含有量が第１溶媒の含有量よりも多いものであった。 In Table 2, the amount of solvent contained in the organic resin film is expressed in ppm. The samples prepared using the mixed solvent all contained the first solvent and the second solvent. Its content was 450 ppm or more and 39830 ppm or less. In addition, the sample No. prepared using the mixed solvent. In 9 to 12, the content of the second solvent was higher than the content of the first solvent.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、本開示に係る有機樹脂フィルムを用いて作製した試料（試料Ｎｏ．９～１２）は、積層圧着試験において剥離部分が認められなかった。試料Ｎｏ．９～１２は、半田耐熱試験Ａの条件および半田耐熱試験Ｂの条件において剥離部分が認められず、表面の銅箔にわずかなフクレも観察されなかった。さらに、試料Ｎｏ．９～１２は、上記の試料Ｎｏ．１および２に比べて、有機樹脂フィルム同士の密着性に優れていた。 As shown in Table 2, in the samples (Sample Nos. 9 to 12) prepared using the organic resin film according to the present disclosure, no peeled portion was observed in the laminated pressure bonding test. Sample No. In Nos. 9 to 12, no peeled portion was observed under the conditions of the solder heat resistance test A and the conditions of the solder heat resistance test B, and no slight blister was observed on the copper foil on the surface. Furthermore, the sample No. 9 to 12 are the above-mentioned sample Nos. Compared with 1 and 2, the adhesion between the organic resin films was excellent.

Claims (8)

  1. 　環状オレフィンコポリマーを主成分とする樹脂、第１溶媒、および該第１溶媒よりも沸点の低い第２溶媒を含み、
    　前記第１溶媒は、トルエン、キシレン、オクタン、デカヒドロナフタレン、エチレングリコールジメチルエーテル、デカンおよびトリデカンからなる群より選択される少なくとも１種の溶媒であり、
    　前記第２溶媒は、シクロヘキサン、ベンゼン、ヘキサン、クロロホルムおよびジクロロエタンからなる群より選択される少なくとも１種の溶媒である、
    有機樹脂フィルム。     It contains a resin containing a cyclic olefin copolymer as a main component, a first solvent, and a second solvent having a boiling point lower than that of the first solvent.
    The first solvent is at least one solvent selected from the group consisting of toluene, xylene, octane, decahydronaphthalene, ethylene glycol dimethyl ether, decane and tridecane.
    The second solvent is at least one solvent selected from the group consisting of cyclohexane, benzene, hexane, chloroform and dichloroethane.
    Organic resin film.
  2. 　前記第１溶媒および前記第２溶媒が、合計で０．２質量％以上１．１質量％以下の割合で含まれる請求項１に記載の有機樹脂フィルム。 The organic resin film according to claim 1, wherein the first solvent and the second solvent are contained in a total ratio of 0.2% by mass or more and 1.1% by mass or less.
  3. 　前記第２溶媒の含有量が前記第１溶媒の含有量よりも多い、請求項１または２に記載の有機樹脂フィルム。 The organic resin film according to claim 1 or 2, wherein the content of the second solvent is larger than the content of the first solvent.
  4. 　前記第１溶媒がトルエンまたはキシレンである、請求項１～３のいずれかに記載の有機樹脂フィルム。 The organic resin film according to any one of claims 1 to 3, wherein the first solvent is toluene or xylene.
  5. 　前記第２溶媒がシクロヘキサンである、請求項１～４のいずれかに記載の有機樹脂フィルム。 The organic resin film according to any one of claims 1 to 4, wherein the second solvent is cyclohexane.
  6. 　前記第１溶媒がトルエンであり、前記第２溶媒の含有量が、前記第１溶媒の含有量の３．４倍以上７．２倍以下である、請求項１～５のいずれかに記載の有機樹脂フィルム。 The invention according to any one of claims 1 to 5, wherein the first solvent is toluene, and the content of the second solvent is 3.4 times or more and 7.2 times or less the content of the first solvent. Organic resin film.
  7. 　請求項１～６のいずれかに記載の有機樹脂フィルムと、該有機樹脂フィルムの少なくとも一方の面に積層された金属箔とを含むことを特徴とする金属張積層板。 A metal-clad laminate comprising the organic resin film according to any one of claims 1 to 6 and a metal foil laminated on at least one surface of the organic resin film.
  8. 　絶縁層と、該絶縁層の主面に配置された導体層とを具備し、前記絶縁層が請求項１～６のいずれかに記載の有機樹脂フィルムにより構成されていることを特徴とする配線基板。 A wiring comprising an insulating layer and a conductor layer arranged on a main surface of the insulating layer, wherein the insulating layer is made of the organic resin film according to any one of claims 1 to 6. substrate.
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JP2015140364A (en) * 2014-01-27 2015-08-03 京セラ株式会社 Dielectric resin and dielectric film, and film capacitor
WO2015133473A1 (en) * 2014-03-03 2015-09-11 京セラ株式会社 Film capacitor, connected capacitor, inverter and electric vehicle
JP2019147930A (en) * 2018-02-28 2019-09-05 三井化学株式会社 Cyclic olefin polymer composition and crosslinked body thereof
JP2020004852A (en) * 2018-06-28 2020-01-09 京セラ株式会社 Laminated uncured sheet

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JP2019147930A (en) * 2018-02-28 2019-09-05 三井化学株式会社 Cyclic olefin polymer composition and crosslinked body thereof
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