JP6123232B2 - Release polyimide film and method for producing multilayer printed wiring board - Google Patents
Release polyimide film and method for producing multilayer printed wiring board Download PDFInfo
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- JP6123232B2 JP6123232B2 JP2012241948A JP2012241948A JP6123232B2 JP 6123232 B2 JP6123232 B2 JP 6123232B2 JP 2012241948 A JP2012241948 A JP 2012241948A JP 2012241948 A JP2012241948 A JP 2012241948A JP 6123232 B2 JP6123232 B2 JP 6123232B2
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- 229920001721 polyimide Polymers 0.000 title claims description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000012790 adhesive layer Substances 0.000 claims description 49
- 239000010410 layer Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 229920000647 polyepoxide Polymers 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 239000010408 film Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 10
- 238000003825 pressing Methods 0.000 description 7
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- 229920001646 UPILEX Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229920000306 polymethylpentene Polymers 0.000 description 4
- 239000011116 polymethylpentene Substances 0.000 description 4
- 229920002050 silicone resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012787 coverlay film Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、離型ポリイミドフィルム及び多層プリント配線板の製造方法に関し、特に、熱板プレス、ロールラミネータ、ダブルベルトプレス等の成型時に使用される離型ポリイミドフィルム及びそれを用いた多層プリント配線板の製造方法に関する。 The present invention relates to a release polyimide film and a method for producing a multilayer printed wiring board, and in particular, a release polyimide film used at the time of molding such as a hot plate press, a roll laminator, a double belt press, and a multilayer printed wiring board using the same. It relates to the manufacturing method.
熱板プレス、ロールラミネータ、ダブルベルトプレス等は、多層プリント配線板の製造において広く使われている装置である。特に、多層プリント配線板を製造するには、片面又は両面に内層回路を形成した絶縁基板上に、プリプレグと呼ばれるガラス布に熱硬化性樹脂を含浸し半硬化状態にした材料を銅箔と重ねて熱板プレスにより積層一体化する。かかる装置において成形加工、積層加工する際に熱硬化樹脂が染み出して、被成形体ないし被積層体とが接着してしまうことがある。そのため、この接着を避けるために離型フィルムが必要となる。特に高温、高圧での成形加工、積層加工においては、耐熱性と機械的強度とに優れる離型フィルムが必要になる。 Hot plate presses, roll laminators, double belt presses, and the like are devices widely used in the production of multilayer printed wiring boards. In particular, in order to manufacture a multilayer printed wiring board, a material obtained by impregnating a glass cloth called a prepreg with a thermosetting resin into a semi-cured state is laminated with a copper foil on an insulating substrate having an inner layer circuit formed on one side or both sides. Laminate and integrate with a hot plate press. When molding and laminating in such an apparatus, the thermosetting resin may ooze out and adhere to the molded body or the laminated body. Therefore, a release film is necessary to avoid this adhesion. In particular, in a molding process and a lamination process at a high temperature and a high pressure, a release film having excellent heat resistance and mechanical strength is required.
また、光学的異方性の溶融相を形成する熱可塑性液晶ポリマーからなるフィルム（以下、「ＬＣＰフィルム」と略すことがある）等を内在する銅張積層板では、銅箔を熱板プレスする際にも、離型フィルムが使用されている。 Further, in a copper-clad laminate including a film made of a thermoplastic liquid crystal polymer (hereinafter, may be abbreviated as “LCP film”) that forms an optically anisotropic molten phase, the copper foil is hot-plate pressed. In some cases, release films are used.
また、フレキシブルプリント配線板の製造工程において、電気回路を形成したフレキシブルプリント配線板本体に対して、ＬＣＰフィルムからなるカバーレイフィルムを熱板プレスにより熱硬化性接着剤で熱接着する際にも、カバーレイフィルムと熱板プレス板とが接着するのを防止するために、離型フィルムが広く使用されている。 Moreover, in the manufacturing process of the flexible printed wiring board, when the cover lay film made of LCP film is thermally bonded with a thermosetting adhesive by a hot plate press to the flexible printed wiring board body on which the electric circuit is formed, A release film is widely used to prevent the coverlay film and the hot plate press plate from adhering to each other.
これらの離型フィルムは、ＬＣＰフィルムを熱溶融する際、熱板プレス成形による高温下で使用すべく、耐熱性を有することが求められている。 These release films are required to have heat resistance so as to be used at a high temperature by hot plate press molding when the LCP film is melted by heat.
また、近年、熱硬化性樹脂やＬＣＰの種類の多様化に加えて、成形時間の短時間化を目的に、より高温で熱板プレスすることも重要となっている。さらに、被成形体ないし被積層体の耐熱性を確保するため、熱硬化性樹脂の反応を十分に進行させることができる高温での熱板プレスが好まれる傾向にある。そのため、２００℃を超える高い温度において、熱硬化性樹脂を熱板プレスで成形することが求められ、高温で耐熱性を有する離型フィルムが期待されている。 In recent years, in addition to diversification of types of thermosetting resins and LCPs, it is also important to hot plate press at higher temperatures for the purpose of shortening the molding time. Furthermore, in order to ensure the heat resistance of the molded body or the laminated body, a hot plate press at a high temperature capable of sufficiently proceeding the reaction of the thermosetting resin tends to be preferred. Therefore, it is required to mold a thermosetting resin with a hot plate press at a high temperature exceeding 200 ° C., and a release film having heat resistance at high temperatures is expected.
なお、従来、離型用フィルムとしては、ポリエチレンテレフタレート樹脂（ＰＥＴ樹脂）、ポリメチルペンテン樹脂（ＰＭＰ樹脂）等からなるフィルムが実用化されている。また、熱可塑性エラストマーからなる離型用フィルムとしては、結晶成分にブチレンテレフタレートを含む結晶性芳香族ポリエステル含有の樹脂組成物からなるフィルムを使用する方法が知られている（例えば、特許文献１参照）。 Conventionally, as a release film, a film made of polyethylene terephthalate resin (PET resin), polymethylpentene resin (PMP resin) or the like has been put into practical use. Further, as a release film made of a thermoplastic elastomer, a method of using a film made of a crystalline aromatic polyester-containing resin composition containing butylene terephthalate as a crystal component is known (see, for example, Patent Document 1). ).
しかし、離型用フィルムとして特許文献１に示すように、ポリエチレンテレフタレート樹脂（ＰＥＴ樹脂）、ポリメチルペンテン樹脂（ＰＭＰ樹脂）あるいは結晶成分にブチレンテレフタレートを含む結晶性芳香族ポリエステル含有の樹脂組成物からなるフィルムを使用する場合、１８０℃前後における一般的な熱板プレス温度において、フィルム変形、融着、破れが起こり、剥離性に欠ける、あるいは、剥離できても接着層に亀裂、割れ、うねりが生じるといった問題があり、平坦性に優れる接着層が得られない。このように、従来のフィルムは、熱板プレス成形において、離型用フィルムとして好適に使用できないのが実情となっている。 However, as disclosed in Patent Document 1, as a release film, a polyethylene terephthalate resin (PET resin), a polymethylpentene resin (PMP resin), or a crystalline aromatic polyester-containing resin composition containing butylene terephthalate as a crystal component. When the film is used, the film is deformed, fused or torn at a general hot plate press temperature of around 180 ° C. and lacks peelability, or even if it can be peeled, the adhesive layer has cracks, cracks, and undulations. There is a problem that it occurs, and an adhesive layer having excellent flatness cannot be obtained. As described above, the conventional film cannot be suitably used as a release film in hot plate press molding.
本発明は、上記に鑑みなされたもので、熱板プレス、ロールラミネータ、ダブルプレス等の成形で多層プリント配線板を得る製造において、被成形体ないし被積層体との剥離性に優れ、しかも、例えば２００℃を超える使用温度においてもフィルムが溶断することのない耐熱強度を併せて有し、表面の平坦性に優れる被成形体ないし被積層体を得ることが可能な離型ポリイミドフィルム、及びこれを用いた多層プリント配線板の製造方法を提供することを目的とする。 The present invention was made in view of the above, in the production of a multilayer printed wiring board by molding such as hot plate press, roll laminator, double press, etc., excellent in peelability from the molded body or laminated body, For example, a release polyimide film that has a heat-resistant strength that prevents the film from fusing even at a use temperature exceeding 200 ° C., and that can obtain a molded body or a laminated body having excellent surface flatness, and this It aims at providing the manufacturing method of the multilayer printed wiring board using this.
本発明者らはこのような問題を解決するために研究を進めた結果、ポリイミドフィルム面上に離型層を有する離型ポリイミドフィルムが上記課題を解決できることを見出し、本発明に至った。 As a result of advancing research to solve such problems, the present inventors have found that a release polyimide film having a release layer on the polyimide film surface can solve the above problems, and have reached the present invention.
すなわち、本発明は下記のとおりである。
［１］ ポリイミドフィルムの一方の面上に、離型層を有する離型ポリイミドフィルム。
［２］ 前記離型層の厚みが０．０５〜５μｍである［１］に記載の離型ポリイミドフィルム。
［３］ 前記ポリイミドフィルムの厚みが１０〜５０μｍである上記［１］又は［２］に記載の離型ポリイミドフィルム。
［４］ 前記ポリイミドフィルムの表面粗さ（Ｒａ）が０．０５μｍ未満である上記［１］〜［３］のいずれかに記載の離型ポリイミドフィルム。
［５］ 前記離型層がシリコーン系樹脂を含む［１］〜［４］のいずれかに記載の離型ポリイミドフィルム。
［６］ 前記離型層のポリイミドフィルムの設けられていない面上に、接着層を有する［１］〜［５］のいずれかに記載の離型ポリイミドフィルム。
［７］ 前記接着層が、エポキシ樹脂、及びエポキシ樹脂硬化剤を含む樹脂組成物を用いてなる［６］に記載の離型ポリイミドフィルム。
That is, the present invention is as follows.
[1] A release polyimide film having a release layer on one surface of the polyimide film.
[2] The release polyimide film according to [1], wherein the release layer has a thickness of 0.05 to 5 μm.
[3] The release polyimide film according to the above [1] or [2], wherein the polyimide film has a thickness of 10 to 50 μm.
[4] The release polyimide film according to any one of [1] to [3], wherein the polyimide film has a surface roughness (Ra) of less than 0.05 μm.
[5] The release polyimide film according to any one of [1] to [4], wherein the release layer includes a silicone resin.
[6] The release polyimide film according to any one of [1] to [5], which has an adhesive layer on a surface of the release layer on which no polyimide film is provided.
[7] The release polyimide film according to [6], wherein the adhesive layer uses a resin composition containing an epoxy resin and an epoxy resin curing agent.
［８］ ポリイミドフィルムの一方の面上に離型層を形成する工程、前記離型層のポリイミドフィルムの設けられていない面上に接着層を形成し、接着層を有する離型ポリイミドフィルムを製造する工程、前記接着層を有する離型ポリイミドフィルムを用いて多層プリント配線板を製造する工程、多層プリント配線板から離型ポリイミドフィルムを除去する工程、を含む多層プリント配線板の製造方法。 [8] A step of forming a release layer on one surface of the polyimide film, an adhesive layer is formed on the surface of the release layer where the polyimide film is not provided, and a release polyimide film having the adhesive layer is manufactured. The manufacturing method of a multilayer printed wiring board including the process to manufacture a multilayer printed wiring board using the mold release polyimide film which has the said contact bonding layer, the process of removing a mold release polyimide film from a multilayer printed wiring board.
本発明によれば、熱板プレス、ロールラミネータ、ダブルプレス等の成形で多層プリント配線板を得る製造において、被成形体ないし被積層体との剥離性に優れ、しかも、例えば２００℃を超える使用温度においてもフィルムが溶断することのない耐熱強度を併せて有し、表面の平坦性に優れる被成形体ないし被積層体を得ることが可能な離型ポリイミドフィルム、及びこれを用いた多層プリント配線板の製造方法を提供することができる。 According to the present invention, in production to obtain a multilayer printed wiring board by molding such as hot plate press, roll laminator, double press, etc., it is excellent in releasability from a molded body or a laminated body and is used, for example, exceeding 200 ° C. A release polyimide film capable of obtaining a molded body or a laminated body having excellent heat-resistant strength that prevents the film from fusing even at temperature and having excellent surface flatness, and multilayer printed wiring using the same A method for manufacturing a plate can be provided.
［離型ポリイミドフィルム］
まず、本発明の離型ポリイミドフィルムについて説明する。本発明の離型ポリイミドフィルムに用いられるポリイミドフィルムとしては、適度な強度を有し、剥離作業性で破れ等を引き起こさなければ特に制限はないが、芳香族化合物が直接イミド結合で連結された芳香族ポリイミドがフィルム強度の点で好ましい。例えば、市販のポリイミドフィルムとして、宇部興産株式会社製、商品名：ユーピレックスＲ、ユーピレックスＳ、ユーピレックスＳＧＡ、東レデュポン株式会社製、商品名：カプトンＨ、カプトンＶ、カプトンＥ、カプトンＥＮ、カプトンＥＮＺＴ、鐘淵化学工業株式会社製、商品名：アピカルＡＨ、アピカルＮＰＩ等が好ましく例示できる。これらの市販フィルムの表面にプラズマ処理、コロナ放電処理等を施したものも好ましい。
[Release polyimide film]
First, the release polyimide film of the present invention will be described. The polyimide film used for the release polyimide film of the present invention is not particularly limited as long as it has an appropriate strength and does not cause tearing or the like due to its release workability. However, an aromatic compound in which aromatic compounds are directly linked by imide bonds. Group polyimide is preferred in terms of film strength. For example, as commercially available polyimide films, Ube Industries, Ltd., trade names: Upilex R, Upilex S, Upilex SGA, Toray DuPont Co., Ltd., trade names: Kapton H, Kapton V, Kapton E, Kapton EN, Kapton ENZT, A product name: Apical AH, Apical NPI, etc., manufactured by Kaneka Chemical Co., Ltd. can be preferably exemplified. Those obtained by subjecting the surface of these commercially available films to plasma treatment, corona discharge treatment or the like are also preferred.
本発明に係るポリイミドフィルムの厚みについては、目的により選択され特に制限はないが、フィルムの追従性と剥離性との観点から、１０〜５０μｍの範囲が好ましい。 The thickness of the polyimide film according to the present invention is selected depending on the purpose and is not particularly limited, but is preferably in the range of 10 to 50 μm from the viewpoint of the followability and peelability of the film.
本発明のポリイミドフィルムの表面粗さ（Ｒａ）は、剥離した後の被成形体ないし被積層体の平坦性を良好なものとする観点から、０．０５μｍ未満であることが好ましい。なお、ここでいう「ポリイミドフィルムの表面粗さ」は、少なくとも離型層が形成される側の面の表面粗さを指す。 The surface roughness (Ra) of the polyimide film of the present invention is preferably less than 0.05 μm from the viewpoint of improving the flatness of the molded body or laminated body after peeling. Here, the “surface roughness of the polyimide film” refers to the surface roughness of at least the surface on which the release layer is formed.
本発明に係るポリイミドフィルムは、高温域で熱溶融しない強度を有することから、２００〜３００℃で用いることが好ましく、当該範囲での貯蔵弾性率（１０Ｈｚ）が１ＧＰａを超えることが好ましい。 Since the polyimide film which concerns on this invention has the intensity | strength which does not heat-melt in a high temperature range, it is preferable to use at 200-300 degreeC, and it is preferable that the storage elastic modulus (10 Hz) in the said range exceeds 1 GPa.
本発明に係る離型層を形成するための離型剤としては、シリコーン（ケイ素（Ｓｉ）の重合体）系樹脂、フッ素系樹脂、ポリオレフィン系樹脂等を好適に用いることができる。また、必要に応じて離型層中に易滑剤、帯電防止剤等を添加することもできる。 As the release agent for forming the release layer according to the present invention, silicone (silicon (Si) polymer) -based resin, fluorine-based resin, polyolefin-based resin, or the like can be suitably used. Further, if necessary, an easy lubricant, an antistatic agent and the like can be added to the release layer.
本発明に係る離型剤としては、価格ならび焼却時に有害なガスが発生しない点からシリコーン系樹脂が好ましく、さらに表面張力も調整し易く、フィルム全体に薄い膜を形成することに適するシリコーン系化合物が好ましい。 As the mold release agent according to the present invention, a silicone resin is preferable because it does not generate harmful gas at the price and incineration, and the surface tension can be easily adjusted, and a silicone compound suitable for forming a thin film on the entire film. Is preferred.
本発明に係る離型剤としては、さらに、離型剤の成分が熱板プレス時に被成形体ないし被積層体に移行し、剥離性に悪影響を与えることが少ない、硬化型のシリコーン樹脂が好ましい。硬化型のシリコーン樹脂としては、シリコーン含有アミノアルキド樹脂等が挙げられる。 The mold release agent according to the present invention is preferably a curable silicone resin in which the component of the mold release agent is transferred to a molded body or a laminated body during hot plate pressing and has little adverse effect on peelability. . Examples of the curable silicone resin include a silicone-containing aminoalkyd resin.
ポリイミドフィルムの一方の面上に離型層を形成する方法としては、リバースロールコーター、グラビアコーター、ロッドコーター、エアドクターコーターあるいはこれら以外の塗布装置を用いて、フィルムに塗布する方法がある。 As a method of forming a release layer on one surface of a polyimide film, there is a method of applying to a film using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater or other coating devices.
離型層の厚さは０．０１〜１０μｍの範囲が好ましく、０．０５〜５μｍの範囲がより好ましい。この層の厚さが０．０１〜１０μｍの範囲にあることで均一な層が得られやすくなり剥離性が向上する。また、離型剤が熱板プレス後に移行して、剥離性に悪影響を与えることを防止し、さらに被成形体ないし被積層体への離型剤成分の移行により被成形体ないし被積層体の耐熱性の低下を抑えることができる。 The thickness of the release layer is preferably in the range of 0.01 to 10 μm, and more preferably in the range of 0.05 to 5 μm. When the thickness of this layer is in the range of 0.01 to 10 μm, a uniform layer is easily obtained, and the peelability is improved. In addition, the release agent is prevented from moving after hot plate pressing and adversely affecting the peelability, and further, the release agent component is transferred to the molded body or the laminated body. A decrease in heat resistance can be suppressed.
接着層は、エポキシ樹脂及びエポキシ樹脂硬化剤を含む樹脂組成物を用いて、離型層上に形成されてなることが好ましい。当該樹脂組成物を用いることで、熱板プレスの工程で接着層を硬化し、熱板プレス後に、接着層と離型層の界面で離型ポリイミドフィルムを除去することがより容易にできる。接着層の厚さは０．０１〜１０μｍの範囲が好ましく、０．０５〜８μｍの範囲がより好ましい。 The adhesive layer is preferably formed on the release layer using a resin composition containing an epoxy resin and an epoxy resin curing agent. By using the resin composition, the adhesive layer is cured in the hot plate press step, and after the hot plate press, the release polyimide film can be more easily removed at the interface between the adhesive layer and the release layer. The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm, and more preferably in the range of 0.05 to 8 μm.
なお、本発明においては、離型ポリイミドフィルムの離型層の設けられていない面上に、接着層を有しても良く、この状態で、熱板プレス工程で使用することもできる。 In addition, in this invention, you may have an adhesive layer on the surface in which the release layer of a release polyimide film is not provided, and can also be used at a hot-plate press process in this state.
［多層プリント配線板の製造方法］
本発明の多層プリント配線板の製造方法は、ポリイミドフィルムの一方の面上に離型層を形成する工程（離型層形成工程）、離型層のポリイミドフィルムの設けられていない面上に接着層を形成し、接着層を有する接着層付き離型ポリイミドフィルムを製造する工程（接着層付き離型ポリイミドフィルム製造工程）、接着層を有する接着層付き離型ポリイミドフィルムを用いて多層プリント配線板を製造する工程（多層プリント配線板製造工程）、多層プリント配線板から離型ポリイミドフィルムを除去する工程（離型ポリイミドフィルム除去工程）、を含む。
上記工程のうち、離型層形成工程、接着層付き離型ポリイミドフィルム製造工程については既述のとおりである。
以下では、多層プリント配線板製造工程及び離型ポリイミドフィルム除去工程について説明する。
[Manufacturing method of multilayer printed wiring board]
The method for producing a multilayer printed wiring board of the present invention includes a step of forming a release layer on one surface of a polyimide film (release layer forming step), and an adhesion to a surface of the release layer on which no polyimide film is provided. forming a layer, step (adhesive layer with a release polyimide film manufacturing process) for producing the release polyimide film with an adhesive layer having an adhesive layer, a multilayer printed wiring board using the release polyimide film with an adhesive layer having an adhesive layer Including a step (multilayer printed wiring board manufacturing step) and a step of removing the release polyimide film from the multilayer printed wiring board (release polyimide film removal step).
Among the above steps, the release layer forming step and the release polyimide film manufacturing step with an adhesive layer are as described above.
Below, a multilayer printed wiring board manufacturing process and a mold release polyimide film removal process are demonstrated.
多層プリント配線板製造工程では、まず、接着層が形成された本発明の接着層付き離型ポリイミドフィルムを、接着層が内側となるようにプリプレグに重ね、これを回路加工した配線板の両面に重ねる。さらに外側に鏡板を重ねてプレス成型する。鏡板を取り外すことで、両面に本発明の接着層付き離型ポリイミドフィルムが配置された多層プリント配線板が製造される。その後、離型ポリイミドフィルムを公知の方法で除去（剥離）して多層プリント配線板が得られる（離型ポリイミドフィルム除去工程）。 In the multilayer printed wiring board manufacturing process, first, the release polyimide film with an adhesive layer of the present invention formed with an adhesive layer is overlaid on the prepreg so that the adhesive layer is on the inside, and this is applied to both sides of the circuit board on which the circuit processing has been performed. Overlapping. Furthermore, the end plate is stacked on the outside and press-molded. By removing the end plate, a multilayer printed wiring board in which the release polyimide film with an adhesive layer of the present invention is disposed on both sides is produced. Thereafter , the release polyimide film is removed (peeled) by a known method to obtain a multilayer printed wiring board (release polyimide film removal step).
上記プレス成型における加熱温度は、１８０〜３００℃とすることが好ましく、２００〜２５０℃とすることがより好ましい。加圧時の圧力は１．０〜４．０ＭＰａとすることが好ましい。 The heating temperature in the press molding is preferably 180 to 300 ° C, and more preferably 200 to 250 ° C. The pressure during pressurization is preferably 1.0 to 4.0 MPa.
なお、必要に応じて剥離（離型ポリイミドフィルム除去工程）の前に、ポリイミドフィルムの上面からドリル加工及びレーザー加工を施した後に離型ポリイミドフィルムを除去しても良い。従来、高温プレスを行う場合、銅箔を用いてプレス成型を行っており、レーザー加工を行う場合、銅箔ごと加工する必要があり、生産性、穴あけ精度に劣っていた。しかし、本発明ではポリイミドフィルムを用いているため、生産性や穴あけ精度が向上する。 In addition, you may remove a mold release polyimide film, after giving a drill process and a laser process from the upper surface of a polyimide film before peeling (mold release polyimide film removal process) as needed. Conventionally, when performing high-temperature pressing, press molding is performed using copper foil, and when performing laser processing, it is necessary to process the entire copper foil, resulting in poor productivity and drilling accuracy. However, since a polyimide film is used in the present invention, productivity and drilling accuracy are improved.
ここで、本発明で使用される多層プリント配線板の製造工程で用いられるプリプレグは、特に限定されるものではない。一般には多官能エポキシ樹脂、エポキシ樹脂硬化剤、硬化促進剤、溶剤と必要に応じて無機フィラーを混合し、積層板用ガラスクロスに含浸・乾燥させて得られる。市販品としては、日立化成工業（株）製ＧＥＡ−６７ＮやＧＥＡ−６７９Ｆ、ＧＥＡ−６７９ＧＴ、ＧＥＡ−７００Ｇ等があるが特に限定されるものではない。 Here, the prepreg used in the production process of the multilayer printed wiring board used in the present invention is not particularly limited. In general, it is obtained by mixing a polyfunctional epoxy resin, an epoxy resin curing agent, a curing accelerator, a solvent and an inorganic filler as required, and impregnating and drying the laminated sheet glass cloth. Commercially available products include GEA-67N, GEA-679F, GEA-679GT, and GEA-700G manufactured by Hitachi Chemical Co., Ltd., but are not particularly limited.
次に実施例により本発明を説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention, the scope of the present invention is not limited to these Examples.
[表面自由エネルギーの測定方法]
離型層表面の表面自由エネルギーは、協和界面科学（株）製の接触角ＣＡ−Ｘ型を用いて水、エチレングリコール、ヨウ化メチレンの接触角を測定し、表面自由エネルギー解析ソフトＥＧ−２（協和界面科学）を用いて算出した。
[Measurement method of surface free energy]
The surface free energy on the surface of the release layer was measured by measuring the contact angles of water, ethylene glycol, and methylene iodide using the contact angle CA-X type manufactured by Kyowa Interface Science Co., Ltd. Calculated using (Kyowa Interface Science).
［接着層用樹脂ワニスの調製］
クレゾールノボラック型エポキシ樹脂（ＹＤＣＮ−７００−１０、新日化エポキシ製造（株）製、商品名）５５質量部、フェノールアラルキル樹脂（ＸＬＣ−ＬＬ、三井化学（株）製、商品名）４５質量部からなる組成物に、シクロヘキサノンを加えて攪拌混練した。これにアクリルゴム（ＨＴＲ−８６０Ｐ−３、ナガセケムテックス（株）製、商品名、重量平均分子量８０万、ガラス転移点：１３℃）２００質量部、硬化促進剤としてキュアゾール２ＰＺ−ＣＮ（四国化成（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）０．５質量部加え、攪拌混練して、均一な接着層用樹脂ワニス（固形分濃度約１５％）を得た。
[Preparation of resin varnish for adhesive layer]
Cresol novolac type epoxy resin (YDCN-700-10, manufactured by Nippon Kayaku Epoxy Manufacturing Co., Ltd., trade name) 55 parts by mass, phenol aralkyl resin (XLC-LL, manufactured by Mitsui Chemicals, Inc., trade name) 45 parts by mass Cyclohexanone was added to the composition comprising and stirred and kneaded. To this, 200 parts by mass of acrylic rubber (HTR-860P-3, manufactured by Nagase ChemteX Corporation, trade name, weight average molecular weight 800,000, glass transition point: 13 ° C.), Curazole 2PZ-CN (Shikoku Chemicals) as a curing accelerator 0.5 part by mass (trade name, 1-cyanoethyl-2-phenylimidazole) manufactured by Co., Ltd. was added and stirred and kneaded to obtain a uniform resin varnish for the adhesive layer (solid content concentration of about 15%).
（実施例１）
・接着層付き離型ポリイミドフィルム：
ポリイミドフィルムとして宇部興産（株）製、ユーピレックス２５ＳＧＡ、厚み２５μｍ、表面粗さＲａ０．０５μｍ未満を用いた。このポリイミドフィルム上にシリコーン含有アミノアルキド樹脂（テスファイン３１９、日立化成ポリマー株式会社製）で調製した調製液を、ダイコータを用いて塗布し、１６０℃４０秒間乾燥させ、厚み０．２μｍの離型層を得た。
なお、離型層面の表面自由エネルギーは２４．７ｍＮ／ｍであった。
得られた離型層付きのポリイミドフィルムの離型層面に接着層用ワニスを塗布し、１４０℃５分間、乾燥させ、厚さ５μｍの接着層を形成して、接着層付き離型ポリイミドフィルムを得た。
Example 1
・ Release polyimide film with adhesive layer:
As the polyimide film, Ube Industries, Ltd., Upilex 25SGA, thickness 25 μm, surface roughness Ra less than 0.05 μm was used. On this polyimide film, a preparation solution prepared with a silicone-containing aminoalkyd resin (Tesfine 319, manufactured by Hitachi Chemical Polymer Co., Ltd.) was applied using a die coater, dried at 160 ° C. for 40 seconds, and a mold release having a thickness of 0.2 μm. A layer was obtained.
The surface free energy of the release layer surface was 24.7 mN / m.
An adhesive layer varnish is applied to the release layer surface of the obtained polyimide film with a release layer, dried at 140 ° C. for 5 minutes to form an adhesive layer with a thickness of 5 μm, and the release polyimide film with an adhesive layer is Obtained.
・積層サンプル：
プリプレグ（日立化成工業（株）製 ＧＥＡ−７００Ｇ ０．１０ｍｍ厚）４枚を重ね、その上下に上記接着層付き離型ポリイミドフィルムのポリイミドフィルム面が外側になるように重ね、さらに鏡板と、クッション紙を重ねて、プレス機を用いて、３．０ＭＰａ、２４０℃で１時間加熱硬化させ積層サンプルを得た。
・ Laminated sample:
4 prepregs (GEA-700G, 0.10 mm thickness, manufactured by Hitachi Chemical Co., Ltd.) are stacked, and the upper and lower layers are stacked so that the polyimide film surface of the release polyimide film with the adhesive layer is on the outside. Paper was piled up and heat-cured at 3.0 MPa and 240 ° C. for 1 hour using a press to obtain a laminated sample.
（実施例２）
ポリイミドフィルムとして、東レ・デュポン（株）製、カプトン１００Ｈ、厚み２５μｍ、表面粗さＲａ０．０５μｍ未満を用いた以外、実施例１と同様に接着層付き離型ポリイミドフィルム及び積層サンプルを得た。
(Example 2)
As the polyimide film, a release polyimide film with an adhesive layer and a laminated sample were obtained in the same manner as in Example 1 except that Toray DuPont Co., Ltd., Kapton 100H, thickness 25 μm, and surface roughness Ra less than 0.05 μm were used.
（実施例３）
離型層として、シリコーン含有アミノアルキド樹脂（ＴＡ３１−２０９Ｅ、日立化成ポリマー株式会社製）の調製液を用いた以外、実施例１と同様に接着層付き離型ポリイミドフィルム及び積層サンプルを得た。
なお、離型層面の表面自由エネルギーは２１．４ｍＮ／ｍであった。
(Example 3)
A release polyimide film with an adhesive layer and a laminated sample were obtained in the same manner as in Example 1 except that a preparation solution of a silicone-containing aminoalkyd resin (TA31-209E, manufactured by Hitachi Chemical Co., Ltd.) was used as the release layer.
The surface free energy of the release layer surface was 21.4 mN / m.
（比較例１）
実施例１の離型層付きのポリイミドフィルムの代わりに、離型層付きポリエチレンテレフタレートフィルム（ユニピールＴＲ１、ユニチカ（株）製、商品名、厚さ３８μｍ）を用いた以外は同様に、接着層付き離型フィルム及び積層サンプルを得た。
(Comparative Example 1)
In place of the polyimide film with a release layer of Example 1 except that the polyethylene terephthalate film with a release layer (Unipeel TR1, manufactured by Unitika Ltd., trade name, thickness 38 μm) was used. A release film and a laminated sample were obtained.
以上のようにして作製した積層サンプルについて、プレス後のフィルム剥離性及び容易に剥離できた剥離後の積層サンプルについて、その接着層の表面粗さの測定を実施した。結果を下記表１に示す。 About the laminated sample produced as mentioned above, the surface roughness of the adhesive layer was measured about the peelable film sample after pressing and the laminated sample after peeling. The results are shown in Table 1 below.
［プレス後の剥離性］
プレス後の積層サンプルから離型フィルムを剥離したときに、離型層と被着体の接着層との界面で剥離できているかどうかを目視により確認した。
○：界面で容易に剥離できる。
×：界面で容易に剥離できない。
界面で容易に剥離できないとは、剥離できない場合、又は剥離後、離型フィルムに接着層の樹脂組成物が付着している場合をいう。
[Peelability after pressing]
When the release film was peeled from the laminated sample after pressing, whether or not the release film was peeled off at the interface between the release layer and the adhesive layer of the adherend was visually confirmed.
○: Easy peeling at the interface.
X: It cannot peel easily at the interface.
The phrase “cannot be easily peeled at the interface” means a case where peeling is not possible, or a case where the resin composition of the adhesive layer is adhered to the release film after peeling.
[表面粗さの測定方法]
各被着体の接着層の表面粗さは、菱化システム社製マイクロマップＭＮ５０００型を用い、表面粗さＲａを測定した。
[Measurement method of surface roughness]
The surface roughness Ra of the adhesion layer of each adherend was measured using a Ryoka System Co., Ltd. micromap MN5000 type.
（比較例２）
ポリイミドフィルムの離型層を形成しなかった以外は実施例１と同様に、ポリイミドフィルム面上に接着層を塗布形成させ、接着層付き多層サンプルを得た。この多層サンプルからポリイミドフィルムの剥離を試みたが、ポリイミドフィルムが破れ、ポリイミドフィルムを単独で剥離できなかった。
(Comparative Example 2)
An adhesive layer was applied and formed on the polyimide film surface in the same manner as in Example 1 except that a release layer for the polyimide film was not formed to obtain a multilayer sample with an adhesive layer. An attempt was made to peel the polyimide film from the multilayer sample, but the polyimide film was torn and the polyimide film could not be peeled alone.
表１から、本発明の接着層付き離型ポリイミドフィルム及び接着層付き積層板の特性は、実施例１〜３に示したように、高温の熱板プレス後に離型ポリイミドフィルムを容易に剥離でき、均一で平滑な接着層面を得ることができた。
一方、ポリイミドフィルム以外のフィルムを用いた比較例１では容易に剥離できず、均一な被着体面が得られないことが確認できた。さらに、比較例２ではポリイミドフィルムが破れ、ポリイミドフィルムを単独で剥離できないことが確認された。
From Table 1, the characteristics of the release polyimide film with adhesive layer and the laminate with adhesive layer of the present invention can be easily peeled off after high temperature hot plate pressing, as shown in Examples 1-3. A uniform and smooth adhesive layer surface could be obtained.
On the other hand, it was confirmed that Comparative Example 1 using a film other than the polyimide film could not be easily peeled off and a uniform adherend surface could not be obtained. Furthermore, in Comparative Example 2, it was confirmed that the polyimide film was torn and the polyimide film could not be peeled alone.
Claims (5)
前記ポリイミドフィルムの表面粗さ（Ｒａ）が０．０５μｍ未満であり、
前記離型層のポリイミドフィルムの設けられていない面上に接着層を有し、
前記接着層が、エポキシ樹脂、及びエポキシ樹脂硬化剤を含む樹脂組成物を用いてなる接着層付き離型ポリイミドフィルム。 On one surface of the polyimide film, it has a release layer,
The surface roughness (Ra) of the polyimide film is less than 0.05 μm,
Having an adhesive layer on the surface of the release layer where the polyimide film is not provided,
A release polyimide film with an adhesive layer, wherein the adhesive layer comprises a resin composition containing an epoxy resin and an epoxy resin curing agent .
前記離型層のポリイミドフィルムの設けられていない面上に、エポキシ樹脂、及びエポキシ樹脂硬化剤を含む樹脂組成物を用いてなる接着層を形成し、接着層を有する接着層付き離型ポリイミドフィルムを製造する工程、
前記接着層を有する接着層付き離型ポリイミドフィルムを用いて多層プリント配線板を製造する工程、
多層プリント配線板から離型ポリイミドフィルムを除去する工程、
を含む多層プリント配線板の製造方法。 Forming a release layer on one surface of a polyimide film having a surface roughness (Ra) of less than 0.05 μm ;
On the surface of the release layer where the polyimide film is not provided, an adhesive layer made of a resin composition containing an epoxy resin and an epoxy resin curing agent is formed, and the release polyimide film with the adhesive layer has an adhesive layer Manufacturing process,
A step of producing a multilayer printed wiring board using a release polyimide film with an adhesive layer having the adhesive layer ,
Removing the release polyimide film from the multilayer printed wiring board;
A method for producing a multilayer printed wiring board comprising:
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| KR102343177B1 (en) * | 2013-12-09 | 2021-12-23 | 쇼와덴코머티리얼즈가부시끼가이샤 | Mold-release polyimide film with adhesive layer, laminated board having mold-release polyimide film with adhesive layer, laminated board, single-layer or multilayer wiring board having mold-release polyimide film with adhesive layer, and method for producing multilayer wiring board |
| JP6679902B2 (en) * | 2015-12-04 | 2020-04-15 | 日立化成株式会社 | Resin composition for plating process, carrier film with resin for plating process and method of manufacturing the same, laminate for wiring board and method of manufacturing wiring board |
| WO2018062266A1 (en) | 2016-09-30 | 2018-04-05 | ユニチカ株式会社 | Mold release sheet |
| JP2018178106A (en) * | 2017-04-06 | 2018-11-15 | 積水化学工業株式会社 | Release film |
| KR20210068495A (en) | 2018-10-04 | 2021-06-09 | 닛토덴코 가부시키가이샤 | Heat-resistant release sheet and thermocompression method |
| JP2022067094A (en) * | 2020-10-19 | 2022-05-02 | 三菱ケミカル株式会社 | Laminate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0418788A (en) * | 1990-05-11 | 1992-01-22 | Fujitsu Ltd | Manufacture of molded wiring board |
| US5234522A (en) * | 1990-12-05 | 1993-08-10 | Hitachi Chemical Company, Inc. | Method of producing flexible printed-circuit board covered with coverlay |
| JP3592018B2 (en) * | 1996-01-22 | 2004-11-24 | 日本テキサス・インスツルメンツ株式会社 | Polyimide adhesive sheet and process film for polyimide |
| JP2821414B2 (en) * | 1996-03-18 | 1998-11-05 | キヤノン株式会社 | Fixing device |
| JP2003027014A (en) * | 2001-07-17 | 2003-01-29 | Kanegafuchi Chem Ind Co Ltd | Adhesive film |
| JP4151370B2 (en) * | 2002-10-07 | 2008-09-17 | 東レ株式会社 | Release film |
| JP2008066576A (en) * | 2006-09-08 | 2008-03-21 | Seiko Epson Corp | Method of manufacturing circuit board |
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