JP2023057084A - Dry film, cured product and electronic component - Google Patents
Dry film, cured product and electronic component Download PDFInfo
- Publication number
- JP2023057084A JP2023057084A JP2023013010A JP2023013010A JP2023057084A JP 2023057084 A JP2023057084 A JP 2023057084A JP 2023013010 A JP2023013010 A JP 2023013010A JP 2023013010 A JP2023013010 A JP 2023013010A JP 2023057084 A JP2023057084 A JP 2023057084A
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- Prior art keywords
- resin
- film
- manufactured
- resin layer
- protective film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011347 resin Substances 0.000 claims abstract description 133
- 230000001681 protective effect Effects 0.000 claims abstract description 77
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- 238000007667 floating Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 6
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- 229920000647 polyepoxide Polymers 0.000 description 67
- 150000001875 compounds Chemical class 0.000 description 34
- -1 polyethylene Polymers 0.000 description 27
- 239000002245 particle Substances 0.000 description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- 229920003986 novolac Polymers 0.000 description 20
- 238000001723 curing Methods 0.000 description 19
- 239000011256 inorganic filler Substances 0.000 description 19
- 229910003475 inorganic filler Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 18
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- 239000004643 cyanate ester Substances 0.000 description 17
- 125000004185 ester group Chemical group 0.000 description 17
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- 239000011229 interlayer Substances 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/094—Multilayer resist systems, e.g. planarising layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
Abstract
Description
本発明は、ドライフィルム、硬化物および電子部品に関する。 The present invention relates to dry films, cured products and electronic parts.
従来、電子機器等に用いられるプリント配線板に設けられるソルダーレジストや層間絶縁層等の保護膜や絶縁層の形成手段の一つとして、ドライフィルム（積層フィルム）が利用されている（例えば特許文献１）。ドライフィルムは、所望の特性を有する樹脂組成物をキャリアフィルムの上に塗布後、乾燥工程を経て得られる樹脂層を有し、一般的には、キャリアフィルムとは反対側の面を保護するための保護フィルムがさらに積層された状態で市場に流通している。ドライフィルムの樹脂層を基板に貼着（以下「ラミネート」とも称する）した後、パターニングや硬化処理を施すことによって、上記のような保護膜や絶縁層を有するプリント配線板を製造することができる。 Conventionally, a dry film (laminated film) has been used as one of the means for forming protective films and insulating layers such as solder resists and interlayer insulating layers provided on printed wiring boards used in electronic devices (e.g., patent documents 1). A dry film has a resin layer obtained by coating a resin composition having desired properties on a carrier film and then performing a drying process, and generally protects the surface opposite to the carrier film. are distributed on the market in a state in which the protective film of the above is further laminated. A printed wiring board having a protective film and an insulating layer as described above can be manufactured by applying patterning and curing treatment after affixing a resin layer of a dry film to a substrate (hereinafter also referred to as "laminating"). .
保護フィルムは、ドライフィルムを基板に粘着するに際し、樹脂層から外されることになるが、その際に樹脂組成物が保護フィルムに転写すること（以下「樹脂の泣き別れ」とも称する）がないように、従来は、ドライフィルムの製造工程において、樹脂組成物に対する保護フィルムの剥離強度が小さくなるように条件を調整していた。特許文献２には、保護フィルム剥離時に樹脂剥がれが生じない保護フィルム付き接着シートとして、保護フィルム剥離強度がキャリアフィルム剥離強度よりも０．００２０ｋｇｆ／ｃｍ以上小さい保護フィルム付き接着シートが開示されている。
The protective film is removed from the resin layer when the dry film is adhered to the substrate. Furthermore, conventionally, in the dry film manufacturing process, the conditions have been adjusted so that the peel strength of the protective film to the resin composition is reduced.
保護フィルムとキャリアフィルムを有する前記三層構造ドライフィルムは、通常はまず、硬化性樹脂組成物を、溶剤量により粘度調整したうえで、キャリアフィルム上に塗布し、次いで、乾燥炉にて乾燥し、キャリアフィルム上に樹脂層を形成し、その後作製したドライフィルムの表面に、保護フィルムの張りあわせを行うことで長尺のドライフィルムが製造される。長尺のドライフィルムの形状は、例えばはば１ｍ、長さ１０００ｍであり、ロール状である。 The three-layer structure dry film having a protective film and a carrier film is usually firstly coated on the carrier film after adjusting the viscosity of the curable resin composition by the amount of solvent, and then dried in a drying oven. A long dry film is produced by forming a resin layer on a carrier film, and then laminating a protective film on the surface of the dry film produced. The long dry film has, for example, a length of 1 m and a length of 1000 m, and is in the form of a roll.
前記長尺のドライフィルムは、要求される長さと幅に応じてスリット加工（裁断）により、例えばはばを５０ｃｍに調整されてドライフィルムとなるが、例えば前記のように、長さ１０００ｍにわたって連続してスリット加工をするに際し、従来のドライフィルムでは、刃に樹脂が付着し、切れ味が悪くなり、結果的に端部における樹脂の割れや浮き、保護フィルムの浮きにつながるとの問題があった。 The long dry film is adjusted to a width of 50 cm by slitting (cutting) according to the required length and width, for example, to become a dry film. When performing slit processing, with conventional dry film, resin adheres to the blade, resulting in poor sharpness, resulting in cracking and lifting of the resin at the edge and lifting of the protective film. .
そこで本発明の目的は、連続してスリット加工をしても、刃に樹脂が付着して切れ味が悪くなることがなく、結果として端部における樹脂の割れや浮き、保護フィルムの浮きが発生しないドライフィルム、該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することにある。 Therefore, the object of the present invention is to prevent resin from adhering to the blade and deteriorating sharpness even when slitting is continuously performed, and as a result, cracking and lifting of the resin at the edge and lifting of the protective film do not occur. An object of the present invention is to provide a dry film, a cured product of a resin layer of the dry film, and an electronic component having the cured product.
発明者らは鋭意検討し、保護フィルムを十分に樹脂層に接着し、樹脂層に対する保護フィルムの剥離強度が一定の条件を満足するドライフィルムによれば、上記課題を解決できることを、またその場合でも、当初懸念した、保護フィルムを樹脂層から外す場合の保護フィルムへの樹脂組成物の転写がないことを見出し、本発明を完成するに至った。すなわち、本発明のドライフィルムは、キャリアフィルムと、樹脂層と、保護フィルムと、を備えるドライフィルムにおいて、前記樹脂層に対する前記保護フィルムの剥離強度が０．０１０ｋｇｆ／ｃｍ以上であり、かつ前記樹脂層に対する前記保護フィルムの剥離強度が、前記樹脂層に対する前記キャリアフィルムの剥離強度よりも大きいことを特徴とするものである。 The inventors have made intensive studies and found that the above problems can be solved by a dry film in which the protective film is sufficiently adhered to the resin layer and the peel strength of the protective film to the resin layer satisfies a certain condition. However, the inventors found that there was no transfer of the resin composition to the protective film when the protective film was removed from the resin layer, which was an initial concern, and completed the present invention. That is, the dry film of the present invention is a dry film comprising a carrier film, a resin layer, and a protective film, wherein the peel strength of the protective film to the resin layer is 0.010 kgf / cm or more, and the resin It is characterized in that the peel strength of the protective film to the layer is greater than the peel strength of the carrier film to the resin layer.
本発明のドライフィルムは、前記保護フィルムの剥離強度が、前記樹脂層に対する前記キャリアフィルムの剥離強度よりも０．００５ｋｇｆ／ｃｍ以上大きいことが好ましい。 In the dry film of the present invention, the peel strength of the protective film is preferably 0.005 kgf/cm or more greater than the peel strength of the carrier film to the resin layer.
本発明のドライフィルムは、厚さが６０μｍ以上であることが好ましい。 The dry film of the present invention preferably has a thickness of 60 μm or more.
本発明のドライフィルムは、前記保護フィルムが粘着性を有することが好ましい。 In the dry film of the present invention, the protective film preferably has adhesiveness.
本発明の硬化物は、前記ドライフィルムの樹脂層を硬化して得られることを特徴とするものである。 The cured product of the present invention is characterized by being obtained by curing the resin layer of the dry film.
本発明の電子部品は、前記硬化物を有することを特徴とするものである。 The electronic component of the present invention is characterized by having the cured product.
本発明によれば、連続してスリット加工をしても、刃に樹脂が付着して切れ味が悪くなることがなく、結果として端部における樹脂の割れや浮き、保護フィルムの浮きが発生しないドライフィルム、該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することができる。 According to the present invention, even if slitting is performed continuously, the sharpness is not deteriorated due to the resin adhering to the blade. A film, a cured product of the resin layer of the dry film, and an electronic component having the cured product can be provided.
＜ドライフィルム＞
図１に本発明のドライフィルムの概略断面図を示す。本発明の三層構造のドライフィルム１１は、樹脂層１２が、キャリアフィルム１３上に形成され、保護フィルム１４を積層した構造を有する。本発明のドライフィルムは、このような三層構造のドライフィルムにおいて、樹脂層に対する保護フィルムの剥離強度が０．０１０ｋｇｆ／ｃｍ以上、かつ樹脂層に対する保護フィルムの剥離強度が、樹脂層に対するキャリアフィルムの剥離強度よりも大きいことを特徴とするものである。ここで、樹脂層に対する保護フィルムの剥離強度の上限値として、例えば０．１５０ｋｇｆ／ｃｍ以下であれば、樹脂組成物が保護フィルムに転写することを良好に防止することができる。
また、本発明のドライフィルムにおいて、樹脂層に対する保護フィルムの剥離強度が、樹脂層に対するキャリアフィルムの剥離強度よりも０．００５ｋｇｆ／ｃｍ以上大きいことが好ましい。ここで、前記剥離強度の差の上限値として、例えば０．１５０ｋｇｆ／ｃｍ以下であれば、樹脂組成物が保護フィルムに転写することを良好に防止することができる。
<Dry film>
FIG. 1 shows a schematic cross-sectional view of the dry film of the present invention. The three-layer dry film 11 of the present invention has a structure in which a resin layer 12 is formed on a
Moreover, in the dry film of the present invention, the peel strength of the protective film to the resin layer is preferably higher than the peel strength of the carrier film to the resin layer by 0.005 kgf/cm or more. Here, if the upper limit of the difference in peel strength is, for example, 0.150 kgf/cm or less, the transfer of the resin composition to the protective film can be satisfactorily prevented.
本発明のドライフィルムは、前述の要件を満足することで、連続してスリット加工をしても、刃に樹脂が付着して切れ味が悪くなることがなく、結果として端部における樹脂の割れや浮き、保護フィルムの浮きが発生しない。このような効果は６０μｍ以上の厚さを有するドライフィルムで顕著であり、１００μｍ以上の厚さを有するドライフィルムでさらに顕著であり、１５０μｍ以上の厚さを有するドライフィルムで特に顕著である。ドライフィルムの厚さの上限値は５００μｍである。 By satisfying the above-mentioned requirements, the dry film of the present invention does not lose sharpness due to adhesion of resin to the blade even if it is continuously slit, and as a result, cracking of the resin at the edge Floating and protective film floating do not occur. Such an effect is remarkable in a dry film having a thickness of 60 μm or more, more remarkable in a dry film having a thickness of 100 μm or more, and particularly remarkable in a dry film having a thickness of 150 μm or more. The upper limit of the dry film thickness is 500 μm.
［保護フィルム］
保護フィルムとは、ドライフィルムの樹脂層の表面に塵等が付着するのを防止するとの目的や、ドライフィルムをスリット加工する際に樹脂層表面の物理的ダメージを防止するとともに取扱性を向上させるとの目的で、樹脂層のキャリアフィルムとは反対の面に設けられる。保護フィルムに用いられる材質としては、たとえばポリエチレン、ポリプロピレン、ポリ塩化ビニル等のポリオレフィン、ＰＥＴ、ＰＥＮ等のポリエステル、ポリカーボネート、ポリイミド等が挙げられる。
[Protective film]
The protective film is intended to prevent dust from adhering to the surface of the resin layer of the dry film, and to prevent physical damage to the surface of the resin layer when slitting the dry film and improve handling. For this purpose, it is provided on the surface of the resin layer opposite to the carrier film. Examples of materials used for the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, polycarbonate, and polyimide.
本発明の保護フィルムとしては、樹脂層に対する保護フィルムの剥離強度が０．０１０ｋｇｆ／ｃｍ以上であり、かつ樹脂層に対する前記保護フィルムの剥離強度が、樹脂層に対する前記キャリアフィルムの剥離強度よりも大きいとの本発明の要件を満たす限り、市販のいずれの保護フィルムを用いることができる。たとえば、王子エフテックス社製２軸延伸ポリプロピレンフィルムＭＡ－４１１、ＭＡ－４２０、ＭＡＭ－４３０等の従来のフィルムも、張り合せ時の圧力や温度を調整し、保護フィルムの剥離強度を高くすることで使用できるが、好ましいフィルムとしては、フタムラ化学社製自己粘着２軸延伸ポリプロピレンフィルム１００Ｍ、１５０Ｍ、３００Ｍおよび日東シンコー社製耐熱性微粘着特殊ポリエステルフィルムＴ－ＡＰＮ１０、ソマール社製のソマタックＷＡシリーズ（ＰＳ－１０５ＷＡ、ＰＳ－１０８０ＷＡ、ＰＳ－５０３ＷＡ等）、寺岡製作所社製のフィルムマスキングテープ（４６５ ＃４０等）、ＰＥＥＫフィルム粘着テープ（４９２０ ０．０１２等）、シリコーンゴム両面粘着テープ（９０３０Ｗ）、リンテック社製の粘着剤（ＭＦ、ＭＡ、エヌタック、ＲＥＰＯＰシリコーン微粘着等）をＰＥＴやＯＰＰフィルム上に形成したもの、日立化成社製の粘着フィルム「ヒタレックス」、Ａ－２４００シリーズ、Ｄ－５７００シリーズ、ＧＳ－１０００シリーズ、Ｌ－１２００シリーズ、Ｌ－３３００シリーズ、ＢＮ－１０００、東洋ケム社製のリオエルムＬＥ９５０シリーズ（ＬＥ９５１、ＬＥ９５７Ｌ）、パナック社製のパナプロテクト（ＨＰ、ＣＴ、ＥＴ、ＭＫ等）、巴川社製の粘着フィルム（ＣＡ０１、ＣＡ２２、ＣＡ９１、ＣＡ３１、ＣＡ３２、くっきりミエール等）、ＤＮＰ社製のＤＮＰ耐熱粘着フィルム等を挙げることができる。 In the protective film of the present invention, the peel strength of the protective film to the resin layer is 0.010 kgf/cm or more, and the peel strength of the protective film to the resin layer is greater than the peel strength of the carrier film to the resin layer. Any commercially available protective film can be used as long as it satisfies the requirements of the present invention. For example, conventional films such as biaxially oriented polypropylene films MA-411, MA-420, MAM-430 manufactured by Oji F-Tex Co., Ltd. can also be adjusted by adjusting the pressure and temperature during lamination to increase the peel strength of the protective film. Preferred films include self-adhesive biaxially stretched polypropylene films 100M, 150M, and 300M manufactured by Futamura Chemical Co., Ltd., heat-resistant slightly adhesive special polyester film T-APN10 manufactured by Nitto Shinko Co., Ltd., and Somatac WA series manufactured by Somar Co., Ltd. ( PS-105WA, PS-1080WA, PS-503WA, etc.), film masking tape manufactured by Teraoka Seisakusho Co., Ltd. (465 #40, etc.), PEEK film adhesive tape (4920 0.012, etc.), silicone rubber double-sided adhesive tape (9030W), Lintec's adhesive (MF, MA, Entac, REPOP silicone weak adhesive, etc.) formed on PET or OPP film, Hitachi Chemical's adhesive film "Hitarex", A-2400 series, D-5700 series , GS-1000 series, L-1200 series, L-3300 series, BN-1000, Rio Elm LE950 series (LE951, LE957L) manufactured by Toyochem, PanaProtect manufactured by Panac (HP, CT, ET, MK, etc.) , adhesive films manufactured by Tomoegawa (CA01, CA22, CA91, CA31, CA32, clear miel, etc.), DNP heat-resistant adhesive films manufactured by DNP, and the like.
ここで、本発明において樹脂層に対する保護フィルムの剥離強度とは、保護フィルムを樹脂層に対して垂直方向（９０°方向）に引き剥がしたときの剥離強度（９０°ピール強度）を言い、保護フィルムを樹脂層に対して引き剥がし角度９０°で引き剥がした時の剥離強度を引張り試験機で測定することにより求めることができる。引張り試験機としては、例えば島津製作所製万能引張り試験機ＡＧ－Ｘが挙げられる。 Here, in the present invention, the peel strength of the protective film against the resin layer refers to the peel strength (90° peel strength) when the protective film is peeled off in the direction perpendicular to the resin layer (90° direction). It can be obtained by measuring the peel strength when the film is peeled off from the resin layer at a peeling angle of 90° with a tensile tester. Examples of the tensile tester include Shimadzu Universal Tensile Tester AG-X.
樹脂層に保護フィルムを張り合わせるに際しては、硬化性樹脂組成物の最低溶融温度前後の温度条件にて、ロールやプレス圧着等により保護フィルムを樹脂層にラミネート処理することが好ましい。ラミネート処理における圧着圧力は０．０１ｋｇｆ／ｃｍ２～２０ｋｇｆ／ｃｍ２が好ましい。ここで、最低溶融温度の定義は以下の通りである。
＜最低溶融温度の定義＞
作製したドライフィルム（４０ｕｍ）を、真空ラミネーターＭＶＬＰ－５００（名機社製）を用い、条件（温度５０℃、時間１２０ｓｅｃ、圧力０．５ＭＰａ、保護フィルム面を剥離し）にて、厚み２００ｕｍ、サイズ５０×５０ｍｍの溶融粘度測定用のサンプルを作製する。ついで、測定サイズφ２０ｍｍの円形に加工し、表裏のＰＥＴフィルムを剥離し測定用のサンプルを作製する。その後、レオメーターＨＡＡＫＥ ＭＡＲＳ４０（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ製）を用い、以下の条件にて溶融粘度の測定を行った時の粘度より定義する。センサーパラレルプレートφ２０ｍｍ、歪２％、周波数１Ｈｚのオシレーションモード、測定サンプルのギャップ１８０ｕｍ、室温から５℃／ｍｉｎの昇温方法にて測定を行い、材料の粘度が最も低くなった時の温度より定義する。
When laminating the protective film to the resin layer, it is preferable to laminate the protective film to the resin layer by rolls, press crimping, or the like under temperature conditions around the minimum melting temperature of the curable resin composition. The compression pressure in the lamination process is preferably 0.01 kgf/cm 2 to 20 kgf/cm 2 . Here, the definition of the minimum melting temperature is as follows.
<Definition of minimum melting temperature>
Using a vacuum laminator MVLP-500 (manufactured by Meiki Co., Ltd.), the prepared dry film (40 um) was dried under the conditions (temperature 50 ° C., time 120 sec, pressure 0.5 MPa, peeling off the protective film surface) to a thickness of 200 um, A sample for melt viscosity measurement with a size of 50×50 mm is prepared. Then, it is processed into a circle with a measurement size of φ20 mm, and the front and back PET films are peeled off to prepare a sample for measurement. After that, using a rheometer HAAKE MARS40 (manufactured by Thermo Fisher), the melt viscosity is measured under the following conditions and defined from the viscosity. Sensor parallel plate φ 20 mm,
ここで、微粘着性を有しない保護フィルムを用いながら、樹脂層に対する保護フィルム剥離強度を、本発明の範囲とすべく大きくするためには、張り合わせ温度を従来の張り合わせ温度よりも高める必要があるが、この場合、張り合わせ温度にむらが生じた場合や、張り合わせ温度が高くなりすぎた場合には、保護フィルムの伸びの問題や、張り合わせ後の収縮時に保護フィルムと樹脂層やキャリアフィルムとの収縮率の違いからカール状態になってしまうとの問題がある。このため、本発明においては張り合わせ温度を高くすることなしに保護フィルムの剥離強度を高めることができるとの理由から、微粘着保護フィルム等の、粘着性を有する保護フィルムを用いることが好ましい。粘着性を有する保護フィルムの粘着層の構成材料としては、スチレン系ポリマーまたはスチレン・イソプレン系ポリマーであることが好ましい。 Here, in order to increase the peel strength of the protective film to the resin layer within the scope of the present invention while using a protective film that does not have slight tackiness, it is necessary to raise the lamination temperature above the conventional lamination temperature. However, in this case, if the lamination temperature becomes uneven or if the lamination temperature becomes too high, problems such as elongation of the protective film and shrinkage of the protective film and the resin layer or carrier film during shrinkage after lamination may occur. There is a problem that it becomes a curled state due to the difference in rate. Therefore, in the present invention, it is preferable to use a tacky protective film such as a slightly tacky protective film because the peel strength of the protective film can be increased without increasing the bonding temperature. A styrene-based polymer or a styrene/isoprene-based polymer is preferable as a constituent material of the adhesive layer of the protective film having adhesiveness.
また、保護フィルムとして、樹脂層への積層後の冷却収縮を少なくすることができるとの観点から２軸延伸ポリプロピレンフィルムを用いることが好ましい。 As the protective film, it is preferable to use a biaxially oriented polypropylene film from the viewpoint that cooling shrinkage after lamination on the resin layer can be reduced.
保護フィルムの厚さは、特に制限されるものではないが概ね１０～１００μｍの範囲で用途に応じて適宜選択される。保護フィルムの樹脂層を設ける面には、エンボス加工やコロナ処理、微粘着処理等の密着性を向上させる処理や、離型処理が施されていることが好ましい。 The thickness of the protective film is not particularly limited, but is appropriately selected in the range of approximately 10 to 100 μm depending on the application. It is preferable that the surface of the protective film on which the resin layer is to be provided is subjected to a treatment for improving adhesion such as embossing, corona treatment, or slight adhesion treatment, or a release treatment.
［樹脂層］
本発明のドライフィルムの樹脂層は、一般にＢステージ状態と言われる状態であり、硬化性樹脂組成物から得られるものであり、具体的には、フィルムに硬化性樹脂組成物を塗布後、乾燥工程を経て得られる。樹脂層の厚さは特に限定されず、例えば、厚さが１～２００μｍであればよい。本発明においては厚みが大きい場合により平坦性に優れることから、例えば、厚さが３０μｍ以上、さらには５０μｍ以上、またさらには１００μｍ以上でも好適に用いることができる。なお、本発明のドライフィルムの樹脂層を複数重ねあわせて厚さが２００μｍを超える樹脂層を形成してもよい。その場合、ロールラミネーターや真空ラミネーターを用いればよい。
[Resin layer]
The resin layer of the dry film of the present invention is in a state generally referred to as a B-stage state, and is obtained from a curable resin composition. Specifically, after applying the curable resin composition to the film, it is dried. Obtained through processes. The thickness of the resin layer is not particularly limited, and may be, for example, 1 to 200 μm. In the present invention, since flatness is more excellent when the thickness is large, for example, a thickness of 30 μm or more, further 50 μm or more, and furthermore 100 μm or more can be suitably used. A resin layer having a thickness exceeding 200 μm may be formed by laminating a plurality of resin layers of the dry film of the present invention. In that case, a roll laminator or a vacuum laminator may be used.
前記樹脂層は、硬化性樹脂を含むことが好ましく、例えば、エポキシ樹脂を含んでいてもよい。エポキシ樹脂は、エポキシ基を有する樹脂であり、従来公知のものをいずれも使用できる。分子中にエポキシ基を２個有する２官能性エポキシ樹脂、分子中にエポキシ基を３個以上有する多官能エポキシ樹脂等が挙げられる。なお、水素添加されたエポキシ樹脂であってもよい。前記樹脂層は、前記エポキシ樹脂として、半固形エポキシ樹脂および結晶性エポキシ樹脂のいずれか少なくとも１種を含む。半固形エポキシ樹脂および結晶性エポキシ樹脂は、それぞれ１種を単独または２種類以上を組合せて用いることができる。また、前記樹脂層は、固形エポキシ樹脂や液状エポキシ樹脂を含有してもよい。本明細書において、固形エポキシ樹脂とは４０℃で固体状であるエポキシ樹脂を言い、半固形エポキシ樹脂とは２０℃で固体状であり、４０℃で液状であるエポキシ樹脂を言い、液状エポキシ樹脂とは２０℃で液状のエポキシ樹脂をいう。液状の判定は、危険物の試験及び性状に関する省令（平成元年自治省令第１号）の別紙第２の「液状の確認方法」に準じて行う。例えば、特開２０１６－０７９３８４号公報の段落２３～２５に記載の方法にて行なう。また、結晶性エポキシ樹脂とは、結晶性の強いエポキシ樹脂を意味し、融点以下の温度では、高分子鎖が規則正しく配列し、固形樹脂でありながらも、溶融時には液状樹脂並みの低粘度となる熱硬化性のエポキシ樹脂をいう。 The resin layer preferably contains a curable resin, and may contain, for example, an epoxy resin. The epoxy resin is a resin having an epoxy group, and any conventionally known resin can be used. Examples include bifunctional epoxy resins having two epoxy groups in the molecule and polyfunctional epoxy resins having three or more epoxy groups in the molecule. A hydrogenated epoxy resin may also be used. The resin layer contains at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin. Semi-solid epoxy resins and crystalline epoxy resins may be used singly or in combination of two or more. Moreover, the resin layer may contain a solid epoxy resin or a liquid epoxy resin. In the present specification, solid epoxy resin refers to an epoxy resin that is solid at 40°C, semi-solid epoxy resin refers to an epoxy resin that is solid at 20°C and liquid at 40°C, and liquid epoxy resin. means an epoxy resin that is liquid at 20°C. Judgment of the liquid state shall be carried out in accordance with the "Methods for confirming the liquid state" in Attachment No. 2 of the Ministerial Ordinance Concerning Testing and Properties of Dangerous Substances (Ministry of Home Affairs Ordinance No. 1 of 1989). For example, the method described in paragraphs 23 to 25 of JP-A-2016-079384 is used. In addition, the crystalline epoxy resin means an epoxy resin with strong crystallinity, and at a temperature below the melting point, the polymer chains are arranged in an orderly manner, and although it is a solid resin, when melted, it has a low viscosity similar to that of a liquid resin. A thermosetting epoxy resin.
半固形エポキシ樹脂としては、ＤＩＣ社製ＥＰＩＣＬＯＮ８６０、ＥＰＩＣＬＯＮ９００－ＩＭ、ＥＰＩＣＬＯＮＥＸＡ―４８１６、ＥＰＩＣＬＯＮ ＥＸＡ－４８２２、東都化成社製エポトートＹＤ－１３４、三菱ケミカル社製ｊＥＲ８３４、ｊＥＲ８７２、住友化学社製ＥＬＡ－１３４等のビスフェノールＡ型エポキシ樹脂；ＤＩＣ社製ＥＰＩＣＬＯＮ ＨＰ－４０３２等のナフタレン型エポキシ樹脂；ＤＩＣ社製ＥＰＩＣＬＯＮ Ｎ－７４０等のフェノールノボラック型エポキシ樹脂等が挙げられる。
半固形状エポキシ樹脂として、ビスフェノールＡ型エポキシ樹脂、ナフタレン型エポキシ樹脂およびフェノールノボラック型エポキシ樹脂からなる群より選ばれる少なくとも１種を含むことが好ましい。半固形状エポキシ樹脂を含むことにより、硬化物のガラス転移温度（Ｔｇ）が高く、ＣＴＥが低くなり、クラック耐性に優れる。
Semi-solid epoxy resins include EPICLON860, EPICLON900-IM, EPICLONEXA-4816, EPICLON EXA-4822 manufactured by DIC, Epotote YD-134 manufactured by Toto Kasei, jER834 and jER872 manufactured by Mitsubishi Chemical, ELA-134 manufactured by Sumitomo Chemical, etc. bisphenol A type epoxy resin; naphthalene type epoxy resin such as EPICLON HP-4032 manufactured by DIC; phenol novolac type epoxy resin such as EPICLON N-740 manufactured by DIC;
As the semi-solid epoxy resin, it is preferable to include at least one selected from the group consisting of bisphenol A type epoxy resin, naphthalene type epoxy resin and phenol novolac type epoxy resin. By containing a semi-solid epoxy resin, the cured product has a high glass transition temperature (Tg), a low CTE, and excellent crack resistance.
結晶性エポキシ樹脂としては、例えば、ビフェニル構造、スルフィド構造、フェニレン構造、ナフタレン構造等を有する結晶性エポキシ樹脂を用いることができる。ビフェニルタイプのエポキシ樹脂は、例えば、三菱ケミカル社製ｊＥＲ ＹＸ４０００、ｊＥＲ ＹＸ４０００Ｈ、ｊＥＲ ＹＬ６１２１Ｈ、ｊＥＲ ＹＬ６６４０、ｊＥＲ ＹＬ６６７７として提供されており、ジフェニルスルフィド型エポキシ樹脂は、例えば、東都化成社製エポトートＹＳＬＶ－１２０ＴＥとして提供されており、フェニレン型エポキシ樹脂は、例えば、東都化成社製エポトートＹＤＣ－１３１２として提供されており、ナフタレン型エポキシ樹脂は、例えば、ＤＩＣ社製ＥＰＩＣＬＯＮ ＨＰ－４０３２、ＥＰＩＣＬＯＮ ＨＰ－４０３２Ｄ、ＥＰＩＣＬＯＮ ＨＰ－４７００として提供されている。また、結晶性エポキシ樹脂として東都化成社製エポトートＹＳＬＶ－９０Ｃ、日産化成社製ＴＥＰＩＣ－Ｓ（トリグリシジルイソシアヌレート）を用いることもできる。 As the crystalline epoxy resin, for example, a crystalline epoxy resin having a biphenyl structure, a sulfide structure, a phenylene structure, a naphthalene structure, or the like can be used. Biphenyl-type epoxy resins are provided as, for example, jER YX4000, jER YX4000H, jER YL6121H, jER YL6640, and jER YL6677 manufactured by Mitsubishi Chemical Corporation, and diphenyl sulfide-type epoxy resins are provided, for example, by Epotote YSLV-120TE manufactured by Toto Kasei Co., Ltd. , and the phenylene type epoxy resin is provided, for example, as Epotote YDC-1312 manufactured by Tohto Kasei Co., Ltd., and the naphthalene type epoxy resin is provided, for example, as EPICLON HP-4032, EPICLON HP-4032D, EPICLON manufactured by DIC. It is offered as HP-4700. As the crystalline epoxy resin, Epotato YSLV-90C manufactured by Tohto Kasei Co., Ltd. and TEPIC-S (triglycidyl isocyanurate) manufactured by Nissan Kasei Co., Ltd. can also be used.
固形エポキシ樹脂としては、ＤＩＣ社製ＨＰ－４７００（ナフタレン型エポキシ樹脂）、ＤＩＣ社製ＥＸＡ４７００（４官能ナフタレン型エポキシ樹脂）、日本化薬社製ＮＣ－７０００（ナフタレン骨格含有多官能固形エポキシ樹脂）等のナフタレン型エポキシ樹脂；日本化薬社製ＥＰＰＮ－５０２Ｈ（トリスフェノールエポキシ樹脂）等のフェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物のエポキシ化物（トリスフェノール型エポキシ樹脂）；ＤＩＣ社製ＥＰＩＣＬＯＮ ＨＰ－７２００Ｈ（ジシクロペンタジエン骨格含有多官能固形エポキシ樹脂）等のジシクロペンタジエンアラルキル型エポキシ樹脂；日本化薬社製ＮＣ－３０００Ｈ（ビフェニル骨格含有多官能固形エポキシ樹脂）等のビフェニルアラルキル型エポキシ樹脂；日本化薬社製ＮＣ－３０００Ｌ等のビフェニル／フェノールノボラック型エポキシ樹脂；ＤＩＣ社製ＥＰＩＣＬＯＮ Ｎ６６０、ＥＰＩＣＬＯＮ Ｎ６９０、Ｎ７７０、日本化薬社製ＥＯＣＮ－１０４Ｓ等のノボラック型エポキシ樹脂；新日鉄住金化学社製ＴＸ０７１２等のリン含有エポキシ樹脂；日産化学社製ＴＥＰＩＣ等のトリス（２，３－エポキシプロピル）イソシアヌレート等が挙げられる。固形エポキシ樹脂を含むことで、硬化物のガラス転移温度が高くなり耐熱性に優れる。 The solid epoxy resins include HP-4700 manufactured by DIC Corporation (naphthalene type epoxy resin), EXA4700 manufactured by DIC Corporation (tetrafunctional naphthalene type epoxy resin), and NC-7000 manufactured by Nippon Kayaku Co., Ltd. (polyfunctional solid epoxy resin containing a naphthalene skeleton). Naphthalene-type epoxy resins such as Nippon Kayaku Co., Ltd. EPPN-502H (trisphenol epoxy resin) and other epoxidized products of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups (trisphenol-type epoxy resins); DIC Dicyclopentadiene aralkyl type epoxy resin such as EPICLON HP-7200H (dicyclopentadiene skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; type epoxy resin; biphenyl / phenol novolac type epoxy resin such as NC-3000L manufactured by Nippon Kayaku; EPICLON N660, EPICLON N690, N770 manufactured by DIC; Phosphorus-containing epoxy resins such as TX0712 manufactured by Kagaku Co.; tris(2,3-epoxypropyl) isocyanurate such as TEPIC manufactured by Nissan Chemical Co.; By containing a solid epoxy resin, the cured product has a high glass transition temperature and excellent heat resistance.
液状エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ｔｅｒｔ－ブチル－カテコール型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、脂環式エポキシ樹脂等が挙げられる。液状エポキシ樹脂を含むことで、ドライフィルムの可とう性に優れる。 Liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, glycidylamine type epoxy resin, aminophenol type epoxy resin. , and alicyclic epoxy resins. By containing the liquid epoxy resin, the dry film has excellent flexibility.
半固形エポキシ樹脂および結晶性エポキシ樹脂の配合量は、合計で、エポキシ樹脂全量基準で５～４０質量％であることが好ましく、１０～３０質量％であることがより好ましい。上記範囲内であると、ドライフィルムの樹脂層のタック性と柔軟性に優れる。 The total blending amount of the semi-solid epoxy resin and the crystalline epoxy resin is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the epoxy resin. Within the above range, the resin layer of the dry film is excellent in tackiness and flexibility.
［無機フィラー］
前記樹脂層は、無機フィラーを含有することが好ましい。無機フィラーを配合することによって、得られる硬化物の硬化収縮を抑制し、密着性、硬度、絶縁層の周囲にある銅等の導体層と熱強度を合わせることによるクラック耐性等の熱特性を向上させることができる。無機フィラーとしては従来公知の無機フィラーが使用でき、特定のものに限定されないが、例えば、硫酸バリウム、チタン酸バリウム、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカなどのシリカ、タルク、クレー、ノイブルグ珪土粒子、ベーマイト、炭酸マグネシウム、炭酸カルシウム、酸化チタン、酸化アルミニウム、水酸化アルミニウム、窒化ケイ素、窒化アルミニウム、ジルコン酸カルシウム等の体質顔料や、銅、錫、亜鉛、ニッケル、銀、パラジウム、アルミニウム、鉄、コバルト、金、白金等の金属粉体が挙げられる。無機フィラーは球状粒子であることが好ましい。中でもシリカが好ましく、硬化性組成物の硬化物の硬化収縮を抑制し、より低ＣＴＥとなり、また、密着性、硬度などの特性を向上させる。また、アルミナのように比重の大きな無機フィラーは一般的に沈降速度が速くなるが、本発明においては沈降を抑制できるため好適に用いることができる。無機フィラーの平均粒子径（メディアン径、Ｄ５０）は、０．０１～１０μｍであることが好ましい。無機フィラーとしては、スリット加工性の観点から、平均粒子径が０．０１～３μｍのシリカであることが好ましい。なお、本明細書において、無機フィラーの平均粒子径は、一次粒子の粒径だけでなく、二次粒子（凝集体）の粒径も含めた平均粒子径である。平均粒子径は、レーザー回折式粒子径分布測定装置により求めることができる。レーザー回折法による測定装置としては、マイクロトラック・ベル社製Ｎａｎｏｔｒａｃ ｗａｖｅなどが挙げられる。
[Inorganic filler]
The resin layer preferably contains an inorganic filler. By blending inorganic fillers, curing shrinkage of the resulting cured product is suppressed, and thermal properties such as adhesion, hardness, and crack resistance are improved by matching the thermal strength with the conductor layer such as copper around the insulating layer. can be made Conventionally known inorganic fillers can be used as the inorganic filler, and although not limited to a specific one, examples include silica such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay , Neuburg silica particles, boehmite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate and other extender pigments, copper, tin, zinc, nickel, silver, palladium , aluminum, iron, cobalt, gold, and platinum. The inorganic filler is preferably spherical particles. Among them, silica is preferable because it suppresses curing shrinkage of the cured product of the curable composition, lowers the CTE, and improves properties such as adhesion and hardness. In addition, although an inorganic filler having a large specific gravity such as alumina generally has a high sedimentation rate, it can be preferably used in the present invention because it can suppress sedimentation. The average particle size (median size, D50) of the inorganic filler is preferably 0.01 to 10 μm. The inorganic filler is preferably silica having an average particle size of 0.01 to 3 μm from the viewpoint of slit workability. In this specification, the average particle size of the inorganic filler is an average particle size including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregate). The average particle size can be obtained with a laser diffraction particle size distribution analyzer. Nanotrac wave manufactured by Microtrac Bell Co., Ltd., etc., can be used as a measuring device using the laser diffraction method.
前記無機フィラーは、表面処理されていてもよい。表面処理としては、カップリング剤による表面処理や、アルミナ処理等の有機基を導入しない表面処理がされていてもよい。無機フィラーの表面処理方法は特に限定されず、公知慣用の方法を用いればよく、硬化性反応基を有する表面処理剤、例えば、硬化性反応基を有機基として有するカップリング剤等で無機フィラーの表面を処理すればよい。 The inorganic filler may be surface-treated. As the surface treatment, a surface treatment with a coupling agent, or a surface treatment that does not introduce an organic group, such as alumina treatment, may be performed. The surface treatment method of the inorganic filler is not particularly limited, and a known and commonly used method may be used, and the inorganic filler is treated with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group as an organic group. surface should be treated.
無機フィラーは、粉体または固体状態でエポキシ樹脂等と配合してもよく、溶剤や分散剤と混合してスラリーとした後でエポキシ樹脂等と配合してもよい。 The inorganic filler may be blended with the epoxy resin or the like in a powder or solid state, or may be blended with the epoxy resin or the like after being mixed with a solvent or dispersant to form a slurry.
無機フィラーは、１種を単独で用いてもよく、２種以上の混合物として用いてもよい。無機フィラーの配合量は、ドライフィルムの樹脂層の固形分全量基準で、１０～９０質量％であることが好ましく、５０～９０質量％であることがより好ましく、６０～９０質量％であることがさらにより好ましい。無機フィラーの配合量が１０質量％以上の場合、熱膨張を抑制して耐熱性が向上し、一方、９０質量％以下の場合、クラックの発生を抑制できる。 An inorganic filler may be used individually by 1 type, and may be used as a mixture of 2 or more types. The amount of the inorganic filler compounded is preferably 10 to 90% by mass, more preferably 50 to 90% by mass, and 60 to 90% by mass, based on the total solid content of the resin layer of the dry film. is even more preferred. When the amount of the inorganic filler is 10% by mass or more, thermal expansion is suppressed and heat resistance is improved.
［硬化剤］
前記樹脂層は、硬化剤を含有することが好ましい。硬化剤としては、フェノール性水酸基を有する化合物、ポリカルボン酸およびその酸無水物、シアネートエステル基を有する化合物、活性エステル基を有する化合物、マレイミド基を有する化合物、脂環式オレフィン重合体等が挙げられる。硬化剤は１種を単独または２種以上を組み合わせて用いることができる。
[Curing agent]
The resin layer preferably contains a curing agent. Examples of curing agents include compounds having a phenolic hydroxyl group, polycarboxylic acids and their acid anhydrides, compounds having a cyanate ester group, compounds having an active ester group, compounds having a maleimide group, and alicyclic olefin polymers. be done. Curing agents may be used singly or in combination of two or more.
本発明において前記樹脂層は、フェノール性水酸基を有する化合物、活性エステル基を有する化合物、シアネートエステル基を有する化合物およびマレイミド基を有する化合物の少なくともいずれか１種を含むことが好ましい。フェノール性水酸基を有する化合物および活性エステル基を有する化合物を使用することにより、低粗度基材や回路との接着性に優れた硬化物を得ることができる。また、シアネートエステルを使用することにより、硬化物のＴｇが高くなり、耐熱性が向上し、マレイミド基を有する化合物を使用することにより、硬化物のＴｇが高くなり、耐熱性が向上するとともに、ＣＴＥを低減することができる。 In the present invention, the resin layer preferably contains at least one of a compound having a phenolic hydroxyl group, a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group. By using a compound having a phenolic hydroxyl group and a compound having an active ester group, it is possible to obtain a cured product having excellent adhesiveness to low-roughness substrates and circuits. Further, by using a cyanate ester, the Tg of the cured product is increased and the heat resistance is improved, and by using a compound having a maleimide group, the Tg of the cured product is increased and the heat resistance is improved, CTE can be reduced.
前記フェノール性水酸基を有する化合物としては、フェノールノボラック樹脂、アルキルフェノールボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエン型フェノール樹脂、Ｘｙｌｏｋ型フェノール樹脂、テルペン変性フェノール樹脂、クレゾール／ナフトール樹脂、ポリビニルフェノール類、フェノール／ナフトール樹脂、α－ナフトール骨格含有フェノール樹脂、トリアジン骨格含有クレゾールノボラック樹脂、ビフェニルアラルキル型フェノール樹脂、ザイロック型フェノールノボラック樹脂等の従来公知のものを用いることができる。
前記フェノール性水酸基を有する化合物の中でも、水酸基当量が１００ｇ／ｅｑ．以上のものが好ましい。水酸基当量が１００ｇ／ｅｑ．以上のフェノール性水酸基を有する化合物としては、例えば、ジシクロペンタジエン骨格フェノールノボラック樹脂（ＧＤＰシリーズ、群栄化学社製）、ザイロック型フェノールノボラック樹脂（ＭＥＨ－７８００、明和化成社製）、ビフェニルアラルキル型ノボラック樹脂（ＭＥＨ－７８５１、明和化成社製）、ナフトールアラルキル型硬化剤（ＳＮシリーズ、新日鉄住金社製）、トリアジン骨格含有クレゾールノボラック樹脂（ＬＡ－３０１８－５０Ｐ、ＤＩＣ社製）、トリアジン骨格含有フェノールノボラック樹脂（ＬＡ－７０５Ｎ、ＤＩＣ社製）などが挙げられる。
Examples of compounds having a phenolic hydroxyl group include phenol novolak resins, alkylphenol borak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene-modified phenol resins, cresol/naphthol resins, polyvinylphenols, Conventionally known resins such as phenol/naphthol resins, α-naphthol skeleton-containing phenol resins, triazine skeleton-containing cresol novolac resins, biphenylaralkyl-type phenol resins, and Zyloc-type phenol novolac resins can be used.
Among the compounds having a phenolic hydroxyl group, those having a hydroxyl equivalent of 100 g/eq. The above are preferred. A hydroxyl equivalent of 100 g/eq. Examples of compounds having a phenolic hydroxyl group include dicyclopentadiene skeleton phenol novolac resins (GDP series, manufactured by Gunei Chemical Co., Ltd.), Zyloc-type phenol novolac resins (MEH-7800, manufactured by Meiwa Kasei Co., Ltd.), and biphenylaralkyl type. Novolac resin (MEH-7851, manufactured by Meiwa Kasei Co., Ltd.), naphthol aralkyl type curing agent (SN series, manufactured by Nippon Steel & Sumikin Co., Ltd.), triazine skeleton-containing cresol novolak resin (LA-3018-50P, manufactured by DIC), triazine skeleton-containing phenol A novolac resin (LA-705N, manufactured by DIC Corporation) and the like can be mentioned.
前記シアネートエステル基を有する化合物は、一分子中に２個以上のシアネートエステル基（－ＯＣＮ）を有する化合物であることが好ましい。シアネートエステル基を有する化合物は、従来公知のものをいずれも使用することができる。シアネートエステル基を有する化合物としては、例えば、フェノールノボラック型シアネートエステル樹脂、アルキルフェノールノボラック型シアネートエステル樹脂、ジシクロペンタジエン型シアネートエステル樹脂、ビスフェノールＡ型シアネートエステル樹脂、ビスフェノールＦ型シアネートエステル樹脂、ビスフェノールＳ型シアネートエステル樹脂が挙げられる。また、一部がトリアジン化したプレポリマーであってもよい。 The compound having a cyanate ester group is preferably a compound having two or more cyanate ester groups (--OCN) in one molecule. Any conventionally known compound having a cyanate ester group can be used. Examples of compounds having a cyanate ester group include phenol novolac type cyanate ester resins, alkylphenol novolac type cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol A type cyanate ester resins, bisphenol F type cyanate ester resins, and bisphenol S type. A cyanate ester resin is mentioned. Also, a prepolymer partially triazined may be used.
市販されているシアネートエステル基を有する化合物としては、フェノールノボラック型多官能シアネートエステル樹脂（ロンザジャパン社製、ＰＴ３０Ｓ）、ビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー（ロンザジャパン社製、ＢＡ２３０Ｓ７５）、ジシクロペンタジエン構造含有シアネートエステル樹脂（ロンザジャパン社製、ＤＴ－４０００、ＤＴ－７０００）等が挙げられる。 Examples of commercially available compounds having a cyanate ester group include a phenol novolak type polyfunctional cyanate ester resin (PT30S, manufactured by Lonza Japan Co., Ltd.), and a prepolymer in which part or all of bisphenol A dicyanate is triazined to form a trimer. (BA230S75, manufactured by Lonza Japan), dicyclopentadiene structure-containing cyanate ester resin (DT-4000, DT-7000, manufactured by Lonza Japan).
前記活性エステル基を有する化合物は、一分子中に２個以上の活性エステル基を有する化合物であることが好ましい。活性エステル基を有する化合物は、一般に、カルボン酸化合物とヒドロキシ化合物との縮合反応によって得ることができる。中でも、ヒドロキシ化合物としてフェノール化合物またはナフトール化合物を用いて得られる活性エステル基を有する化合物が好ましい。フェノール化合物またはナフトール化合物としては、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、カテコール、α－ナフトール、β－ナフトール、１，５－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、２，６－ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエニルジフェノール、フェノールノボラック等が挙げられる。また、活性エステル基を有する化合物としては、ナフタレンジオールアルキル／安息香酸型でもよい。 The compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. A compound having an active ester group can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among them, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferred. Phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol , dicyclopentadienyl diphenol, phenol novolac, and the like. Further, the compound having an active ester group may be naphthalenediol alkyl/benzoic acid type.
市販されている活性エステル基を有する化合物としては、ジシクロペンタジエン型のジフェノール化合物、例えば、ＨＰＣ８０００－６５Ｔ（ＤＩＣ社製）、ＨＰＣ８１００－６５Ｔ（ＤＩＣ社製）、ＨＰＣ８１５０－６５Ｔ（ＤＩＣ社製）が挙げられる。 Examples of commercially available compounds having an active ester group include dicyclopentadiene-type diphenol compounds such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), and HPC8150-65T (manufactured by DIC). is mentioned.
前記マレイミド基を有する化合物は、マレイミド骨格を有する化合物であり、従来公知のものをいずれも使用できる。マレイミド基を有する化合物は、２以上のマレイミド骨格を有することが好ましく、Ｎ，Ｎ’－１，３－フェニレンジマレイミド、Ｎ，Ｎ’－１，４－フェニレンジマレイミド、Ｎ，Ｎ’－４，４－ジフェニルメタンビスマレイミド、１，２－ビス（マレイミド）エタン、１，６－ビスマレイミドヘキサン、１，６－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、２，２’－ビス－［４－（４－マレイミドフェノキシ）フェニル］プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、ビス（３－エチル－５－メチル－４－マレイミドフェニル）メタン、ビスフェノールＡジフェニルエーテルビスマレイミド、ポリフェニルメタンマレイミド、およびこれらのオリゴマー、ならびにマレイミド骨格を有するジアミン縮合物のうちの少なくとも何れか１種であることがより好ましい。前記オリゴマーは、上述のマレイミド基を有する化合物のうちのモノマーであるマレイミド基を有する化合物を縮合させることにより得られたオリゴマーである。 The compound having a maleimide group is a compound having a maleimide skeleton, and any conventionally known compound can be used. The compound having a maleimide group preferably has two or more maleimide skeletons, such as N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-4 ,4-diphenylmethanebismaleimide, 1,2-bis(maleimido)ethane, 1,6-bismaleimidohexane, 1,6-bismaleimido-(2,2,4-trimethyl)hexane, 2,2′-bis- [4-(4-maleimidophenoxy)phenyl]propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis( At least one of 3-ethyl-5-methyl-4-maleimidophenyl)methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, oligomers thereof, and diamine condensates having a maleimide skeleton is more preferred. The oligomer is an oligomer obtained by condensing a compound having a maleimide group, which is a monomer among the compounds having a maleimide group described above.
市販されているマレイミド基を有する化合物としては、ＢＭＩ－１０００（４，４’－ジフェニルメタンビスマレイミド、大和化成工業社製）、ＢＭＩ－２３００（フェニルメタンビスマレイミド、大和化成工業社製）、ＢＭＩ－３０００（ｍ－フェニレンビスマレイミド、大和化成工業社製）、ＢＭＩ－５１００（３，３’－ジメチル－５，５’－ジメチル－４，４’－ジフェニルメタンビスマレイミド、大和化成工業社製）、ＢＭＩ－７０００（４－メチル－１，３，－フェニレンビスマレイミド、大和化成工業社製）、ＢＭＩ－ＴＭＨ（（１，６－ビスマレイミド－２，２，４－トリメチル）ヘキサン、大和化成工業社製）などが挙げられる。 Examples of commercially available compounds having a maleimide group include BMI-1000 (4,4′-diphenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-2300 (phenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI- 3000 (m-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-5100 (3,3′-dimethyl-5,5′-dimethyl-4,4′-diphenylmethanebismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI -7000 (4-methyl-1,3,-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Kasei Kogyo Co., Ltd. ) and the like.
硬化剤の配合量は、エポキシ樹脂１００質量部に対し２０～１００質量部であることが好ましく、２５～９０質量部であることがより好ましい。 The amount of the curing agent is preferably 20 to 100 parts by mass, more preferably 25 to 90 parts by mass, per 100 parts by mass of the epoxy resin.
前記樹脂層を形成する硬化性樹脂組成物の具体例としては、熱硬化性樹脂組成物、光硬化性熱硬化性樹脂組成物、光重合開始剤を含有する光硬化性熱硬化性樹脂組成物、光塩基発生剤を含有する光硬化性熱硬化性樹脂組成物、光酸発生剤を含有する光硬化性熱硬化性樹脂組成物、ネガ型光硬化性熱硬化性樹脂組成物およびポジ型感光性熱硬化性樹脂組成物、アルカリ現像型光硬化性熱硬化性樹脂組成物、溶剤現像型光硬化性熱硬化性樹脂組成物、膨潤剥離型熱硬化性樹脂組成物、溶解剥離型熱硬化性樹脂組成物が挙げられるが、これらに限定されるものではない。 Specific examples of the curable resin composition forming the resin layer include a thermosetting resin composition, a photocurable thermosetting resin composition, and a photocurable thermosetting resin composition containing a photopolymerization initiator. , a photocurable thermosetting resin composition containing a photobase generator, a photocurable thermosetting resin composition containing a photoacid generator, a negative photocurable thermosetting resin composition and a positive photosensitive thermosetting resin composition, alkali-developable photocurable thermosetting resin composition, solvent-developable photocurable thermosetting resin composition, swelling-releasable thermosetting resin composition, dissolution-releasable thermosetting Examples include, but are not limited to, resin compositions.
以下では、一例として、光硬化性成分を含まない熱硬化性樹脂組成物で樹脂層を形成する場合について、上記成分以外に含み得る成分について説明する。 In the following, as an example, components that can be included in addition to the above components will be described in the case of forming a resin layer with a thermosetting resin composition that does not contain a photocurable component.
前記樹脂層は、エポキシ樹脂以外の熱硬化性樹脂を含有してもよく、例えば、イソシアネート化合物、ブロックイソシアネート化合物、アミノ樹脂、ベンゾオキサジン樹脂、カルボジイミド樹脂、シクロカーボネート化合物、多官能オキセタン化合物、エピスルフィド樹脂などの公知慣用の熱硬化性樹脂が使用できる。 The resin layer may contain thermosetting resins other than epoxy resins, such as isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins. and other known and commonly used thermosetting resins can be used.
前記樹脂層は、得られる硬化膜の機械的強度を向上させるために、さらに熱可塑性樹脂を含有することができる。熱可塑性樹脂は、溶剤に可溶であることが好ましい。溶剤に可溶である場合、ドライフィルムの柔軟性が向上し、クラックの発生や粉落ちを抑制できる。熱可塑性樹脂としては、熱可塑性ポリヒドロキシポリエーテル樹脂や、エピクロルヒドリンと各種２官能フェノール化合物の縮合物であるフェノキシ樹脂或いはその骨格に存在するヒドロキシエーテル部の水酸基を各種酸無水物や酸クロリドを使用してエステル化したフェノキシ樹脂、ポリビニルアセタール樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ブロック共重合体等が挙げられる。熱可塑性樹脂は１種を単独または２種以上を組み合わせて用いることができる。 The resin layer may further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film. The thermoplastic resin is preferably soluble in solvents. When it is soluble in a solvent, the flexibility of the dry film is improved, and the occurrence of cracks and falling powder can be suppressed. Thermoplastic resins include thermoplastic polyhydroxy polyether resins, phenoxy resins that are condensates of epichlorohydrin and various bifunctional phenol compounds, and various acid anhydrides and acid chlorides that replace the hydroxyl groups of the hydroxy ether portion present in the skeleton. and esterified phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, block copolymers, and the like. Thermoplastic resins can be used singly or in combination of two or more.
前記樹脂層は高分子樹脂を含有する。前記高分子樹脂のガラス転移点は、－４０～２０℃であることが好ましく、－１５～１５℃であることがより好ましく、－５～１５℃であることが特に好ましい。－５～１５℃であると、硬化物の反りを良好に抑制することができる。
また、前記高分子樹脂の重量平均分子量は高いほど無機フィラーの沈降防止効果が大きいことから、１０万以上であることが好ましく、２０万以上であることがより好ましい。上限値としては、例えば、１００万以下である。
The resin layer contains a polymer resin. The glass transition point of the polymer resin is preferably -40 to 20°C, more preferably -15 to 15°C, and particularly preferably -5 to 15°C. When the temperature is -5 to 15°C, warping of the cured product can be suppressed satisfactorily.
In addition, the higher the weight-average molecular weight of the polymer resin, the greater the sedimentation-preventing effect of the inorganic filler. The upper limit is, for example, 1,000,000 or less.
高分子樹脂としては、ブタジエン骨格、アミド骨格、イミド骨格、アセタール骨格、カーボネート骨格、エステル骨格、ウレタン骨格、アクリル骨格及びシロキサン骨格から選択される１種以上の骨格を有する高分子樹脂などが挙げられる。例えば、ブタジエン骨格を有する高分子樹脂（日本曹達社製「Ｇ－１０００」、「Ｇ－３０００」、「ＧＩ－１０００」、「ＧＩ－３０００」、出光興産社製「Ｒ－４５ＥＰＩ」、ダイセル社製「ＰＢ３６００」、「エポフレンドＡＴ５０１」、クレイバレー社製「Ｒｉｃｏｎ１３０」、「Ｒｉｃｏｎ１４２」、「Ｒｉｃｏｎ１５０」、「Ｒｉｃｏｎ６５７」、「Ｒｉｃｏｎ１３０ＭＡ」）、ブタジエン骨格とポリイミド骨格を有する高分子樹脂（特開２００６－３７０８３号公報記載のもの）、アクリル骨格を有する高分子樹脂（ナガセケムテックス社製「ＳＧ－Ｐ３」、「ＳＧ－６００ＬＢ」、「ＳＧ－２８０」、「ＳＧ－７９０」、「ＳＧ－Ｋ２」、根上工業社製「ＳＮ－５０」、「ＡＳ－３０００Ｅ」、「ＭＥ－２０００」）などが挙げられる。 Examples of polymer resins include polymer resins having one or more skeletons selected from butadiene skeletons, amide skeletons, imide skeletons, acetal skeletons, carbonate skeletons, ester skeletons, urethane skeletons, acrylic skeletons, and siloxane skeletons. . For example, polymer resins having a butadiene skeleton (“G-1000”, “G-3000”, “GI-1000”, “GI-3000” manufactured by Nippon Soda Co., Ltd., “R-45EPI” manufactured by Idemitsu Kosan Co., Ltd., Daicel "PB3600", "Epofriend AT501" manufactured by Clay Valley, "Ricon130", "Ricon142", "Ricon150", "Ricon657", "Ricon130MA" manufactured by Clay Valley), polymer resin having a butadiene skeleton and a polyimide skeleton (JP 2006 -37083), polymer resins having an acrylic skeleton ("SG-P3", "SG-600LB", "SG-280", "SG-790", "SG-K2" manufactured by Nagase ChemteX) ”, “SN-50”, “AS-3000E”, “ME-2000” manufactured by Neagari Kogyo Co., Ltd.).
熱可塑性樹脂の配合量は、樹脂層の固形分全量基準で、好ましくは０．５～２０質量％、より好ましくは０．５～１０質量％である。熱可塑性樹脂の配合量が上記範囲内であると、均一な粗化面状態を得られやすい。 The blending amount of the thermoplastic resin is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the resin layer. When the blending amount of the thermoplastic resin is within the above range, it is easy to obtain a uniform roughened surface state.
さらに、前記樹脂層は、必要に応じてゴム状粒子を含有することができる。このようなゴム状粒子としては、ポリブタジエンゴム、ポリイソプロピレンゴム、ウレタン変性ポリブタジエンゴム、エポキシ変性ポリブタジエンゴム、アクリロニトリル変性ポリブタジエンゴム、カルボキシル基変性ポリブタジエンゴム、カルボキシル基または水酸基で変性したアクリロニトリルブタジエンゴム、およびそれらの架橋ゴム粒子、コアシェル型ゴム粒子等が挙げられ、１種を単独または２種以上を組み合わせて用いることができる。これらのゴム状粒子は、得られる硬化膜の柔軟性を向上させたり、クラック耐性が向上したり、酸化剤による表面粗化処理を可能とし、銅箔等との密着強度を向上させるために添加される。 Furthermore, the resin layer may contain rubber-like particles as necessary. Examples of such rubbery particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, carboxyl group- or hydroxyl group-modified acrylonitrile-butadiene rubber, and These crosslinked rubber particles, core-shell type rubber particles and the like can be mentioned, and one type can be used alone or two or more types can be used in combination. These rubber-like particles are added to improve the flexibility of the resulting cured film, improve the crack resistance, enable surface roughening treatment with an oxidizing agent, and improve the adhesion strength to copper foil, etc. be done.
ゴム状粒子の平均粒子径は０．００５～１μｍの範囲が好ましく、０．２～１μｍの範囲がより好ましい。本発明におけるゴム状粒子の平均粒子径は、レーザー回折式粒子径分布測定装置により求めることができる。例えば、適当な有機溶剤にゴム状粒子を超音波などにより均一に分散させ、日機装社製Ｎａｎｏｔｒａｃ ｗａｖｅを用いて、ゴム状粒子の粒度分布を質量基準で作成し、そのメディアン径を平均粒子径とすることで測定することができる。 The average particle size of the rubber-like particles is preferably in the range of 0.005-1 μm, more preferably in the range of 0.2-1 μm. The average particle size of the rubber-like particles in the present invention can be determined with a laser diffraction particle size distribution analyzer. For example, the rubber-like particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the rubber-like particles is prepared on a mass basis using a Nanotrac wave manufactured by Nikkiso Co., Ltd. The median diameter is taken as the average particle diameter. can be measured by
ゴム状粒子の配合量は、樹脂層の固形分全量基準で、０．５～１０質量％であることが好ましく、１～５質量％であることがより好ましい。０．５質量％以上の場合、クラック耐性が得られ、導体パターン等との密着強度を向上できる。１０質量％以下の場合、熱膨張係数（ＣＴＥ）が低下し、ガラス転移温度（Ｔｇ）が上昇して硬化特性が向上する。 The amount of the rubber-like particles compounded is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the total solid content of the resin layer. When it is 0.5% by mass or more, crack resistance can be obtained, and the adhesion strength to the conductor pattern or the like can be improved. If it is 10% by mass or less, the coefficient of thermal expansion (CTE) is lowered, the glass transition temperature (Tg) is raised, and the curing properties are improved.
前記樹脂層は、硬化促進剤を含有することができる。硬化促進剤は、熱硬化反応を促進させるものであり、密着性、耐薬品性、耐熱性等の特性をより一層向上させるために使用される。このような硬化促進剤の具体例としては、イミダゾールおよびその誘導体；アセトグアナミン、ベンゾグアナミン等のグアナミン類；ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ｍ－キシレンジアミン、ジアミノジフェニルスルフォン、ジシアンジアミド、尿素、尿素誘導体、メラミン、多塩基ヒドラジド等のポリアミン類；これらの有機酸塩および／またはエポキシアダクト；三フッ化ホウ素のアミン錯体；エチルジアミノ－Ｓ－トリアジン、２，４－ジアミノ－Ｓ－トリアジン、２，４－ジアミノ－６－キシリル－Ｓ－トリアジン等のトリアジン誘導体類；トリメチルアミン、トリエタノールアミン、Ｎ，Ｎ－ジメチルオクチルアミン、Ｎ－ベンジルジメチルアミン、ピリジン、Ｎ－メチルモルホリン、ヘキサ（Ｎ－メチル）メラミン、２，４，６－トリス（ジメチルアミノフェノール）、テトラメチルグアニジン、ｍ－アミノフェノール等のアミン類；ポリビニルフェノール、ポリビニルフェノール臭素化物、フェノールノボラック、アルキルフェノールノボラック等のポリフェノール類；トリブチルホスフィン、トリフェニルホスフィン、トリス－２－シアノエチルホスフィン等の有機ホスフィン類；トリ－ｎ－ブチル（２，５－ジヒドロキシフェニル）ホスホニウムブロマイド、ヘキサデシルトリブチルホスホニウムクロライド等のホスホニウム塩類；ベンジルトリメチルアンモニウムクロライド、フェニルトリブチルアンモニウムクロライド等の４級アンモニウム塩類；前記多塩基酸無水物；ジフェニルヨードニウムテトラフルオロボロエート、トリフェニルスルホニウムヘキサフルオロアンチモネート、２，４，６－トリフェニルチオピリリウムヘキサフルオロホスフェート等の光カチオン重合触媒；スチレン－無水マレイン酸樹脂；フェニルイソシアネートとジメチルアミンの等モル反応物や、トリレンジイソシアネート、イソホロンジイソシアネート等の有機ポリイソシアネートとジメチルアミンの等モル反応物、金属触媒等の従来公知の硬化促進剤が挙げられる。硬化促進剤の中でも、ＢＨＡＳＴ（Ｂｉａｓｅｄ Ｈｉｇｈｌｙ Ａｃｃｅｌｅｒａｔｅｄ Ｓｔｒｅｓｓ Ｔｅｓｔ）耐性が得られることから、ホスホニウム塩類が好ましい。 The resin layer may contain a curing accelerator. The curing accelerator accelerates the thermosetting reaction and is used to further improve properties such as adhesion, chemical resistance and heat resistance. Specific examples of such curing accelerators include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, polyamines such as melamine and polybasic hydrazides; organic acid salts and/or epoxy adducts thereof; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4- triazine derivatives such as diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, Amines such as 2,4,6-tris(dimethylaminophenol), tetramethylguanidine and m-aminophenol; Polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak and alkylphenol novolak; tributylphosphine and triphenylphosphine , tris-2-cyanoethylphosphine and other organic phosphines; tri-n-butyl (2,5-dihydroxyphenyl)phosphonium bromide, hexadecyltributylphosphonium chloride and other phosphonium salts; Quaternary ammonium salts; the polybasic acid anhydrides; photocationic polymerization catalysts such as diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate; Maleic anhydride resin; equimolar reaction products of phenyl isocyanate and dimethylamine, equimolar reaction products of organic polyisocyanates such as tolylene diisocyanate and isophorone diisocyanate and dimethylamine, and conventionally known curing accelerators such as metal catalysts. . Among the curing accelerators, phosphonium salts are preferable because BHAST (Biased Highly Accelerated Stress Test) resistance can be obtained.
硬化促進剤は、１種を単独または２種以上混合して用いることができる。硬化促進剤の使用は必須ではないが、特に硬化を促進したい場合には、エポキシ樹脂１００質量部に対して好ましくは０．０１～５質量部の範囲で用いることができる。金属触媒の場合、シアネートエステル基を有する化合物１００質量部に対して金属換算で１０～５５０ｐｐｍが好ましく、２５～２００ｐｐｍがより好ましい。 A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types. Although the use of a curing accelerator is not essential, it can be used preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin, especially when curing is desired to be accelerated. In the case of a metal catalyst, it is preferably 10 to 550 ppm, more preferably 25 to 200 ppm, in terms of metal with respect to 100 parts by mass of the compound having a cyanate ester group.
有機溶剤としては、特に制限はないが、例えば、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤などを挙げることができる。具体的には、メチルエチルケトン、シクロヘキサノン、メチルブチルケトン、メチルイソブチルケトン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、酢酸イソブチル、エチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテートなどのエステル類；エタノール、プロパノール、２－メトキシプロパノール、ｎ－ブタノール、イソブチルアルコール、イソペンチルアルコール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等の他、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）、テトラクロロエチレン、テレビン油等が挙げられる。また、丸善石油化学社製スワゾール１０００、スワゾール１５００、三共化学社製ソルベント＃１００、ソルベント＃１５０、シェルケミカルズジャパン社製シェルゾールＡ１００、シェルゾールＡ１５０、出光興産社製イプゾール１００番、イプゾール１５０番等の有機溶剤を用いてもよい。有機溶剤は、１種を単独で用いてもよく、２種以上の混合物として用いることができる。 The organic solvent is not particularly limited, but examples include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. can. Specifically, ketones such as methyl ethyl ketone, cyclohexanone, methyl butyl ketone, methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, Glycol ethers such as butyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; acetic acid Esters such as ethyl, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate; ethanol, propanol, 2-methoxy Alcohols such as propanol, n-butanol, isobutyl alcohol, isopentyl alcohol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; In addition to solvents and the like, N,N-dimethylformamide (DMF), tetrachlorethylene, turpentine oil and the like can be used. In addition, Swazol 1000 and Swazol 1500 manufactured by Maruzen Petrochemical Co., Ltd. Solvent #100 and Solvent #150 manufactured by Sankyo Chemical Co., Ltd. Shellsol A100 and A150 manufactured by Shell Chemicals Japan Co., Ltd. Ipsol 100 and Ipsol 150 manufactured by Idemitsu Kosan Co., Ltd. of organic solvents may be used. The organic solvent may be used singly or as a mixture of two or more.
前記樹脂層中の残留溶剤量は、０．５～７．０質量％であることが好ましい。残留溶剤が７．０質量％以下であると、熱硬化時の突沸を抑え、表面の平坦性がより良好となる。また、溶融粘度が下がり過ぎて樹脂が流れてしまうことを抑制でき、平坦性が良好となる。残留溶剤が０．５質量％以上であると、ラミネート時の流動性が良好で、平坦性および埋め込み性がより良好となる。 The amount of residual solvent in the resin layer is preferably 0.5 to 7.0% by mass. When the residual solvent content is 7.0% by mass or less, bumping during thermosetting is suppressed, and the surface flatness becomes better. In addition, it is possible to prevent the resin from flowing due to an excessive decrease in melt viscosity, thereby improving flatness. When the residual solvent is 0.5% by mass or more, the fluidity during lamination is good, and the flatness and embedding properties are further improved.
前記樹脂層は、さらに必要に応じて、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の従来公知の着色剤、アスベスト、オルベン、ベントン、微紛シリカ等の従来公知の増粘剤、シリコーン系、フッ素系、高分子系等の消泡剤および／またはレベリング剤、チアゾール系、トリアゾール系、シランカップリング剤等の密着性付与剤、難燃剤、チタネート系、アルミニウム系の従来公知の添加剤類を用いることができる。 If necessary, the resin layer may contain conventionally known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, asbestos, orben, and bentone. , conventionally known thickeners such as finely divided silica, silicone-based, fluorine-based, polymer-based defoaming agents and / or leveling agents, thiazole-based, triazole-based, silane coupling agents and other adhesion-imparting agents, Conventionally known additives such as flame retardants, titanate-based and aluminum-based additives can be used.
［キャリアフィルム］
キャリアフィルムとは、ドライフィルムの樹脂層を支持する役割を有するものであり、該樹脂層を形成する際に、硬化性樹脂組成物が塗布されるフィルムである。キャリアフィルムとしては、例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等の熱可塑性樹脂からなるフィルム、および、表面処理した紙等を用いることができる。これらの中でも、耐熱性、機械的強度、取扱性等の観点から、ポリエステルフィルムを好適に使用することができる。キャリアフィルムの厚さは、特に制限されるものではないが概ね１０～１５０μｍの範囲で用途に応じて適宜選択される。キャリアフィルムの樹脂層を設ける面には、離型処理が施されていてもよい。また、キャリアフィルムの樹脂層を設ける面には、スパッタもしくは極薄銅箔が形成されていてもよい。
[Carrier film]
The carrier film has a role of supporting the resin layer of the dry film, and is a film to which the curable resin composition is applied when forming the resin layer. Examples of carrier films include thermoplastic resin films such as polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyimide films, polyamideimide films, polyethylene films, polytetrafluoroethylene films, polypropylene films, and polystyrene films, and Surface-treated paper or the like can be used. Among these, a polyester film can be preferably used from the viewpoint of heat resistance, mechanical strength, handleability, and the like. Although the thickness of the carrier film is not particularly limited, it is appropriately selected in the range of approximately 10 to 150 μm depending on the application. A releasing treatment may be applied to the surface of the carrier film on which the resin layer is to be provided. Sputtering or ultra-thin copper foil may be formed on the surface of the carrier film on which the resin layer is to be formed.
本発明のドライフィルムを用いたプリント配線板の製造方法としては、従来公知の方法を用いればよい。例えば、樹脂層が熱硬化性樹脂組成物からなる場合には、下記のような方法でプリント配線板を製造することができる。ドライフィルムから保護フィルムを剥離し、回路パターンが形成された回路基板に加熱ラミネートした後、熱硬化させる。熱硬化は、オーブン中で硬化、もしくは熱板プレスで硬化させてもよい。回路が形成された基材と本発明のドライフィルムをラミネートもしくは熱板プレスする際に、銅箔もしくは回路形成された基材を同時に積層することもできる。回路パターンが形成された基材上の所定の位置に対応する位置に、レーザー照射またはドリルでパターンやビアホールを形成し、回路配線を露出させることで、プリント配線板を製造することができる。この際、パターンやビアホール内の回路配線上に除去しきれないで残留した成分（スミア）が存在する場合にはデスミア処理を行う。キャリアフィルムは、ラミネート後、熱硬化後、レーザー加工後またはデスミア処理後のいずれかに、剥離すればよい。なお、層間回路の接続方法は、カッパーピラーによる接続でもよい。 As a method for producing a printed wiring board using the dry film of the present invention, a conventionally known method may be used. For example, when the resin layer is made of a thermosetting resin composition, the printed wiring board can be produced by the following method. After peeling off the protective film from the dry film and heat-laminating it on a circuit board having a circuit pattern formed thereon, it is thermally cured. For heat curing, curing may be performed in an oven or using a hot plate press. When the circuit-formed substrate and the dry film of the present invention are laminated or hot-plate-pressed, the copper foil or the circuit-formed substrate can be laminated at the same time. A printed wiring board can be manufactured by forming patterns and via holes by laser irradiation or drilling at positions corresponding to predetermined positions on a substrate on which a circuit pattern is formed and exposing circuit wiring. At this time, if there is a residual component (smear) that cannot be completely removed on the pattern or the circuit wiring in the via hole, desmear processing is performed. The carrier film may be peeled off after lamination, after heat curing, after laser processing, or after desmear treatment. Note that a method of connecting the interlayer circuits may be a connection using a copper pillar.
本発明のドライフィルムは、電子部品、特にプリント配線板の永久保護膜の形成に好ましく用いることができ、中でもソルダーレジスト層、層間絶縁層、フレキシブルプリント配線板のカバーレイの形成に好ましく用いることができる。特に、本発明のドライフィルムは、無機フィラー含有量の多い硬化物を形成する用途に好ましく用いることができる。本発明のドライフィルムを用いて、配線を貼り合わせることによって配線板を形成してもよい。また、半導体チップ用の封止材としても用いることができる。 The dry film of the present invention can be preferably used for forming a permanent protective film for electronic parts, particularly for printed wiring boards, and is particularly preferably used for forming solder resist layers, interlayer insulation layers, and coverlays for flexible printed wiring boards. can. In particular, the dry film of the present invention can be preferably used for forming a cured product with a high inorganic filler content. A wiring board may be formed by bonding wiring using the dry film of the present invention. It can also be used as a sealing material for semiconductor chips.
以下、本発明の実施例、参考例および比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。なお、以下において「部」および「％」とあるのは、特に断りのない限り全て質量基準である。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, reference examples and comparative examples of the present invention, but the present invention is not limited to the following examples. In the following description, "parts" and "%" are based on mass unless otherwise specified.
＜硬化性樹脂組成物の調製＞
表１および２に記載の材料と溶剤を容器に入れ、５０℃に加温しながら撹拌し、ついでそれぞれ樹脂およびカップリング剤を加えた。樹脂が溶解したことを確認したのちに、フィラー成分を加え十分に撹拌をおこなった。その後、３本ロールミルにて混練して硬化性樹脂組成物１～４を調整した。
<Preparation of curable resin composition>
The materials and solvents listed in Tables 1 and 2 were placed in a vessel, stirred while warming to 50°C, and then the resin and coupling agent were added respectively. After confirming that the resin had dissolved, the filler component was added and sufficiently stirred. Then,
＜ドライフィルムの作製＞
調整した硬化性樹脂組成物を、粘度０．５～２０ｄＰａ・ｓ（回転粘度計５ｒｐｍ、２５℃）になるように溶剤の量を調整して、ヒラノテクシード製スタンダードラボコーターを用い、樹脂層の膜厚が乾燥後４０μｍになるようにキャリアフィルム（ＰＥＴフィルム；東洋紡社製ＴＮ－１００，厚さ３８μｍ）に塗布し、次いで、８０℃～１００℃に温度勾配のついた乾燥炉にて樹脂層の残留溶剤が０．５～２．５質量％となるように乾燥し、キャリアフィルム上に樹脂層を形成した。ついで、作製したドライフィルムの表面に、ニップロール表面温度で１１０℃、圧力０．１ｋｇｆ／ｃｍ２に設定し、表中に記載の保護フィルム（王子エフテックス社製ＯＰＰフィルムＭＡ－４１１、フタムラ化学社製自己粘着ＯＰＰフィルム１００Ｍ、または日東シンコー社製耐熱性微粘着特殊ポリエステルフィルムＴ－ＡＰＮ１０）の張りあわせを行い、参考例１、実施例１～５および比較例１の三層構造のロール状ドライフィルムを１０００ｍ分作製した。
具体的には、粘着性を有しない保護フィルムＭＡ－４１１を用い、通常の張り合わせ温度条件で保護フィルムを硬化性樹脂組成物に張り合わせて比較例１を作製した。これに対し、同じ粘着性を有しない保護フィルムＭＡ－４１１を用い、保護フィルムの張り合わせ温度を通常の張り合わせ温度条件より高めて参考例１を作製し、さらに、粘着性を有しない保護フィルムＭＡ－４１１の代わりに粘着性を有する保護フィルム１００ＭおよびＴ－ＡＰＮ１０を用いて実施例１～５を作製した。
<Preparation of dry film>
Adjust the amount of solvent so that the adjusted curable resin composition has a viscosity of 0.5 to 20 dPa s (rotational viscometer 5 rpm, 25 ° C.). It is applied to a carrier film (PET film; TN-100 manufactured by Toyobo Co., Ltd., thickness 38 μm) so that the thickness becomes 40 μm after drying, and then the resin layer is dried in a drying furnace with a temperature gradient of 80 ° C. to 100 ° C. It was dried so that the residual solvent was 0.5 to 2.5% by mass, and a resin layer was formed on the carrier film. Then, on the surface of the prepared dry film, the nip roll surface temperature was set to 110 ° C. and the pressure was set to 0.1 kgf / cm 2 , and the protective film described in the table (OPP film MA-411 manufactured by Oji F-Tex Co., Ltd., Futamura Chemical Co., Ltd. Self-adhesive OPP film 100M manufactured by Nitto Shinko Co., Ltd. or heat-resistant slightly adhesive special polyester film T-APN 10) manufactured by Nitto Shinko Co., Ltd.) is laminated, and the three-layer structure roll dry of Reference Example 1, Examples 1 to 5 and Comparative Example 1 A film of 1000 m was produced.
Specifically, Comparative Example 1 was prepared by laminating a protective film MA-411 having no adhesiveness to a curable resin composition under normal lamination temperature conditions. On the other hand, using the same non-adhesive protective film MA-411, Reference Example 1 was prepared by raising the lamination temperature of the protective film from the normal lamination temperature condition, and furthermore, the non-adhesive protective film MA- Examples 1-5 were prepared using protective film 100M and T-APN10 with adhesive instead of 411.
＜剥離強度の測定＞
得られた三層構造のドライフィルムについて、（Ａ）樹脂層に対するキャリアフィルムの剥離強度および（Ｂ）樹脂層に対する保護フィルムの剥離強度を測定した。得られたドライフィルムを厚み１．６ｍｍのＦＲ４上に接着剤を用い固定し、フィルムの表面に幅１０ｍｍ、長さ１５０ｍｍの切れ込みを入れ、フィルムの一端を引き剥がした。その後、フィルムの端部を掴みジグにて固定し、島津製作所製万能引張り試験機ＡＧ－Ｘにて、ピール強度の測定を実施した。実験方法は、ＪＩＳ－Ｃ－６４８１に準拠し、温度２５℃、引き剥がし角度９０°、速度５０ｍｍ／分にて測定を行った。測定結果を表３中に示す。
<Measurement of peel strength>
For the obtained dry film having a three-layer structure, (A) the peel strength of the carrier film to the resin layer and (B) the peel strength of the protective film to the resin layer were measured. The obtained dry film was fixed on FR4 having a thickness of 1.6 mm using an adhesive, and the surface of the film was cut with a width of 10 mm and a length of 150 mm, and one end of the film was peeled off. After that, the edge of the film was grabbed and fixed with a jig, and the peel strength was measured with a universal tensile tester AG-X manufactured by Shimadzu Corporation. The experimental method conformed to JIS-C-6481, and the measurement was performed at a temperature of 25°C, a peeling angle of 90°, and a speed of 50 mm/min. Table 3 shows the measurement results.
＜樹脂のハガレの評価＞
得られた三層構造のロール状ドライフィルムについて、オートカッター装置ＴＳ－３５０Ｐ（坂下鉄工社製）を用い、１０００ｍ分連続してスリット加工を実施した後、スリット面の樹脂端部の状態を評価した。評価基準は以下の通りとした。評価結果を表３中に示す。
〇：１０００ｍ加工後も樹脂端部に割れ、保護フィルムの剥離がなかった。
×：１０００ｍ加工後、樹脂端部に割れ、保護フィルムの剥離（３ｍｍ程度の浮き）が観察された。
<Evaluation of peeling of resin>
The resulting roll-shaped dry film with a three-layer structure was continuously slit for 1000 m using an auto cutter TS-350P (manufactured by Sakashita Tekko Co., Ltd.), and then the state of the resin edge on the slit surface was evaluated. bottom. The evaluation criteria were as follows. Evaluation results are shown in Table 3.
◯: Even after processing for 1000 m, the end of the resin was cracked and the protective film was not peeled off.
x: After 1,000 m of processing, cracks were observed at the resin ends, and peeling of the protective film (floating of about 3 mm) was observed.
＜樹脂組成物の転写（樹脂の泣き別れ）評価＞
作製した長尺の３層構造のドライフィルム（厚み４０ｕｍ、幅４９０ｍｍ、長さ１００ｍ分のロール製品）を、オートカットラミネータＨＬＭ－Ａ６０－Ｔ（日立化成社製）にセットし、巻き取りロールで保護フィルムを剥がした後、ラミネート速度１ｍ／ｍｉｎ、ロール温度で９０℃、ロール圧力０．２ＭＰａにて、サイズ５００×５００ｍｍ、厚み０．８ｍｍの銅張板に連続して２０枚仮張りテストを実施した。評価基準は以下の通りとした。評価結果を表３中に示す。
〇：保護フィルムの巻き取り、仮張り（熱圧着）部分までの間の、保護フィルムの巻き取りロール部分で樹脂層のハガレが確認されなかった。
×：保護フィルムの巻き取りロール部分で樹脂層のハガレが確認された。
<Evaluation of Transfer of Resin Composition (Farewell of Resin)>
The prepared long three-layer dry film (thickness 40 um, width 490 mm, length 100 m roll product) is set in an autocut laminator HLM-A60-T (manufactured by Hitachi Chemical Co., Ltd.), and a winding roll is used. After peeling off the protective film, at a lamination speed of 1 m / min, a roll temperature of 90 ° C., and a roll pressure of 0.2 MPa, 20 copper-clad plates with a size of 500 × 500 mm and a thickness of 0.8 mm were continuously subjected to a temporary adhesion test. carried out. The evaluation criteria were as follows. Evaluation results are shown in Table 3.
◯: No peeling of the resin layer was observed in the protective film winding roll portion between the protective film winding and temporary stretching (thermocompression bonding) portions.
x: Peeling of the resin layer was confirmed at the take-up roll portion of the protective film.
＊１：ＤＩＣ社製ＥＰＩＣＬＯＮ８４０（液状エポキシ樹脂、エポキシ当量１８５ｇ／ｅｑ）
＊２：ＤＩＣ社製ＥＰＩＣＬＯＮ８６０（ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量２４５ｇ／ｅｑ）
＊３：ＤＩＣ社製ＥＰＩＣＬＯＮ ＨＰ－５０００（ナフタレン骨格変性多官能エポキシ樹脂、エポキシ当量２５２ｇ／ｅｑ）
＊４：明和化成社製ＨＦ－１Ｍ、フェノールノボラック樹脂、水酸基当量１０６ｇ／ｅｑ
＊５：ＤＩＣ社製ＥＰＩＣＬＯＮＨＰＣ－８０００、活性エステル樹脂、活性当量２２３ｇ／ｅｑ、固形
＊６： ジメチルアミノピリジン
＊７：四国化成社製２Ｅ４ＭＺ、２－エチル－４－メチルイミダゾール
＊８：フェノキシ樹脂、
＊９：アドマテックス社製ＳＯ－Ｃ１、球状シリカ、平均粒子径（Ｄ５０）＝２００ｎｍ
＊１０：ビスフェノールＦ型アクリレート樹脂、日本化薬社製
＊１１：ＤＩＣ社製：アミドイミド構造を有するカルボキシル基含有樹脂
＊１２：トリシクロ［５．２．１．０ ２，６］デカンジメタノールジアクリレート、新中村化学社製
＊１３：三菱ケミカル社製ｊＥＲ８２８、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１８９ｇ／ｅｑ、液状
＊１４：ＤＩＣ社製、ジシクロペンタジエン型
＊１５：ＩＧＭ Ｒｅｓｉｎｓ Ｂ．Ｖ．製Ｏｍｎｉｒａｄ ３６９、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン
＊１６：硫酸バリウム、堺化学社製
*1: EPICLON840 manufactured by DIC (liquid epoxy resin, epoxy equivalent 185 g/eq)
*2: EPICLON860 manufactured by DIC (bisphenol A type solid epoxy resin, epoxy equivalent 245 g/eq)
*3: EPICLON HP-5000 manufactured by DIC (naphthalene skeleton-modified polyfunctional epoxy resin, epoxy equivalent 252 g/eq)
* 4: HF-1M manufactured by Meiwa Kasei Co., Ltd., phenol novolac resin, hydroxyl equivalent 106 g / eq
*5: EPICLONHPC-8000 manufactured by DIC, active ester resin, active equivalent 223 g/eq, solid *6: Dimethylaminopyridine *7: 2E4MZ manufactured by Shikoku Kasei Co., Ltd., 2-ethyl-4-methylimidazole *8: Phenoxy resin,
*9: Admatechs SO-C1, spherical silica, average particle size (D 50 ) = 200 nm
*10: Bisphenol F-type acrylate resin, manufactured by Nippon Kayaku *11: manufactured by DIC: carboxyl group-containing resin having an amide imide structure *12: tricyclo[5.2.1.0 2,6] decanedimethanol diacrylate , manufactured by Shin-Nakamura Chemical Co., Ltd. *13: jER828 manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 189 g/eq, liquid *14: manufactured by DIC, dicyclopentadiene type *15: IGM Resins B.I. V. Omnirad 369, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one *16: barium sulfate, manufactured by Sakai Chemical Co., Ltd.
上記表に示す結果から、本発明によれば、連続してスリット加工をしても、刃に樹脂が付着して切れ味が悪くなることがなく、結果として端部における樹脂の割れや浮き、保護フィルムの浮きが発生しないドライフィルムが得られることが分かる。 From the results shown in the above table, according to the present invention, even if slitting is continuously performed, the sharpness is not deteriorated due to the resin adhering to the blade, and as a result, the resin cracks, floats, and protects the edge. It can be seen that a dry film in which film floating does not occur can be obtained.
１１ 三層構造のドライフィルム
１２ 樹脂層
１３ キャリアフィルム
１４ 保護フィルム
11 dry film with three-layer structure 12
Claims (5)
前記樹脂層に対する前記保護フィルムの剥離強度が０．０１０ｋｇｆ／ｃｍ以上０．１５０ｋｇｆ／ｃｍ以下であることを特徴とするドライフィルム。 A dry film comprising a carrier film, a resin layer made of a curable resin composition, and a protective film having adhesiveness,
A dry film, wherein the peel strength of the protective film to the resin layer is 0.010 kgf/cm or more and 0.150 kgf/cm or less.
An electronic component comprising the cured product according to claim 4 .
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