JP2021138944A - Adhesive film, laminate with adhesive film including the same, and metallic foil laminate including the same - Google Patents

Adhesive film, laminate with adhesive film including the same, and metallic foil laminate including the same Download PDF

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JP2021138944A
JP2021138944A JP2021032113A JP2021032113A JP2021138944A JP 2021138944 A JP2021138944 A JP 2021138944A JP 2021032113 A JP2021032113 A JP 2021032113A JP 2021032113 A JP2021032113 A JP 2021032113A JP 2021138944 A JP2021138944 A JP 2021138944A
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adhesive film
resin
parts
curing
weight
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JP7164645B2 (en
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ソン・グン・キム
Seong Geun Kim
ジャミン・ク
Jeong-Min Kweon
ソン・チュ・ユ
Sung Ju Yoo
チョン・ミン・クォン
Jeong Min Kweon
ヒョン・ギュ・パク
Hyun Gyu Park
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Innox Advanced Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Abstract

To provide an adhesive film which is low in a dielectric constant, a dielectric loss, and moisture absorptivity.SOLUTION: There are provided an adhesive film that is formed of a composition for an adhesive film containing a binder resin, an epoxy resin and a filler, in which the binder resin contains a carboxylic acid-modified olefinic resin and a polyphenylene ether-based resin, the adhesive film after curing has a dielectric constant (Dk) measured at 1 GHz to 10 GHz and 20°C to 80°C of 2.6 or less and a dielectric loss (Df) of 0.005 or less, and the adhesive film after curing has moisture absorptivity of 0.1% or less; a laminate with an adhesive film including the same; and a metallic foil laminate including the same.SELECTED DRAWING: Figure 1

Description

本発明は、接着フィルム、これを含む接着フィルム付き積層体、及びこれを含む金属箔積層体に関する。より詳細に本発明は、広範囲な温度及び全周波数における誘電率及び誘電損失が低く、吸湿率が低くて、接着性と耐熱性に優れた接着フィルム、これを含む接着フィルム付き積層体、及びこれを含む金属箔積層体に関する。 The present invention relates to an adhesive film, a laminate with an adhesive film containing the adhesive film, and a metal foil laminate containing the adhesive film. More specifically, the present invention relates to an adhesive film having a low dielectric constant and dielectric loss at a wide range of temperatures and all frequencies, a low moisture absorption rate, and excellent adhesiveness and heat resistance, a laminate with an adhesive film containing the same, and a laminate thereof. The present invention relates to a metal leaf laminate containing.

最近、電子製品の集積化、小型化、薄膜化、高密度化、高屈曲化の流れに伴い、より狭い空間でも内装が容易な印刷回路基板（ｐｒｉｎｔｅｄ ｃｉｒｃｕｉｔ ｂｏａｒｄ、ＰＣＢ）の必要性が増大してきた。特に最近、繰り返した屈曲性を有する軟性印刷回路基板（ｆｌｅｘｉｂｌｅ ｐｒｉｎｔｅｄ ｃｉｒｃｕｉｔ ｂｏａｒｄ、ＦＰＣＢ）が開発された。軟性印刷回路基板は、スマートフォン、携帯用モバイル電子機器などの技術の発展によって使用が急激に増加しつつ、需要が増えている。 Recently, with the trend of integration, miniaturization, thin film, high density, and high bending of electronic products, the need for printed circuit boards (PCBs) that can be easily installed even in a narrower space has increased. rice field. Particularly recently, flexible printed circuit boards (FPCBs) with repeated flexibility have been developed. Demand for flexible printed circuit boards is increasing while their use is rapidly increasing due to the development of technologies such as smartphones and portable mobile electronic devices.

通常、軟性回路基板は、基材フィルムとしてポリイミド樹脂などからなる基材フィルムに、金属箔として銅箔が積層されている。基材フィルムと金属箔は、接着フィルムによって互いに接着される。従来の接着フィルムとして、ポリイミド系接着剤、アクリロニトリルブタジエンラバー系接着剤などで形成されていた。しかし、ポリイミド系接着剤、アクリロニトリルブタジエンラバー系接着剤などでは、誘電率と吸湿率を低くするのに限界があった。 Usually, in a flexible circuit board, a copper foil as a metal foil is laminated on a base film made of a polyimide resin or the like as a base film. The base film and the metal leaf are adhered to each other by the adhesive film. As a conventional adhesive film, it has been formed of a polyimide-based adhesive, an acrylonitrile-butadiene rubber-based adhesive, or the like. However, with polyimide-based adhesives, acrylonitrile-butadiene rubber-based adhesives, and the like, there is a limit in reducing the dielectric constant and the moisture absorption rate.

本発明の背景技術は、韓国公開特許第２０１６−００８３２０４号などに開示されている。 The background technique of the present invention is disclosed in Korean Publication No. 2016-0083204 and the like.

本発明の目的は、誘電率、誘電損失及び吸湿率の低い接着フィルムを提供することである。 An object of the present invention is to provide an adhesive film having a low dielectric constant, a dielectric loss and a hygroscopicity.

本発明の他の目的は、接着力と耐熱性に優れた接着フィルムを提供することである。 Another object of the present invention is to provide an adhesive film having excellent adhesive strength and heat resistance.

本発明のさらに他の目的は、周波数変化及び温度変化による誘電率と誘電損失の変化率が低い接着フィルムを提供することである。 Still another object of the present invention is to provide an adhesive film having a low rate of change in dielectric constant and dielectric loss due to frequency change and temperature change.

本発明のさらに他の目的は、最低溶融粘度の低い接着フィルムを提供することである。 Yet another object of the present invention is to provide an adhesive film having a low minimum melt viscosity.

本発明のさらに他の目的は、抵抗が低く、イオンの移動が適正範囲を確保することのできる接着フィルムを提供することである。 Yet another object of the present invention is to provide an adhesive film having low resistance and capable of ensuring an appropriate range of ion movement.

本発明のさらに他の目的は、本発明の接着フィルムを備える接着フィルム付き積層体及び金属箔積層体を提供することである。 Still another object of the present invention is to provide a laminate with an adhesive film and a metal leaf laminate provided with the adhesive film of the present invention.

本発明の接着フィルムは、バインダー樹脂、エポキシ樹脂及びフィラーを含む組成物で形成され、前記バインダー樹脂は、カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂を含み、前記接着フィルムは、硬化後、１ＧＨｚ〜１０ＧＨｚ及び２０℃〜８０℃で測定された誘電率（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ、Ｄｋ）が２．６以下、誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ、Ｄｆ）が０．００５以下であり、前記接着フィルムは、硬化後の吸湿率が０．１％以下である。 The adhesive film of the present invention is formed of a composition containing a binder resin, an epoxy resin and a filler, the binder resin contains a carboxylic acid-modified olefin resin and a polyphenylene ether resin, and the adhesive film is 1 GHz after curing. The dielectric constant (Dk) measured at 10 GHz and 20 ° C. to 80 ° C. is 2.6 or less, the dielectric loss (Df) is 0.005 or less, and the adhesive film is after curing. The moisture absorption rate is 0.1% or less.

一具体例において、前記組成物は、硬化剤を含んでいなくてもよい。 In one embodiment, the composition may not contain a curing agent.

一具体例において、前記カルボン酸変性オレフィン系樹脂は、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、無数マレイン酸、無数イタコン酸、無数フマル酸のうち１種以上によって変性されたオレフィン系樹脂を含んでいてもよい。 In one specific example, the carboxylic acid-modified olefin resin is an olefin modified by one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, innumerable maleic acid, innumerable itaconic acid, and innumerable fumaric acid. It may contain a based resin.

一具体例において、前記カルボン酸変性オレフィン系樹脂は、酸価が０．５〜１．５ｍｇＣＨ3ＯＮａ／ｇであってもよい。 In one specific example, the carboxylic acid-modified olefin resin may have an acid value of 0.5 to 1.5 mgCH 3 ONa / g.

一具体例において、前記ポリフェニレンエーテル系樹脂と、前記カルボン酸変性オレフィン系樹脂とのガラス転移温度差は、１００℃〜２５０℃であってもよい。 In one specific example, the glass transition temperature difference between the polyphenylene ether-based resin and the carboxylic acid-modified olefin-based resin may be 100 ° C. to 250 ° C.

一具体例において、前記カルボン酸変性オレフィン系樹脂は、カルボン酸変性された線状ポリプロピレン系樹脂を含んでいてもよい。 In one specific example, the carboxylic acid-modified olefin-based resin may contain a carboxylic acid-modified linear polypropylene-based resin.

一具体例において、前記バインダー樹脂総和１００重量部のうち、前記カルボン酸変性オレフィン系樹脂は、４０重量部〜８０重量部、前記ポリフェニレンエーテル系樹脂は、２０重量部〜６０重量部で含まれていてもよい。 In one specific example, out of 100 parts by weight of the total binder resin, the carboxylic acid-modified olefin resin is contained in an amount of 40 parts by weight to 80 parts by weight, and the polyphenylene ether resin is contained in an amount of 20 parts by weight to 60 parts by weight. You may.

一具体例において、前記フィラーは、無機ナノシリカとフッ素樹脂フィラーとの混合物を含んでいてもよい。 In one specific example, the filler may contain a mixture of an inorganic nanosilica and a fluororesin filler.

一具体例において、前記バインダー樹脂１００重量部に対して、前記エポキシ樹脂を１重量部〜１０重量部、前記フィラーを５重量部〜４０重量部で含んでいてもよい。 In one specific example, the epoxy resin may be contained in an amount of 1 part to 10 parts by weight and the filler in an amount of 5 parts to 40 parts by weight with respect to 100 parts by weight of the binder resin.

一具体例において、前記接着フィルムは、同一周波数において、硬化後の誘電損失に対する硬化後の誘電率の比（硬化後の誘電率／硬化後の誘電損失）が６５０以上であってもよい。 In one specific example, the adhesive film may have a ratio of the dielectric constant after curing to the dielectric loss after curing (dielectric constant after curing / dielectric loss after curing) of 650 or more at the same frequency.

一具体例において、前記接着フィルムは、硬化後のガラス転移温度が６０℃〜８０℃であってもよい。 In one specific example, the adhesive film may have a glass transition temperature of 60 ° C. to 80 ° C. after curing.

本発明の接着フィルム付き積層体は、ポリイミド系樹脂フィルム及び前記ポリイミド系樹脂フィルムの少なくとも一面に備えられた本発明の接着フィルムを備える。 The laminate with an adhesive film of the present invention includes a polyimide resin film and an adhesive film of the present invention provided on at least one surface of the polyimide resin film.

本発明の金属箔積層体は、ポリイミド系樹脂フィルム、前記ポリイミド系樹脂フィルムの少なくとも一面に備えられた接着フィルム、及び前記接着フィルムの一面に備えられた金属箔を備え、前記接着フィルムは、前記ポリイミド系樹脂フィルムと前記金属箔との間に備えられ、前記接着フィルムは、本発明の接着フィルムを備える。 The metal foil laminate of the present invention includes a polyimide resin film, an adhesive film provided on at least one surface of the polyimide resin film, and a metal foil provided on one surface of the adhesive film. It is provided between the polyimide resin film and the metal foil, and the adhesive film includes the adhesive film of the present invention.

本発明は、誘電率、誘電損失及び吸湿率の低い接着フィルムを提供した。 The present invention provides an adhesive film having low dielectric constant, dielectric loss and moisture absorption.

本発明は、接着力と耐熱性に優れた接着フィルムを提供した。 The present invention provides an adhesive film having excellent adhesive strength and heat resistance.

本発明は、周波数変化及び温度変化による誘電率と誘電損失の変化率が低い接着フィルムを提供した。 The present invention provides an adhesive film having a low rate of change in dielectric constant and dielectric loss due to frequency change and temperature change.

本発明は、最低溶融粘度の低い接着フィルムを提供した。 The present invention provides an adhesive film having a low minimum melt viscosity.

本発明は、抵抗が低く、イオンの移動が適正範囲を確保することのできる接着フィルムを提供した。 The present invention provides an adhesive film having low resistance and capable of ensuring an appropriate range of ion movement.

本発明は、本発明の接着フィルムを備える接着フィルム付き積層体及び金属箔積層体を提供した。 The present invention provides a laminate with an adhesive film and a metal foil laminate provided with the adhesive film of the present invention.

本発明の一実施例の接着フィルム付き積層体の断面図。FIG. 3 is a cross-sectional view of a laminate with an adhesive film according to an embodiment of the present invention. 本発明の一実施例の金属箔積層体の断面図。FIG. 3 is a cross-sectional view of a metal leaf laminate according to an embodiment of the present invention. 実施例１、比較例１、比較例２の接着フィルムの周波数変化による誘電率と誘電損失を示した図面。図３における△は実施例１、◇は比較例１、□は比較例２の結果である。The drawing which showed the dielectric constant and the dielectric loss by the frequency change of the adhesive film of Example 1, Comparative Example 1, and Comparative Example 2. In FIG. 3, Δ is the result of Example 1, ◇ is the result of Comparative Example 1, and □ is the result of Comparative Example 2. 実施例１、比較例２の接着フィルムの温度変化による誘電率と誘電損失を示した図面。図４における○は実施例１、□は比較例２の結果である。The drawing which showed the dielectric constant and the dielectric loss by the temperature change of the adhesive film of Example 1 and Comparative Example 2. In FIG. 4, ◯ is the result of Example 1 and □ is the result of Comparative Example 2.

本発明を下記の実施例によって、本発明の属する技術分野における通常の知識を有する者が容易に実施することができるように詳説する。本発明は、複数の異なる形態に具現することができ、ここで説明する実施例に限定されるものではない。図面における本発明を明確に説明するために、説明と関係ない部分は省略しており、全明細書における同一又は類似の構成要素に対しては、同じ図面符号を付している。図面における各構成要素の長さ、厚さなどは、本発明を説明するために示されたものであり、本発明は、図面に記載の長さ、厚さなどに限定されるものではない。 The present invention will be described in detail by the following examples so that a person having ordinary knowledge in the technical field to which the present invention belongs can easily carry out the present invention. The present invention can be embodied in a plurality of different forms and is not limited to the examples described herein. In order to clearly explain the present invention in the drawings, parts unrelated to the description are omitted, and the same or similar components in the entire specification are designated by the same drawing reference numerals. The length, thickness, etc. of each component in the drawings are shown for the purpose of explaining the present invention, and the present invention is not limited to the length, thickness, etc. described in the drawings.

本明細書における数値範囲を記載する際、「Ｘ〜Ｙ」は、「Ｘ以上Ｙ以下（Ｘ≦かつ≦Ｙ）」を意味する。 When describing the numerical range in the present specification, “X to Y” means “X or more and Y or less (X ≦ and ≦ Y)”.

本発明の発明者は、バインダー樹脂、エポキシ樹脂及びフィラーを含む組成物で形成される接着フィルムにおいて、前記バインダー樹脂として、カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂を必ず含ませることにより、接着フィルムの硬化後の誘電率（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ、Ｄｋ）、誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ、Ｄｆ）及び吸湿率が著しく低くなることを確認したうえで本発明を完成した。 The inventor of the present invention adheres by always including a carboxylic acid-modified olefin resin and a polyphenylene ether resin as the binder resin in an adhesive film formed of a composition containing a binder resin, an epoxy resin and a filler. The present invention was completed after confirming that the dielectric constant (Dk), the dielectric loss (Df) and the moisture absorption rate after curing of the film were remarkably low.

本明細書における「誘電率」、「誘電損失」は、１ＧＨｚ〜１０ＧＨｚ及び２０℃〜８０℃で測定された値を意味する。好ましくは、誘電率及び誘電損失は、１０ＧＨｚ及び２５℃で測定された値である。 In the present specification, "dielectric constant" and "dielectric loss" mean values measured at 1 GHz to 10 GHz and 20 ° C to 80 ° C. Preferably, the dielectric constant and the dielectric loss are values measured at 10 GHz and 25 ° C.

下記に詳述するが、本発明の接着フィルムは、半硬化状態（Ｂステージ）である。 As described in detail below, the adhesive film of the present invention is in a semi-cured state (B stage).

本明細書で特に記述しない限り、「硬化後」における「硬化」は、接着フィルムを１５０℃〜１９０℃で４５分〜９０分間硬化させることを意味する。すなわち、例えば、「硬化後の誘電率」は、接着フィルムを上述した条件で硬化させた後に測定された誘電率を意味する。 Unless otherwise stated herein, "curing" in "after curing" means curing the adhesive film at 150 ° C. to 190 ° C. for 45 to 90 minutes. That is, for example, "dielectric constant after curing" means the dielectric constant measured after the adhesive film is cured under the above-mentioned conditions.

本発明の接着フィルムは、広範囲な周波数及び広範囲な温度範囲のいずれもでも、硬化後の誘電率及び誘電損失が低くて、下記に詳述する金属箔積層時、信頼性を高めることができる。 The adhesive film of the present invention has low dielectric constant and dielectric loss after curing in both a wide range of frequencies and a wide range of temperatures, and can improve reliability when laminating metal foils described in detail below.

一具体例において、接着フィルムは、硬化後の誘電率が２．６以下、例えば、０〜２．６であってもよい。上記範囲で、接着フィルムが付着する素子に対する静電気又は電気の移動を最小限にすることにより、接着フィルムに対する電気的影響を最小限にすることができる。 In one specific example, the adhesive film may have a dielectric constant of 2.6 or less after curing, for example, 0 to 2.6. Within the above range, the electrical influence on the adhesive film can be minimized by minimizing the movement of static electricity or electricity to the element to which the adhesive film adheres.

一具体例において、接着フィルムは、硬化後の誘電損失が０．００５以下、例えば、０．０００１〜０．００４９であってもよい。上記範囲で、接着フィルムが付着する素子に対する静電気又は電気の移動を最小限にすることにより、接着フィルムに対する電気的影響を最小限にすることができる。 In one specific example, the adhesive film may have a dielectric loss after curing of 0.005 or less, for example, 0.0001 to 0.0049. Within the above range, the electrical influence on the adhesive film can be minimized by minimizing the movement of static electricity or electricity to the element to which the adhesive film adheres.

本発明の接着フィルムは、上述した誘電率と誘電損失を確保しながらも、周波数変化及び温度変化による誘電率の変化率と誘電損失の変化率が低いことを特徴とする。その結果、広範囲な周波数内でも、均一な誘電率と誘電損失を確保することによって、実用可能性を高めることができ、広範囲な温度内でも、均一な誘電率と誘電損失を確保することによって、接着フィルムの温度変化による信頼性を確保するようにすることができる。 The adhesive film of the present invention is characterized in that the rate of change of the dielectric constant and the rate of change of the dielectric loss due to frequency change and temperature change are low while ensuring the above-mentioned dielectric constant and dielectric loss. As a result, practicality can be enhanced by ensuring uniform dielectric constant and dielectric loss even within a wide range of frequencies, and by ensuring uniform dielectric constant and dielectric loss even within a wide range of temperatures. It is possible to ensure the reliability due to the temperature change of the adhesive film.

一具体例において、接着フィルムは、下記式１の周波数変化量による誘電率の変化率が０．６％以下、例えば、０％〜０．６％であってもよく、下記式２の周波数変化量による誘電損失の変化率が０．０１％以下、例えば、０％〜０．０１％であってもよい。上記範囲で、上述した実用可能性と信頼性を確保することができる： In one specific example, the adhesive film may have a dielectric constant change rate of 0.6% or less due to the frequency change amount of the following formula 1, for example, 0% to 0.6%, and the frequency change of the following formula 2 The rate of change in dielectric loss depending on the amount may be 0.01% or less, for example, 0% to 0.01%. Within the above range, the above-mentioned practicality and reliability can be ensured:

［式１］
誘電率の変化率＝｜Ｄｋ（＠１０ＧＨｚ）−Ｄｋ（＠１ＧＨｚ）｜／｜１０−１｜×１００ [Equation 1]
Permittivity change rate = | Dk (@ 10GHz) -Dk (@ 1GHz) | / | 10-1 | × 100

（上記式１において、
Ｄｋ（＠１０ＧＨｚ）は、硬化後、接着フィルムの周波数１０ＧＨｚにおける誘電率、
Ｄｋ（＠１ＧＨｚ）は、硬化後、接着フィルムの周波数１ＧＨｚにおける誘電率） (In the above formula 1,
Dk (@ 10 GHz) is the dielectric constant of the adhesive film at a frequency of 10 GHz after curing.
Dk (@ 1 GHz) is the dielectric constant of the adhesive film at a frequency of 1 GHz after curing)

［式２］
誘電損失の変化率＝｜Ｄｆ（＠１０ＧＨｚ）−Ｄｆ（＠１ＧＨｚ）｜／｜１０−１｜×１００ [Equation 2]
Rate of change in dielectric loss = | Df (@ 10GHz) -Df (@ 1GHz) | / | 10-1 | × 100

（上記式２において、
Ｄｆ（＠１０ＧＨｚ）は、硬化後、接着フィルムの周波数１０ＧＨｚにおける誘電損失、
Ｄｆ（＠１ＧＨｚ）は、硬化後、接着フィルムの周波数１ＧＨｚにおける誘電損失） (In the above formula 2,
Df (@ 10 GHz) is the dielectric loss of the adhesive film at a frequency of 10 GHz after curing.
Df (@ 1 GHz) is the dielectric loss of the adhesive film at a frequency of 1 GHz after curing)

通常、接着フィルムの誘電率は、測定周波数が高くなるほど、その値が低くなり、接着フィルムの誘電損失は、測定周波数が高くなるほど、その値が増加するのが一般的である。本発明の接着フィルムは、上述した低い誘電率と誘電損失を確保しながらも、周波数変化における誘電率の変化率と誘電損失の変化率を低くすることにより、下記に詳述する積層体における実用可能性と信頼性を高めることができた。 Generally, the dielectric constant of the adhesive film decreases as the measurement frequency increases, and the dielectric loss of the adhesive film increases as the measurement frequency increases. The adhesive film of the present invention can be put into practical use in a laminate described in detail below by reducing the rate of change of the dielectric constant and the rate of change of the dielectric loss with frequency change while ensuring the above-mentioned low dielectric constant and dielectric loss. I was able to increase the possibility and reliability.

一具体例において、接着フィルムは、下記式３の温度変化量による誘電率の変化率が０．３％以下、例えば、０％〜０．３％であってもよく、下記式４の温度変化量による誘電損失の変化率が０．００２％以下、例えば、０％〜０．００１５％であってもよい。上記範囲で、上述した実用可能性と信頼性を確保することができる： In one specific example, the adhesive film may have a rate of change in dielectric constant of 0.3% or less due to the amount of temperature change in the following formula 3, for example, 0% to 0.3%, and the temperature change in the following formula 4 may occur. The rate of change in dielectric loss depending on the amount may be 0.002% or less, for example, 0% to 0.0015%. Within the above range, the above-mentioned practicality and reliability can be ensured:

［式３］
誘電率の変化率＝｜Ｄｋ（＠８０℃）−Ｄｋ（＠２０℃）｜／｜８０−２０｜×１００ [Equation 3]
Permittivity change rate = | Dk (@ 80 ° C) -Dk (@ 20 ° C) | / | 80-20 | × 100

（上記式３において、
Ｄｋ（＠８０℃）は、硬化後、接着フィルムの８０℃における誘電率、
Ｄｋ（＠２０℃）は、硬化後、接着フィルムの２０℃における誘電率） (In the above formula 3,
Dk (@ 80 ° C) is the dielectric constant of the adhesive film at 80 ° C after curing.
Dk (@ 20 ° C) is the dielectric constant of the adhesive film at 20 ° C after curing)

［式４］
誘電損失の変化率＝｜Ｄｆ（＠８０℃）−Ｄｆ（＠２０℃）｜／｜８０−２０｜×１００ [Equation 4]
Rate of change in dielectric loss = | Df (@ 80 ° C) -Df (@ 20 ° C) | / | 80-20 | × 100

（上記式４において、
Ｄｆ（＠８０℃）は、硬化後、接着フィルムの周波数８０℃における誘電損失、
Ｄｆ（＠２０℃）は、硬化後、接着フィルムの周波数２０℃における誘電損失） (In the above formula 4,
Df (@ 80 ° C) is the dielectric loss of the adhesive film at a frequency of 80 ° C after curing.
Df (@ 20 ° C) is the dielectric loss of the adhesive film at a frequency of 20 ° C after curing)

通常、接着フィルムの誘電率と誘電損失は、測定温度値が高くなるほど、その値が高くなるのが一般的である。本発明の接着フィルムは、上述した誘電率と誘電損失を確保しながらも、温度変化における誘電率の変化率と誘電損失の変化率を低くすることにより、下記に詳述する積層体における実用可能性と信頼性を高めることができた。 Generally, the higher the measured temperature value, the higher the dielectric constant and the dielectric loss of the adhesive film. The adhesive film of the present invention can be put into practical use in the laminate described in detail below by reducing the rate of change of the dielectric constant and the rate of change of the dielectric loss with respect to temperature while ensuring the above-mentioned dielectric constant and dielectric loss. I was able to improve the sex and reliability.

一実施例において、接着フィルムは、同一周波数において、硬化後の誘電損失に対する硬化後の誘電率の比（硬化後の誘電率／硬化後の誘電損失）が６５０以上、例えば、６５０〜１２００であってもよい。上記範囲で、接着フィルムを下記に詳述する積層体に適用する際、接着信頼性を高め、被着体間に接着性、電気特性を改善することができる。 In one embodiment, the adhesive film has a ratio of the dielectric constant after curing (dielectric constant after curing / dielectric loss after curing) of 650 or more, for example, 650 to 1200, at the same frequency. You may. Within the above range, when the adhesive film is applied to the laminate described in detail below, the adhesive reliability can be improved, and the adhesiveness and electrical characteristics between the adherends can be improved.

本明細書における「吸湿率」は、接着フィルムに対して、ＩＰＣ−ＴＭ−６５０ ２．６．２．１によって、２５℃で２４時間浸水（ｉｍｍｅｒｓｉｏｎ）させて測定された値を意味する。通常、基材フィルムと金属箔を接着させる接着フィルムにおいて、透湿度が測定される。透湿度は、当業者に知られたように、高温高湿の条件で接着フィルムを放置した後、接着フィルムを通る水分の度合いを測定したものである。他方、本発明の接着フィルムは、接着フィルムを完全に浸水した状態で測定された吸湿率を著しく低くしたことを特徴とする。 As used herein, the "moisture absorption rate" means a value measured by immersing an adhesive film in water at 25 ° C. for 24 hours with IPC-TM-650 2.6.2.1. Usually, the moisture permeability is measured in an adhesive film that adheres a base film and a metal foil. As is known to those skilled in the art, the moisture permeability is a measurement of the degree of moisture passing through the adhesive film after the adhesive film is left to stand under high temperature and high humidity conditions. On the other hand, the adhesive film of the present invention is characterized in that the hygroscopicity measured in a state where the adhesive film is completely submerged is significantly reduced.

一具体例において、接着フィルムは、硬化後の吸湿率が０．１％以下、例えば、０．０１％〜０．０６％であってもよい。上記範囲における部品実装時、大気中から材料内へ流入した水分による悪影響を減らして、各材料間の接着性や電気特性に問題が生じることを防ぐことができる。 In one specific example, the adhesive film may have a moisture absorption rate of 0.1% or less after curing, for example, 0.01% to 0.06%. When mounting components in the above range, it is possible to reduce the adverse effects of moisture flowing into the material from the atmosphere and prevent problems in the adhesiveness and electrical characteristics between the materials.

接着フィルムは、上述した範囲で誘電率、誘電損失及び吸湿率を同時に満たすことができる。よって、接着フィルムを下記に詳述する金属箔積層体に適用する際、接着信頼性を高めて、被着体間に接着性、電気特性を改善することができる。例えば、接着フィルムは、金属箔積層体のように、基材フィルムと金属箔を接着させる用途に使用することができる。これについては、下記に詳述する。 The adhesive film can simultaneously satisfy the dielectric constant, the dielectric loss and the moisture absorption in the above range. Therefore, when the adhesive film is applied to the metal foil laminate described in detail below, the adhesive reliability can be improved and the adhesiveness and electrical characteristics between the adherends can be improved. For example, the adhesive film can be used for bonding a base film and a metal foil, such as a metal foil laminate. This will be described in detail below.

本発明の接着フィルムは、上述した電気特性、バリアー特性のほかも、柔軟性を確保することによって、下記に詳述する積層体における基材フィルムと金属板の接着に使用され、特に、軟性印刷回路基板の製造を容易にすることができる。 The adhesive film of the present invention is used for adhering a base film and a metal plate in a laminate described in detail below by ensuring flexibility in addition to the above-mentioned electrical properties and barrier properties, and in particular, flexible printing. The production of the circuit board can be facilitated.

本発明の接着フィルムは、下記に詳述する金属箔積層体に適用されるほど、基材フィルム、例えば、ポリイミドフィルムと金属箔、例えば、銅板に対する剥離強度（ｐｅｅｌ ｓｔｒｅｎｇｔｈ）に優れ、接着信頼性にも優れる。 The adhesive film of the present invention has excellent peel strength against a base film, for example, a polyimide film and a metal foil, for example, a copper plate, and has adhesive reliability so as to be applied to a metal foil laminate described in detail below. Also excellent.

一具体例において、接着フィルムは、ポリイミドフィルム、接着フィルム、ポリイミドフィルムが順次に積層された積層体に対して測定された硬化後の剥離強度が１．０Ｋｇｆ／ｃｍ以上であってもよい。上記範囲で、接着フィルムを下記に詳述する積層体に適用する際、接着信頼性を高めることができる。例えば、前記剥離強度は、１．５Ｋｇｆ／ｃｍ〜３．０Ｋｇｆ／ｃｍであってもよい。 In one specific example, the adhesive film may have a peel strength after curing of 1.0 Kgf / cm or more measured for a laminate in which a polyimide film, an adhesive film, and a polyimide film are sequentially laminated. Within the above range, when the adhesive film is applied to the laminate described in detail below, the adhesive reliability can be improved. For example, the peel strength may be 1.5 Kgf / cm to 3.0 Kgf / cm.

他の具体例において、接着フィルムは、ポリイミドフィルム、接着フィルム、金属箔が順次に積層された積層体に対して測定された硬化後の剥離強度が１．０Ｋｇｆ／ｃｍ以上であってもよい。上記範囲で、接着フィルムを下記に詳述する積層体に適用する際、接着信頼性を高めることができる。例えば、前記剥離強度は、１．５Ｋｇｆ／ｃｍ〜３．０Ｋｇｆ／ｃｍであってもよい。本明細書における「剥離強度」は、ＩＰＣ−ＴＭ−６５０ ２．４．８Ｃ基準に従って測定された値を意味する。 In another specific example, the adhesive film may have a peel strength after curing of 1.0 Kgf / cm or more measured with respect to a laminate in which a polyimide film, an adhesive film, and a metal foil are sequentially laminated. Within the above range, when the adhesive film is applied to the laminate described in detail below, the adhesive reliability can be improved. For example, the peel strength may be 1.5 Kgf / cm to 3.0 Kgf / cm. "Peeling strength" as used herein means a value measured according to the IPC-TM-650 2.4.8C standard.

接着フィルムは、硬化後のガラス転移温度が６０℃〜８０℃、例えば、６０℃〜７０℃であってもよい。上記範囲で、優れた耐屈曲性効果があり得る。 The adhesive film may have a glass transition temperature of 60 ° C. to 80 ° C. after curing, for example, 60 ° C. to 70 ° C. Within the above range, there may be an excellent bending resistance effect.

接着フィルムは、下記式５による質量損失比率が５％起こる温度が３００℃〜５００℃、例えば、３５０℃〜４５０℃であってもよい。上記範囲で、接着フィルムは、耐熱性に優れ、下記に詳述する積層体に使用することができる。 The adhesive film may have a temperature at which a mass loss ratio of 5% according to the following formula 5 occurs at 300 ° C. to 500 ° C., for example, 350 ° C. to 450 ° C. Within the above range, the adhesive film has excellent heat resistance and can be used for the laminate described in detail below.

［式５］
質量損失比率＝｜硬化後、接着フィルムの加温後の質量−硬化後、接着フィルムの最初質量｜／硬化後、接着フィルムの最初質量×１００ [Equation 5]
Mass loss ratio = | Mass after curing and heating of adhesive film-Initial mass of adhesive film after curing | / Initial mass of adhesive film after curing x 100

前記質量損失比率が５％起こる温度は、ＴＧＡ（ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ ａｎａｌｙｓｉｓ）によって測定することができる。具体的には、接着フィルムの最初質量１０ｍｇに対して、最初温度２５℃で始めて、昇温速度１０℃／分の速度に加温させて測定することができる。 The temperature at which the mass loss ratio occurs at 5% can be measured by TGA (thermogravimetric analysis). Specifically, the initial mass of the adhesive film is 10 mg, and the temperature can be measured by starting at an initial temperature of 25 ° C. and heating to a heating rate of 10 ° C./min.

接着フィルムは、硬化後の表面抵抗（ｓｕｒｆａｃｅ ｒｅｓｉｓｔｉｖｉｔｙ）が１×１０9〜１０×１０9ＭΩ、例えば、２×１０9〜１０×１０9ＭΩであってもよい。接着フィルムは、硬化後の体積抵抗（ｖｏｌｕｍｅ ｒｅｓｉｓｔｉｖｉｔｙ）が１×１０9〜１０×１０9ＭΩ・ｃｍ)、例えば、２×１０9〜１０×１０9ＭΩ・ｃｍであってもよい。上記範囲で、良好な絶縁効果があり得る。本明細書における表面抵抗、体積抵抗は、それぞれＩＰＣ−ＴＭ−６５０ ２．５．１７．１によって測定することができる。 The adhesive film may have a surface resistivity of 1 × 10 9 to 10 × 10 9 MΩ after curing, for example, 2 × 10 9 to 10 × 10 9 MΩ. The adhesive film may have a volume resistivity of 1 × 10 9 to 10 × 10 9 MΩ · cm after curing, for example, 2 × 10 9 to 10 × 10 9 MΩ · cm. Within the above range, a good insulating effect can be obtained. The surface resistance and volume resistance in the present specification can be measured by IPC-TM-650 2.5.17.1.

接着フィルムは、厚さが５μｍ〜５０μｍであってもよい。上記範囲で、下記に詳述する積層体に使用することができる。 The adhesive film may have a thickness of 5 μm to 50 μm. Within the above range, it can be used for the laminate described in detail below.

接着フィルムは、８５℃、８５％相対湿度、１０００時間下で、５０Ｖの電圧印加時、イオンの移動（ｉｏｎ ｍｉｇｒａｔｉｏｎ）が１×１０13Ω以上であってもよい。上記範囲で、回路間の耐絶縁効果があり得る。 The adhesive film may have an ion migration of 1 × 10 13 Ω or more when a voltage of 50 V is applied at 85 ° C., 85% relative humidity, and 1000 hours. Within the above range, there may be an insulation resistance effect between circuits.

接着フィルムは、ポリイミドフィルム／硬化後の接着フィルム／ポリイミドフィルムにおける半田付け抵抗（ｓｏｌｄｅｒ ｒｅｓｉｓｔａｎｃｅ）が２６０〜２８８℃／１０秒であり、ポリイミドフィルム／硬化後の接着フィルム／金属箔における半田付け抵抗が２６０〜３００℃／１０秒であってもよい。上記範囲で、良好な耐熱性効果があり得る。半田付け抵抗は、ＩＰＣ−ＴＭ−６５０ ２．４．１３Ｆによって測定することができるが、これに制限されるものではない。 The adhesive film has a solder response of the polyimide film / the cured adhesive film / the polyimide film at 260 to 288 ° C./10 seconds, and the solder resistance of the polyimide film / the cured adhesive film / the metal foil. It may be 260 to 300 ° C./10 seconds. Within the above range, a good heat resistance effect can be obtained. Soldering resistance can be measured by IPC-TM-650 2.4.13F, but is not limited thereto.

本発明の接着フィルムは、下記に詳述する組成物によって具現することができる。以下では、本発明の組成物について説明する。 The adhesive film of the present invention can be embodied by the compositions detailed below. Hereinafter, the composition of the present invention will be described.

前記組成物は、バインダー樹脂、エポキシ樹脂及びフィラーを含み、前記バインダー樹脂は、カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂を含む。接着フィルム用組成物は、バインダー樹脂としてカルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル樹脂を必ず含まなければならない。カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂のうちいずれかでもないか、いずれかでも、下記に詳述する樹脂のほか、他の種類の樹脂に置換される場合、本発明の効果を十分に具現することができない。 The composition contains a binder resin, an epoxy resin and a filler, and the binder resin contains a carboxylic acid-modified olefin resin and a polyphenylene ether resin. The composition for an adhesive film must always contain a carboxylic acid-modified olefin resin and a polyphenylene ether resin as a binder resin. When either of the carboxylic acid-modified olefin resin and the polyphenylene ether resin is substituted with the resin described in detail below or another type of resin, the effect of the present invention can be sufficiently achieved. It cannot be realized.

一具体例において、バインダー樹脂は、カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂の２種樹脂のみからなってもよい。 In one specific example, the binder resin may consist of only two types of resins, a carboxylic acid-modified olefin resin and a polyphenylene ether resin.

本発明の組成物は、カルボン酸変性オレフィン系樹脂に含まれたカルボン酸基とエポキシ樹脂との間の反応によって接着フィルムを形成する。これによって、前記組成物は、硬化剤を含まない。 The composition of the present invention forms an adhesive film by the reaction between the carboxylic acid group contained in the carboxylic acid-modified olefin resin and the epoxy resin. As a result, the composition does not contain a curing agent.

カルボン酸変性オレフィン系樹脂は、前記組成物のうち一成分であって、接着フィルムの接着性と柔軟性及び電気特性を付与する。 The carboxylic acid-modified olefin resin is one component of the composition and imparts the adhesiveness, flexibility and electrical properties of the adhesive film.

カルボン酸変性オレフィン系樹脂は、カルボン酸変性、線状ポリオレフィン系樹脂を含んでいてもよい。このとき、線状は、直線状又は分岐状のポリオレフィン系樹脂を含んでいてもよく、好ましくは、直線状ポリオレフィン系樹脂を含んでいてもよい。一具体例において、オレフィン系樹脂は、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリブチレン系樹脂のうち１種以上を含んでいてもよい。好ましくは、オレフィン系樹脂は、ポリプロピレン系樹脂を含んでいてもよく、これは、上述したポリフェニレンエーテル系樹脂と共に含むとき、本発明の効果を容易に具現することができる。 The carboxylic acid-modified olefin-based resin may contain a carboxylic acid-modified, linear polyolefin-based resin. At this time, the linear shape may contain a linear or branched polyolefin-based resin, and preferably may contain a linear polyolefin-based resin. In one specific example, the olefin-based resin may contain one or more of a polyethylene-based resin, a polypropylene-based resin, and a polybutylene-based resin. Preferably, the olefin-based resin may contain a polypropylene-based resin, which can easily realize the effects of the present invention when included together with the above-mentioned polyphenylene ether-based resin.

カルボン酸変性オレフィン系樹脂は、所定の変性物質、例えば、不飽和カルボン酸又はその無水物によって変性されたポリオレフィン系樹脂を含んでいてもよい。不飽和カルボン酸又はその無水物は例えば、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、無数マレイン酸、無数イタコン酸、無数フマル酸のうち１種以上を含んでいてもよい。好ましくは、前記変性物質は、無水マレイン酸であってもよい。 The carboxylic acid-modified olefin-based resin may contain a polyolefin-based resin modified with a predetermined modified substance, for example, an unsaturated carboxylic acid or an anhydride thereof. The unsaturated carboxylic acid or its anhydride may contain, for example, one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, innumerable maleic acid, innumerable itaconic acid, and innumerable fumaric acid. Preferably, the modified substance may be maleic anhydride.

カルボン酸変性オレフィン系樹脂は、酸価が０．５〜１．５ｍｇＣＨ3ＯＮａ／ｇであってもよい。上記範囲で、良好な接着性、耐熱性を具現することができる。前記「酸価」は、ＡＳＴＭ Ｄ １６１３方法により測定することができる。 The carboxylic acid-modified olefin resin may have an acid value of 0.5 to 1.5 mg CH 3 ONa / g. Within the above range, good adhesiveness and heat resistance can be realized. The "acid value" can be measured by the ASTM D 1613 method.

カルボン酸変性オレフィン系樹脂は、ガラス転移温度が５℃〜１００℃、例えば、１０℃〜５０℃であってもよい。上記範囲で、良好な屈曲性を提供する効果があり得る。 The carboxylic acid-modified olefin resin may have a glass transition temperature of 5 ° C. to 100 ° C., for example, 10 ° C. to 50 ° C. Within the above range, it may have the effect of providing good flexibility.

カルボン酸変性オレフィン系樹脂は、バインダー樹脂総和１００重量部のうち、４０重量部〜８０重量部で含まれていてもよい。上記範囲で、本発明の誘電率と吸湿率に至ることができ、耐絶縁効果があり得る。好ましくは、カルボン酸変性オレフィン系樹脂は、バインダー樹脂総和１００重量部のうち、５０重量部〜８０重量部で含まれていてもよい。 The carboxylic acid-modified olefin resin may be contained in 40 parts by weight to 80 parts by weight out of 100 parts by weight of the total binder resin. Within the above range, the dielectric constant and the hygroscopicity of the present invention can be reached, and an insulation resistance effect can be obtained. Preferably, the carboxylic acid-modified olefin resin may be contained in 50 parts by weight to 80 parts by weight out of 100 parts by weight of the total binder resin.

ポリフェニレンエーテル系樹脂は、前記組成物のうち一成分であって、接着フィルムの接着性と柔軟性及び電気特性を付与する。 The polyphenylene ether-based resin is one component of the above composition and imparts the adhesiveness, flexibility and electrical properties of the adhesive film.

ポリフェニレンエーテル系樹脂は、非変性ポリフェニレンエーテル、変性ポリフェニレンエーテルのうち１種以上を含んでいてもよい。好ましくは、ポリフェニレンエーテル系樹脂は、非変性ポリフェニレンエーテルを含んでいてもよい。 The polyphenylene ether-based resin may contain one or more of a non-modified polyphenylene ether and a modified polyphenylene ether. Preferably, the polyphenylene ether-based resin may contain a non-modified polyphenylene ether.

ポリフェニレンエーテル系樹脂は、カルボン酸変性オレフィン系樹脂に比べ、ガラス転移温度が高い種類を使用することができる。これによって、本発明の効果を容易に具現することができる。ポリフェニレンエーテル系樹脂と、カルボン酸変性オレフィン系樹脂とのガラス転移温度差は、１００℃〜２５０℃、例えば、１００℃〜１５０℃であってもよい。ポリフェニレンエーテル系樹脂は、ガラス転移温度が１００℃超３００℃以下、例えば、１１０℃〜２００℃であってもよい。上記範囲で、優れた柔軟性効果があり得る。 As the polyphenylene ether-based resin, a type having a higher glass transition temperature than the carboxylic acid-modified olefin-based resin can be used. Thereby, the effect of the present invention can be easily realized. The glass transition temperature difference between the polyphenylene ether-based resin and the carboxylic acid-modified olefin-based resin may be 100 ° C. to 250 ° C., for example, 100 ° C. to 150 ° C. The polyphenylene ether-based resin may have a glass transition temperature of more than 100 ° C. and 300 ° C. or lower, for example, 110 ° C. to 200 ° C. Within the above range, there can be an excellent flexibility effect.

ポリフェニレンエーテル系樹脂は、バインダー樹脂総和１００重量部のうち、２０重量部〜６０重量部で含まれていてもよい。上記範囲で、本発明の誘電率と吸湿率に至ることができる。好ましくは、ポリフェニレンエーテル系樹脂は、バインダー樹脂総和１００重量部のうち、２０重量部〜５０重量部で含まれていてもよい。 The polyphenylene ether-based resin may be contained in 20 parts by weight to 60 parts by weight out of 100 parts by weight of the total binder resin. Within the above range, the dielectric constant and hygroscopicity of the present invention can be reached. Preferably, the polyphenylene ether-based resin may be contained in 20 parts by weight to 50 parts by weight out of 100 parts by weight of the total binder resin.

エポキシ樹脂は、上述したバインダー樹脂、特に、カルボン酸変性オレフィン系樹脂のカルボン酸基と反応して、接着性、耐熱性を高めることができる。 The epoxy resin can react with the above-mentioned binder resin, particularly the carboxylic acid group of the carboxylic acid-modified olefin resin, to improve the adhesiveness and heat resistance.

エポキシ樹脂は、バインダー樹脂の総和１００重量部に対して、１重量部〜１０重量部で含まれていてもよい。上記範囲で、本発明の誘電率と吸湿率に至ることができ、優れた接着力効果があり得る。 The epoxy resin may be contained in an amount of 1 part to 10 parts by weight with respect to 100 parts by weight of the total amount of the binder resin. Within the above range, the dielectric constant and the hygroscopicity of the present invention can be reached, and an excellent adhesive force effect can be obtained.

エポキシ樹脂は、２個以上のエポキシ基を有する当業者に知られた通常のエポキシ樹脂を含んでいてもよい。例えば、エポキシ樹脂は、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Ｓ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ゴム変性エポキシ樹脂、脂肪酸変性エポキシ樹脂、ウレタン変性エポキシ樹脂、低塩素型エポキシ樹脂、シラン変性エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、多官能性ノボラック型エポキシ樹脂、グリシジルエーテル系エポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビスフェノールＡノボラックエポキシ樹脂などを含んでいてもよいが、これらに制限されるものではない。好ましくは、エポキシ樹脂は、クレゾールノボラックエポキシ樹脂を含んでいてもよい。 The epoxy resin may contain ordinary epoxy resins known to those skilled in the art that have two or more epoxy groups. For example, the epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, rubber modified epoxy resin, fatty acid modified epoxy resin, urethane modified epoxy resin, low chlorine type epoxy resin. , Silane-modified epoxy resin, dicyclopentadiene type epoxy resin, polyfunctional novolac type epoxy resin, glycidyl ether type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, etc. may be contained. , Not limited to these. Preferably, the epoxy resin may include a cresol novolac epoxy resin.

一方、本発明の組成物は、硬化剤を含まない。本発明の接着フィルムは、エポキシ樹脂のエポキシ基と、上述したバインダー樹脂のうち、カルボン酸の反応のみによって接着フィルムを製造することにより、さらなる硬化剤を必要としない。 On the other hand, the composition of the present invention does not contain a curing agent. The adhesive film of the present invention does not require a further curing agent by producing the adhesive film only by the reaction of the epoxy group of the epoxy resin and the above-mentioned binder resin with a carboxylic acid.

これのために、エポキシ樹脂中のエポキシ基の総モル数に対する、バインダー樹脂中のカルボン酸基の総モル数の比は、１以上、例えば、１〜２であってもよい。上記範囲で、硬化剤なく、本発明の接着フィルムを具現することができる。 Therefore, the ratio of the total number of moles of carboxylic acid groups in the binder resin to the total number of moles of epoxy groups in the epoxy resin may be 1 or more, for example, 1 to 2. Within the above range, the adhesive film of the present invention can be realized without a curing agent.

フィラーは、無機フィラー、有機フィラーのうち１種以上を含んでいてもよい。好ましくは、フィラーは、無機フィラーと有機フィラーとの混合物を使用することができる。これによって、上述したバインダー樹脂、エポキシ樹脂と組み合わせ時、本発明の吸湿率、誘電率に容易に至ることができる。 The filler may contain one or more of an inorganic filler and an organic filler. Preferably, the filler can be a mixture of an inorganic filler and an organic filler. Thereby, when combined with the above-mentioned binder resin and epoxy resin, the hygroscopicity and dielectric constant of the present invention can be easily reached.

無機フィラーは、金属、非金属、金属酸化物、非金属酸化物のうち１種以上を含んでいてもよい。例えば、無機フィラーは、シリカ、チタニア、アルミナ、酸化亜鉛、銅、銀のうち１種以上を含んでいてもよい。好ましくは、無機フィラーは、シリカ例えば、無機ナノシリカを含んでいてもよい。無機フィラーは、平均粒径（Ｄ５０）が５ｎｍ〜１０００ｎｍ、好ましくは、１０ｎｍ〜１００ｎｍであってもよい。上記範囲で、安定した体積変化率効果があり得る。 The inorganic filler may contain one or more of metal, non-metal, metal oxide, and non-metal oxide. For example, the inorganic filler may contain one or more of silica, titania, alumina, zinc oxide, copper, and silver. Preferably, the inorganic filler may contain silica, eg, inorganic nanosilica. The inorganic filler may have an average particle size (D50) of 5 nm to 1000 nm, preferably 10 nm to 100 nm. Within the above range, there can be a stable volume change rate effect.

有機フィラーは、フッ素樹脂フィラーを含んでいてもよい。フッ素樹脂フィラーは、例えば、ポリテトラフルオロエチレンフィラー、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体フィラー、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体フィラー、テトラフルオロエチレン−エチレン共重合体フィラー、ポリクロロトリフルオロエチレンフィラーのうち１種以上を含んでいてもよい。好ましくは、有機フィラーは、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体フィラーを含んでいてもよい。有機フィラーは、平均粒径（Ｄ５０）が１〜１００μｍ、好ましくは、５〜５０μｍであってもよい。上記範囲で、良好な低誘電効果があり得る。 The organic filler may contain a fluororesin filler. Fluororesin fillers include, for example, polytetrafluoroethylene filler, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer filler, tetrafluoroethylene-hexafluoropropylene copolymer filler, tetrafluoroethylene-ethylene copolymer filler, and polychloro. It may contain one or more of the trifluoroethylene fillers. Preferably, the organic filler may include a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer filler. The organic filler may have an average particle size (D50) of 1 to 100 μm, preferably 5 to 50 μm. Within the above range, a good low dielectric effect can be achieved.

無機フィラーと有機フィラーは、本発明の接着剤組成物のうち特定の含量比率で含まれていてもよい。例えば、無機フィラー１００重量部に対して、有機フィラーは、１００重量部〜６００重量部で含まれていてもよい。上記範囲で、低誘電率及び耐熱性を改善する効果があり得る。 The inorganic filler and the organic filler may be contained in a specific content ratio in the adhesive composition of the present invention. For example, the organic filler may be contained in an amount of 100 parts by weight to 600 parts by weight with respect to 100 parts by weight of the inorganic filler. Within the above range, there may be an effect of improving low dielectric constant and heat resistance.

フィラーは、バインダー樹脂１００重量部に対して、５重量部〜４０重量部で含まれていてもよい。上記範囲で、良好な耐熱性と誘電率値が低くなり得る。 The filler may be contained in an amount of 5 to 40 parts by weight with respect to 100 parts by weight of the binder resin. In the above range, good heat resistance and dielectric constant value can be low.

本発明の組成物は、 必要に応じてか焼剤、レベリング剤、紫外線吸収剤、難燃剤などの添加剤、増粘剤のうち１種以上をさらに含んでいてもよいが、これらに制限されるものではない。 The composition of the present invention may further contain one or more of an additive such as a calcination agent, a leveling agent, an ultraviolet absorber, a flame retardant, and a thickener, if necessary, but is limited thereto. It's not something.

本発明の組成物は、溶剤をさらに含むことにより、接着フィルムの塗布性を高めることができる。前記溶剤は、ジメチルホルムアミド、メチルエチルケトン、ジメチルアセトアミドのうち１種以上を含んでいてもよいが、これに制限されるものではない。 The composition of the present invention can enhance the coatability of the adhesive film by further containing a solvent. The solvent may contain, but is not limited to, one or more of dimethylformamide, methylethylketone, and dimethylacetamide.

接着フィルムは、上述した組成物を基材フィルム又は離型フィルムに所定の厚さに塗布し、乾燥及び熱処理することにより、半分硬化状態に製造することができる。例えば、接着フィルムは、５０℃〜１８０℃で１分〜１０分間熱処理することにより、半硬化状態に製造することができる。 The adhesive film can be produced in a semi-cured state by applying the above-mentioned composition to a base film or a release film to a predetermined thickness, drying and heat-treating. For example, the adhesive film can be produced in a semi-cured state by heat-treating at 50 ° C. to 180 ° C. for 1 minute to 10 minutes.

以下では、本発明の一実施例の接着フィルム付き積層体を説明する。 Hereinafter, a laminate with an adhesive film according to an embodiment of the present invention will be described.

本発明の接着フィルム付き積層体は、基材フィルム、基材フィルムの少なくとも一面に備えられた接着フィルムを備え、前記接着フィルムは、本発明の接着フィルムを含む。本発明の接着フィルム付き積層体は、カバーレイフィルムを含んでいてもよいが、これに制限されるものではない。 The laminate with an adhesive film of the present invention includes a base film and an adhesive film provided on at least one surface of the base film, and the adhesive film includes the adhesive film of the present invention. The laminate with an adhesive film of the present invention may include, but is not limited to, a coverlay film.

図１を参照すれば、接着フィルム付き積層体は、基材フィルム１０、基材フィルム１０の一面に備えられた第１の接着フィルム２０及び基材フィルム１０の他の一面に備えられた第２の接着フィルム３０を備え、第１の接着フィルム２０、第２の接着フィルム３０のうち１種以上は、本発明の接着フィルムを含んでいてもよい。 Referring to FIG. 1, the laminate with the adhesive film is provided on the base film 10, the first adhesive film 20 provided on one side of the base film 10, and the second provided on the other side of the base film 10. The adhesive film 30 of the above is provided, and one or more of the first adhesive film 20 and the second adhesive film 30 may contain the adhesive film of the present invention.

基材フィルム１０は、ポリイミド樹脂で形成されたフィルムを含む。ポリイミド樹脂は、高耐熱性を提供する樹脂であって、接着フィルム付き積層体をカバーレイフィルムの用途に使用するのに好適であるようにすることができる。基材フィルム１０の厚さは、５μｍ〜１００μｍ、好ましくは、５μｍ〜７５μｍであってもよい。上記範囲で、カバーレイフィルムの基材フィルムとして使用することができ、軟性と剛性をいずれも具現することができる。 The base film 10 includes a film made of a polyimide resin. The polyimide resin is a resin that provides high heat resistance, and can make a laminate with an adhesive film suitable for use in a coverlay film application. The thickness of the base film 10 may be 5 μm to 100 μm, preferably 5 μm to 75 μm. Within the above range, it can be used as a base film for a coverlay film, and both softness and rigidity can be realized.

第１の接着フィルム２０、第２の接着フィルム３０は、それぞれ上述した本発明の接着フィルムであってもよく、第１の接着フィルム２０、第２の接着フィルム３０のうちいずれかのみ本発明の接着フィルムであってもよい。第１の接着フィルム２０、第２の接着フィルム３０は、半硬化状態、すなわち、Ｂステージ状態の接着フィルムであってもよい。 The first adhesive film 20 and the second adhesive film 30 may be the adhesive films of the present invention described above, respectively, and only one of the first adhesive film 20 and the second adhesive film 30 of the present invention may be used. It may be an adhesive film. The first adhesive film 20 and the second adhesive film 30 may be adhesive films in a semi-cured state, that is, in a B stage state.

第１の接着フィルム２０、第２の接着フィルム３０は、互いに厚さが同一であるか相違してもよく、例えば、上述した本発明の接着フィルムの厚さ範囲であってもよい。 The first adhesive film 20 and the second adhesive film 30 may have the same or different thicknesses from each other, and may be, for example, in the thickness range of the adhesive film of the present invention described above.

以下では、本発明の一実施例の金属箔積層体を説明する。 Hereinafter, the metal leaf laminate according to an embodiment of the present invention will be described.

本発明の金属箔積層体は、基材フィルム、基材フィルムの少なくとも一面に備えられた接着フィルム、及び前記接着フィルムの一面に備えられた金属箔を備え、前記接着フィルムは、本発明の接着フィルムを含む。本発明の金属箔積層体は、印刷回路基板、例えば、軟性回路基板を含んでいてもよい。 The metal foil laminate of the present invention includes a base film, an adhesive film provided on at least one surface of the base film, and a metal foil provided on one surface of the adhesive film, and the adhesive film is the adhesive of the present invention. Includes film. The metal foil laminate of the present invention may include a printed circuit board, for example, a flexible circuit board.

図２を参照すれば、金属箔積層体は、基材フィルム１０、基材フィルム１０の一面に備えられた第１の接着フィルム２０、第１の接着フィルム２０の一面に備えられた第１の金属箔４０、基材フィルム１０の他の一面に備えられた第２の接着フィルム３０、第２の接着フィルム３０の一面に備えられた第２の金属箔５０、とを備えることができる。 Referring to FIG. 2, the metal leaf laminate is a base film 10, a first adhesive film 20 provided on one surface of the base film 10, and a first adhesive film 20 provided on one surface of the first adhesive film 20. The metal foil 40, the second adhesive film 30 provided on the other surface of the base film 10, and the second metal foil 50 provided on one surface of the second adhesive film 30 can be provided.

基材フィルム１０、第１の接着フィルム２０、第２の接着フィルム３０に関する説明は、上記図１で説明したとおりである。第１の金属箔４０、第２の金属箔５０は、銅箔、銀箔、アルミニウム箔、ステンレス箔のうち１種以上を含み、好ましくは、銅箔を含んでいてもよい。第１の金属箔４０、第２の金属箔５０は同様、銅箔であってもよく、いずれかは銅箔、他の一つは銅箔のほか、金属箔であってもよい。第１の金属箔４０、第２の金属箔５０それぞれの厚さは、同一であるか相違してもよく、例えば、１μｍ〜２００μｍ、例えば、３μｍ〜７０μｍであってもよい。 The description of the base film 10, the first adhesive film 20, and the second adhesive film 30 is as described in FIG. The first metal foil 40 and the second metal foil 50 include one or more of copper foil, silver foil, aluminum foil, and stainless steel foil, and preferably include copper foil. Similarly, the first metal foil 40 and the second metal foil 50 may be copper foils, one of which may be a copper foil, the other of which may be a copper foil, or a metal foil. The thickness of each of the first metal leaf 40 and the second metal leaf 50 may be the same or different, and may be, for example, 1 μm to 200 μm, for example, 3 μm to 70 μm.

以下では、実施例によって本発明をより具体的に説明するが、かかる実施例は、単に説明するための目的であり、本発明を制限するものに解釈してはならない。 Hereinafter, the present invention will be described in more detail by way of examples, but such examples are for purposes of explanation only and should not be construed as limiting the present invention.

実施例１
カルボン酸変性されたポリプロピレン系樹脂（ＳＭ０４０Ａ、東洋紡、酸価：１．０ｍｇＣＨ3ＯＮａ／ｇ）５５重量部、ポリフェニレンエーテル系樹脂（ＰＰＯ、サビック、−ＯＨ値：８００ｍｇＫＯＨ／ｇ）２０重量部を混合し、クレゾールノボラックエポキシ樹脂（ＹＤＣＮ１Ｐ、ｋｕｋｄｏ化学、ＥＥＷ：２００ｇ／ｅｑ）３重量部、無機ナノシリカ（Ｒ９７２、エボニック、平均粒径（Ｄ５０）：１７ｎｍ）６重量部、フッ素樹脂フィラー（ＰＦＡ、ＡＧＣ、平均粒径（Ｄ５０）：１０μｍ）１５重量部を混合し、溶剤メチルエチルケトン１５０重量部をさらに添加して、組成物を製造した。下記表１における「−」は、該成分が含まれていないことを意味する。 Example 1
A mixture of 55 parts by weight of a carboxylic acid-modified polypropylene resin (SM040A, Toyo Boseki, acid value: 1.0 mgCH 3 ONa / g) and 20 parts by weight of a polyphenylene ether resin (PPO, savic, -OH value: 800 mgKOH / g). However, 3 parts by weight of cresol novolac epoxy resin (YDCN1P, kukdo chemistry, EEW: 200 g / eq), 6 parts by weight of inorganic nanosilica (R972, ebonic, average particle size (D50): 17 nm), fluororesin filler (PFA, AGC, An average particle size (D50): 10 μm) was mixed with 15 parts by weight, and 150 parts by weight of the solvent methyl ethyl ketone was further added to prepare a composition. “-” In Table 1 below means that the component is not contained.

製造した組成物をポリイミドフィルムに所定の厚さでコーティングし、１３０℃で３分間乾燥及び熱処理して、半硬化状態の接着フィルム（厚さ：２５μｍ）を製造した。 The produced composition was coated on a polyimide film to a predetermined thickness, dried and heat-treated at 130 ° C. for 3 minutes to produce a semi-cured adhesive film (thickness: 25 μm).

実施例２〜実施例３
実施例１における各成分の含量を、下記表１のように変更したことを除いては、実施例１と同じ方法により半硬化状態の接着フィルムを製造した。 Example 2 to Example 3
An adhesive film in a semi-cured state was produced by the same method as in Example 1 except that the content of each component in Example 1 was changed as shown in Table 1 below.

比較例１
ポリフェニレンエーテル系樹脂（ＰＰＯ、サビック、−ＯＨ値：８００ｍｇＫＯＨ／ｇ）６重量部、 非ハロゲン系エポキシ樹脂として、ｐ−Ａｍｉｎｏ Ｐｈｅｎｏｌ型（ｊＥＲ６３０、 Ｍｉｔｓｕｂｉｓｈｉ Ｃｈｅｍｉｃａｌ、ＥＥＷ：１００ｇ／ｅｑ）４３重量部、ビフェニルエポキシ樹脂（ＮＣ３０００Ｈ、日本化薬、ＥＥＷ：２９０ｇ／ｅｑ）２１重量部、カルボン酸基含有のアクリロニトリルブタジエンゴム（Ｎｉｐｏｌ１０７２、日本ゼオン、−ＣＯＯＨ：８重量％）２１重量部、エポキシ樹脂用硬化剤として４、４−ジアミノジフェニルスルホン（ＤＤＳ、Ｓｉｇｍａ−Ａｌｄｒｉｃｈ、ＥＥＷ：６４ｇ／ｅｑ）９重量部、 硬化促進剤としてウンデシルイミダゾール（Ｃ１１Ｚ、四国化成）０．２重量部を混合し、溶剤メチルエチルケトン１３０重量部をさらに添加して、組成物を製造した。 Comparative Example 1
6 parts by weight of polyphenylene ether resin (PPO, Savik, -OH value: 800 mgKOH / g), 43 parts by weight of p-Amino Phenol type (jER630, Mitsubishi Chemical, EEW: 100 g / eq) as a non-halogen epoxy resin, biphenyl 21 parts by weight of epoxy resin (NC3000H, Nippon Kayaku, EEW: 290 g / eq), 21 parts by weight of acrylonitrile butadiene rubber containing carboxylic acid group (Nipol1072, Nippon Zeon, -COOH: 8% by weight), as a curing agent for epoxy resin 9 parts by weight of 4,4-diaminodiphenyl sulfone (DDS, Sigma-Aldrich, EEW: 64 g / eq) and 0.2 parts by weight of undecylimidazole (C11Z, Shikoku Kasei) as a curing accelerator are mixed, and 130 parts by weight of solvent methyl ethyl ketone is mixed. Parts were further added to produce a composition.

製造した組成物をポリイミドフィルムに所定の厚さでコーティングし、１３０℃で３分間乾燥及び熱処理して、半硬化状態の接着フィルム（厚さ：２５μｍ）を製造した。 The produced composition was coated on a polyimide film to a predetermined thickness, dried and heat-treated at 130 ° C. for 3 minutes to produce a semi-cured adhesive film (thickness: 25 μm).

比較例２
非ハロゲンエポキシ樹脂ｐ−Ａｍｉｎｏ Ｐｈｅｎｏｌ型（ｊＥＲ６３０、 Ｍｉｔｓｕｂｉｓｈｉ Ｃｈｅｍｉｃａｌ、ＥＥＷ：１００ｇ／ｅｑ）５重量部、 非ハロゲン変性ポリイミドアマイド（ＰＩＡＤ２００、アラカワ）６０重量部、非ハロゲン変性ポリイミドアマイド（ＰＩＡＤ１５０Ｌ、アラカワ）２５重量部、エステル変性硬化剤（ＨＰＣ−８１５０、ＤＩＣ）１０重量部、硬化促進剤として２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ、四国化成）０．０５重量部を混合し、溶剤メチルエチルケトン１３０重量部をさらに添加して、組成物を製造した。 Comparative Example 2
Non-halogen epoxy resin p-Amino Phenol type (jER630, Mitsubishi Chemical, EEW: 100 g / eq) 5 parts by weight, non-halogen modified polyimide amide (PIAD200, Arakawa) 60 parts by weight, non-halogen modified polyimide amide (PIAD150L, Arakawa) 25 A mixture of 10 parts by weight of an ester-modified curing agent (HPC-8150, DIC) and 0.05 parts by weight of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei) as a curing accelerator is mixed, and 130 parts by weight of solvent methylethylketone is mixed. Was further added to produce a composition.

製造した組成物をポリイミドフィルムに所定の厚さでコーティングし、１３０℃で３分間乾燥及び熱処理して、半硬化状態の接着フィルム（厚さ：２５μｍ）を製造した。 The produced composition was coated on a polyimide film to a predetermined thickness, dried and heat-treated at 130 ° C. for 3 minutes to produce a semi-cured adhesive film (thickness: 25 μm).

比較例３
カルボン酸変性スチレン系エラストマー（ＳＭ３００Ａ、東洋紡、酸価：１０ ｍｇＣＨ3ＯＮａ／ｇ）７重量部、ポリプロピレン系樹脂（ＪＳＳ−３９５Ｎ、酸価：０ｍｇＣＨ3ＯＮａ／ｇ、湖南石油化学）５５重量部、ポリフェニレンエーテル系樹脂（ＰＰＯ、−ＯＨ値：８００ｍｇＫＯＨ／ｇ、サビック）１４重量部、クレゾールノボラックエポキシ樹脂（ＹＤＣＮ１Ｐ、ＥＥＷ：２００ｇ／ｅｑ、ｋｕｋｄｏ化学）２重量部、無機ナノシリカ（Ｒ９７２、平均粒径（Ｄ５０）：１７ｎｍ、エボニック）４重量部、フッ素樹脂フィラー（ＰＦＡ、平均粒径（Ｄ５０）：１０μｍ、ＡＧＣ）１７重量部、硬化剤（ＤＤＳ、Ｓｉｇｍａ−Ａｌｄｒｉｃｈ）１重量部を混合し、溶剤メチルエチルケトン１２０重量部をさらに添加して、組成物を製造した。 Comparative Example 3
Carboxylic acid-modified styrene elastomer (SM300A, Toyo Boseki, acid value: 10 mgCH 3 ONa / g) 7 parts by weight, polypropylene resin (JSS-395N, acid value: 0 mgCH 3 ONa / g, Hunan Petrochemical) 55 parts by weight, Polyphenylene ether resin (PPO, -OH value: 800 mgKOH / g, Savik) 14 parts by weight, cresol novolac epoxy resin (YDCN1P, EEW: 200 g / eq, kukdo chemical) 2 parts by weight, inorganic nanosilica (R972, average particle size (R972, average particle size (R972)) D50): 17 nm, epoxy) 4 parts by weight, fluororesin filler (PFA, average particle size (D50): 10 μm, AGC) 17 parts by weight, curing agent (DDS, Sigma-Aldrich) 1 part by weight, solvent methyl ethyl ketone An additional 120 parts by weight was added to prepare the composition.

製造した組成物をポリイミドフィルムに所定の厚さでコーティングし、１３０℃で３分間乾燥及び熱処理して、半分硬化状態の接着フィルム（厚さ：２５μｍ）を製造した。 The produced composition was coated on a polyimide film to a predetermined thickness, dried and heat-treated at 130 ° C. for 3 minutes to produce a semi-cured adhesive film (thickness: 25 μm).

実施例と比較例の接着フィルムを１６０℃で６０分間熱処理して、完全硬化状態の接着フィルムを製造した。 The adhesive films of Examples and Comparative Examples were heat-treated at 160 ° C. for 60 minutes to produce a completely cured adhesive film.

硬化状態の接着フィルムに対して下記物性を評価し、その結果を下記表２、表３、図３及び図４に示した。 The following physical characteristics were evaluated for the cured adhesive film, and the results are shown in Tables 2, 3, 3 and 4 below.

（１）剥離強度（単位：Ｋｇｆ／ｃｍ）：剥離強度は、ＩＰＣ−ＴＭ−６５０ ２．４．８Ｃに従って評価した。ポリイミド（ＰＩ）フィルム／接着フィルム／ポリイミドフィルム、ポリイミドフィルム／接着フィルム／銅箔（Ｃｕ）に対して、２５℃、剥離角度１８０゜、剥離速度５０ｍｍ／ｍｉｎによって剥離強度を評価した。 (1) Peeling strength (unit: Kgf / cm): The peeling strength was evaluated according to IPC-TM-650 2.4.8C. The peel strength of the polyimide (PI) film / adhesive film / polyimide film and the polyimide film / adhesive film / copper foil (Cu) was evaluated at 25 ° C., a peeling angle of 180 °, and a peeling speed of 50 mm / min.

（２）半田付け抵抗（単位：℃／超）：半田付け抵抗は、ＩＰＣ−ＴＭ−６５０ ２．４．１３Ｆによって測定した。ポリイミド（ＰＩ）フィルム／接着フィルム／ポリイミド（ＰＩ）フィルム、ポリイミド（ＰＩ）フィルム／接着フィルム／銅箔（Ｃｕ）に対して、半田付け抵抗を測定した。 (2) Soldering resistance (unit: ° C./super): The soldering resistance was measured by IPC-TM-650 2.4.13F. The soldering resistance of the polyimide (PI) film / adhesive film / polyimide (PI) film and the polyimide (PI) film / adhesive film / copper foil (Cu) was measured.

（３）誘電率（単位：なし）と誘電損失（単位：なし）：接着フィルムに対して２５℃、周波数１０ＧＨｚ、 Ｎｅｔｗｏｒｋ Ａｎａｌｙｚｅｒ（ＭＳ４６４２Ｂ ３６５８５Ｋ、Ａｎｒｉｔｓｕ Ｃｏ．）を用いて、誘電率（Ｄｋ）と誘電損失（Ｄｆ）を評価した。 (3) Dielectric constant (unit: none) and dielectric loss (unit: none): With respect to the adhesive film, the dielectric constant (Dk) was determined by using a network analyzer (MS4642B 36585K, Anritsu Co.) at 25 ° C. and a frequency of 10 GHz. The dielectric loss (Df) was evaluated.

（４）熱膨脹係数（単位：ｐｐｍ／℃）：ＩＰＣ−ＴＭ−６５０ ２．４．４１．３によって、ＴＭＡ（ｔｈｅｒｍｏｍｅｃｈａｎｉｃａｌ ａｎａｌｙｚｅｒ）を用いてα１、α２を分析した。 (4) Thermal expansion coefficient (unit: ppm / ° C.): α1 and α2 were analyzed using TMA (thermomechanical analyzer) according to IPC-TM-650 2.4.41.3.

（５）ガラス転移温度（Ｔｇ、単位：℃）：接着フィルムに対して、ＤＭＡ（ｄｙｎａｍｉｃ ｍｅｃｈａｎｉｃａｌ ａｎａｌｙｚｅｒ）を用いて、ｔａｎδモジュラスが最大になる温度をガラス転移温度とした。 (5) Glass transition temperature (Tg, unit: ° C.): Using DMA (dynamic mechanical analysis) with respect to the adhesive film, the temperature at which the tan δ modulus was maximized was defined as the glass transition temperature.

（６）５％質量損失温度（単位：℃）：接着フィルムに対して、５％質量損失は、ＴＧＡ（ｔｈｅｒｍｏｇｒａｖｉｍｅｔｒｉｃ ａｎａｌｙｓｉｓ）によって分析した。 (6) 5% mass loss temperature (unit: ° C.): 5% mass loss was analyzed by TGA (thermogravimetric analysis) with respect to the adhesive film.

（７）表面抵抗と体積抵抗（各々の単位：ＭΩ、ＭΩ・ｃｍ）：接着フィルムに対して、表面抵抗と体積抵抗は、ＩＰＣ−ＴＭ−６５０ ２．５．１７に従って評価した。 (7) Surface resistance and volume resistance (each unit: MΩ, MΩ · cm): For the adhesive film, the surface resistance and volume resistance were evaluated according to IPC-TM-650 2.5.17.

（８）イオンの移動（ｉｏｎ−ｍｉｇｒａｔｉｏｎ、単位：Ω）：接着フィルムに対して、イオンの移動の特性は、８５℃／８５ＲＨ％／１０００時間、５０Ｖ、Ｌ／Ｓ=５０μｍ／５０μｍと評価した。 (8) Ion migration (ion-migration, unit: Ω): The characteristics of ion migration with respect to the adhesive film were evaluated as 85 ° C./85RH%/1000 hours, 50V, L / S = 50μm / 50μm. ..

（９）吸湿率（単位：％）：接着フィルムに対して、吸湿率は、ＩＰＣ−ＴＭ−６５０ ２．６．２．１Ａによって測定した。 (9) Hygroscopicity (Unit:%): With respect to the adhesive film, the hygroscopicity was measured by IPC-TM-650 2.6.2.1A.

（１０）周波数変化による誘電率と誘電損失：（３）と同じ方法により誘電率と誘電損失を測定するものの、２５℃における周波数を１ＧＨｚ、３ＧＨｚ、５ＧＨｚ、１０ＧＨｚに変更しながら、誘電率と誘電損失を測定した。 (10) Dielectric constant and dielectric loss due to frequency change: Although the dielectric constant and dielectric loss are measured by the same method as in (3), the dielectric constant and dielectric loss are changed while changing the frequency at 25 ° C. to 1 GHz, 3 GHz, 5 GHz, and 10 GHz. The loss was measured.

（１１）温度変化による誘電率と誘電損失：（３）と同じ方法により誘電率と誘電損失を測定するものの、１０ＧＨｚにおける測定温度を２０℃、４０℃、６０℃、８０℃に変更しながら、誘電率と誘電損失を測定した。 (11) Dielectric constant and dielectric loss due to temperature change: Although the dielectric constant and dielectric loss are measured by the same method as in (3), while changing the measurement temperature at 10 GHz to 20 ° C, 40 ° C, 60 ° C, and 80 ° C, Dielectric constant and dielectric loss were measured.

Figure 2021138944
Figure 2021138944

Figure 2021138944
Figure 2021138944

Figure 2021138944
Figure 2021138944

上記表２のように、本発明の接着フィルムは、誘電率と吸湿率が低かったし、上述した本発明の効果を全て具現することができる。また、上記表３、図３、図４のように、接着フィルムは、誘電率が低い、かつ、周波数、温度変化による誘電率の変化率が低かった。 As shown in Table 2 above, the adhesive film of the present invention had a low dielectric constant and a hygroscopicity, and all the effects of the present invention described above can be realized. Further, as shown in Tables 3, 3 and 4, the adhesive film had a low dielectric constant and a low rate of change in the dielectric constant due to changes in frequency and temperature.

他方、従来のアクリロニトリルブタジエン系接着フィルムである比較例１、ポリイミド系接着フィルムである比較例２、カルボン酸変性されていないオレフィン系樹脂と硬化剤を含む比較例３は、本発明の効果を得ることができなかった。 On the other hand, Comparative Example 1 which is a conventional acrylonitrile butadiene adhesive film, Comparative Example 2 which is a polyimide adhesive film, and Comparative Example 3 containing an olefin resin not modified with carboxylic acid and a curing agent obtain the effect of the present invention. I couldn't.

本発明の単純変形ないし変更は、この分野における通常の知識を有する者によって容易に実施することができ、このような変形や変更は、いずれも本発明の領域に含まれるといえる。 Simple modifications or modifications of the present invention can be easily carried out by a person having ordinary knowledge in this field, and any such modifications or modifications can be said to be included in the domain of the present invention.

Claims (16)

バインダー樹脂、エポキシ樹脂及びフィラーを含む組成物で形成される接着フィルムであって、前記バインダー樹脂は、カルボン酸変性オレフィン系樹脂及びポリフェニレンエーテル系樹脂を含み、
前記接着フィルムは、硬化後、１ＧＨｚ〜１０ＧＨｚ及び２０℃〜８０℃で測定された誘電率（ｄｉｅｌｅｃｔｒｉｃ ｃｏｎｓｔａｎｔ、Ｄｋ）が２．６以下、誘電損失（ｄｉｅｌｅｃｔｒｉｃ ｌｏｓｓ、Ｄｆ）が０．００５以下であり、前記接着フィルムは、硬化後の吸湿率が０．１％以下である、接着フィルム。 An adhesive film formed of a composition containing a binder resin, an epoxy resin and a filler, wherein the binder resin contains a carboxylic acid-modified olefin resin and a polyphenylene ether resin.
After curing, the adhesive film has a dielectric constant (Dk) of 2.6 or less and a dielectric loss (Df) of 0.005 or less measured at 1 GHz to 10 GHz and 20 ° C to 80 ° C. The adhesive film is an adhesive film having a moisture absorption rate of 0.1% or less after curing. 前記組成物は、硬化剤を含まないものである、
請求項１に記載の接着フィルム。 The composition does not contain a curing agent.
The adhesive film according to claim 1. 前記カルボン酸変性オレフィン系樹脂は、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、フマル酸、無数マレイン酸、無数イタコン酸、無数フマル酸のうち１種以上によって変性されたオレフィン系樹脂を含むものである、
請求項１に記載の接着フィルム。 The carboxylic acid-modified olefin resin contains an olefin resin modified by one or more of acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, innumerable maleic acid, innumerable itaconic acid, and innumerable fumaric acid. ,
The adhesive film according to claim 1. 前記エポキシ樹脂中のエポキシ基の総モル数に対する、前記バインダー樹脂中のカルボン酸基の総モル数の比は、１〜２のものである、
請求項１に記載の接着フィルム。 The ratio of the total number of moles of carboxylic acid groups in the binder resin to the total number of moles of epoxy groups in the epoxy resin is 1 to 2.
The adhesive film according to claim 1. 前記ポリフェニレンエーテル系樹脂と、前記カルボン酸変性オレフィン系樹脂とのガラス転移温度差は、１００℃〜２５０℃のものである、
請求項１に記載の接着フィルム。 The glass transition temperature difference between the polyphenylene ether-based resin and the carboxylic acid-modified olefin-based resin is 100 ° C. to 250 ° C.
The adhesive film according to claim 1. 前記カルボン酸変性オレフィン系樹脂は、カルボン酸変性された線状ポリプロピレン系樹脂を含むものである、
請求項１に記載の接着フィルム。 The carboxylic acid-modified olefin-based resin contains a carboxylic acid-modified linear polypropylene-based resin.
The adhesive film according to claim 1. 前記バインダー樹脂総和１００重量部のうち、前記カルボン酸変性スチレン系エラストマーは、４０重量部〜８０重量部、前記ポリフェニレンエーテル系樹脂は、２０重量部〜６０重量部で含まれるものである、
請求項１に記載の接着フィルム。 Of the total 100 parts by weight of the binder resin, the carboxylic acid-modified styrene elastomer is contained in an amount of 40 parts by weight to 80 parts by weight, and the polyphenylene ether resin is contained in an amount of 20 parts by weight to 60 parts by weight.
The adhesive film according to claim 1. 前記フィラーは、無機ナノシリカとフッ素樹脂フィラーとの混合物を含むものである、
請求項１に記載の接着フィルム。 The filler contains a mixture of an inorganic nanosilica and a fluororesin filler.
The adhesive film according to claim 1. 前記バインダー樹脂１００重量部に対して、前記エポキシ樹脂を１重量部〜１０重量部、前記フィラーを５重量部〜４０重量部で含むものである、
請求項１に記載の接着フィルム。 The epoxy resin is contained in an amount of 1 part to 10 parts by weight and the filler is contained in an amount of 5 parts to 40 parts by weight with respect to 100 parts by weight of the binder resin.
The adhesive film according to claim 1. 前記接着フィルムは、同一周波数において、硬化後の誘電損失に対する硬化後の誘電率の比（硬化後の誘電率／硬化後の誘電損失）が６５０以上のものである、
請求項１に記載の接着フィルム。 The adhesive film has a ratio of the dielectric constant after curing (dielectric constant after curing / dielectric loss after curing) of 650 or more to the dielectric loss after curing at the same frequency.
The adhesive film according to claim 1. 前記接着フィルムは、硬化後のガラス転移温度が６０℃〜８０℃のものである、
請求項１に記載の接着フィルム。 The adhesive film has a glass transition temperature of 60 ° C. to 80 ° C. after curing.
The adhesive film according to claim 1. ポリイミド系樹脂フィルム、前記ポリイミド系樹脂フィルムの少なくとも一面に備えられた接着フィルムを備え、前記接着フィルムは、請求項１〜請求項１１のうちいずれか一項の接着フィルムを含むものである、接着フィルム付き積層体。 A polyimide resin film and an adhesive film provided on at least one surface of the polyimide resin film are provided, and the adhesive film includes the adhesive film according to any one of claims 1 to 11. With an adhesive film. Laminated body. 前記接着フィルム付き積層体は、カバーレイフィルムを含むものである、
請求項１２に記載の接着フィルム付き積層体。 The laminate with an adhesive film includes a coverlay film.
The laminate with an adhesive film according to claim 12. ポリイミド系樹脂フィルム、前記ポリイミド系樹脂フィルムの少なくとも一面に備えられた接着フィルム、及び前記接着フィルムの一面に備えられた金属箔を備え、前記接着フィルムは、前記ポリイミド系樹脂フィルムと前記金属箔との間に備えられ、
前記接着フィルムは、請求項１〜請求項１１のうちいずれか一項の接着フィルムを備えるものである、金属箔積層体。 A polyimide resin film, an adhesive film provided on at least one surface of the polyimide resin film, and a metal foil provided on one surface of the adhesive film are provided, and the adhesive film includes the polyimide resin film and the metal foil. Prepared between
The adhesive film is a metal leaf laminate comprising the adhesive film according to any one of claims 1 to 11. 前記金属箔は、銅箔を含むものである、
請求項１４に記載の金属箔積層体。 The metal foil includes a copper foil.
The metal leaf laminate according to claim 14. 前記金属箔積層体は、軟性回路基板を含むものである、
請求項１４に記載の金属箔積層体。 The metal leaf laminate includes a flexible circuit board.
The metal leaf laminate according to claim 14.
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