TW202130766A - Adhesive film, laminate, and printed wiring board - Google Patents

Adhesive film, laminate, and printed wiring board Download PDF

Info

Publication number
TW202130766A
TW202130766A TW109141231A TW109141231A TW202130766A TW 202130766 A TW202130766 A TW 202130766A TW 109141231 A TW109141231 A TW 109141231A TW 109141231 A TW109141231 A TW 109141231A TW 202130766 A TW202130766 A TW 202130766A
Authority
TW
Taiwan
Prior art keywords
adhesive film
mass
less
parts
group
Prior art date
Application number
TW109141231A
Other languages
Chinese (zh)
Inventor
小栁英之
薗田遼
入澤隼人
川楠哲生
Original Assignee
日商東洋紡股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 日商東洋紡股份有限公司 filed Critical 日商東洋紡股份有限公司
Publication of TW202130766A publication Critical patent/TW202130766A/en

Links

Classifications

    • 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
    • C09J123/30—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 by oxidation
    • 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
    • C09J7/35—Heat-activated
    • 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
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Abstract

To provide an adhesive film that has high adhesiveness with respect to metal substrates and resin substrates such as polyimides, that enables a high solder heat resistance to be achieved, and that provides excellent film handling ability and low-dielectric characteristics. An adhesive film characterized by comprising an acid-modified polyolefin (a), an oligophenylene ether (b) that has a number average molecular weight not more than 3000, an epoxy resin (c), and a carbodiimide compound (d), and characterized by containing an organic solvent (e) at an amount of 1-8 mass% with respect to the adhesive film.

Description

黏接薄膜、疊層體、以及印刷配線板Adhesive film, laminate, and printed wiring board

本發明關於黏接薄膜。更詳細而言，關於樹脂基材與樹脂基材或金屬基材之黏接所使用的黏接薄膜。尤其關於撓性印刷配線板(以下簡稱FPC)用黏接薄膜，以及關於包含該黏接薄膜之覆蓋層薄膜、疊層板、設有樹脂之銅箔及黏結片。The present invention relates to adhesive films. In more detail, it is an adhesive film used for bonding a resin substrate and a resin substrate or a metal substrate. In particular, it relates to adhesive films for flexible printed wiring boards (hereinafter referred to as FPC), as well as covering films, laminates, copper foils and adhesive sheets containing the adhesive films.

撓性印刷配線板(FPC)由於具有優良的彎曲性而可對應於個人電腦(PC)、智慧型手機等的多功能化、小型化，因此常被使用來將電子電路基板納入狹小複雜的內部。近年，電子設備的小型化、輕量化、高密度化、高輸出化進展，並由於它們的流行而使得對配線板(電子電路基板)之性能的要求愈益提高。尤其伴隨FPC中的傳送訊號之高速化，訊號的高頻化正在進展。伴隨於此，就FPC而言，在高頻區域之低介電特性(低介電常數、低介電損耗正切)的要求提高。為了達成如此的低介電特性，已有減少FPC之基材、黏接劑的介電體損失之方法。就黏接劑而言，以聚烯烴與環氧化物的組合(專利文獻1)之開發正在進行。 [先前技術文獻] [專利文獻]Flexible printed wiring boards (FPC) have excellent flexibility and can correspond to the multi-function and miniaturization of personal computers (PC), smart phones, etc., so they are often used to incorporate electronic circuit boards into small and complex interiors. . In recent years, the miniaturization, weight reduction, high density, and high output of electronic devices have progressed, and due to their popularity, the requirements for the performance of wiring boards (electronic circuit boards) have increased. Especially with the increase of the transmission signal speed in FPC, the high frequency of the signal is progressing. Along with this, as far as FPC is concerned, the requirements for low dielectric properties (low dielectric constant, low dielectric loss tangent) in the high-frequency region have increased. In order to achieve such low dielectric properties, there have been methods to reduce the dielectric loss of the FPC substrate and adhesive. As for the adhesive, the development of a combination of polyolefin and epoxide (Patent Document 1) is underway. [Prior Technical Literature] [Patent Literature]

[專利文獻1]WO2016/047289號公報[Patent Document 1] WO2016/047289 Publication

[發明所欲解決之課題][The problem to be solved by the invention]

但是，專利文獻1在補強板、層間所使用的黏接劑之耐熱性難謂優良。此外，關於黏接薄膜中的溶劑量未進行考慮，而有薄膜操作性不足的課題。又，使用了結晶性高的酸改性聚烯烴之黏接薄膜，會有不易填埋電路配線圖案的凹凸之傾向。However, in Patent Document 1, the heat resistance of the adhesive used in the reinforcing plate and between the layers is hardly said to be excellent. In addition, the amount of solvent in the adhesive film is not considered, and there is a problem of insufficient film handling. In addition, the adhesive film using acid-modified polyolefin with high crystallinity tends to be difficult to fill the unevenness of the circuit wiring pattern.

本發明為了解決上述課題而深入探討後之結果發現，具有特定組成之黏接薄膜，其和聚醯亞胺薄膜等樹脂基材或銅箔等金屬基材之高黏接性、焊料耐熱性、及薄膜操作性優良，乃至完成本發明。In order to solve the above-mentioned problems, the present invention has intensively studied and found that an adhesive film with a specific composition has high adhesiveness, solder heat resistance, And the film has excellent operability, and even completed the present invention.

亦即，本發明目的為提供具有對聚醯亞胺薄膜等樹脂基材及金屬基材雙方之良好的黏接性，且焊料耐熱性優良，此外，乾燥後的黏性、電路填埋性等薄膜操作性亦優良的黏接薄膜。 [解決課題之手段]That is, the object of the present invention is to provide good adhesion to both resin substrates such as polyimide films and metal substrates, and excellent solder heat resistance, in addition, adhesiveness after drying, circuit embedding properties, etc. Adhesive film with excellent film handling properties. [Means to solve the problem]

一種黏接薄膜，其特徵為含有： 酸改性聚烯烴(a)， 數目平均分子量3000以下之寡聚伸苯基醚(b)， 環氧樹脂(c)，及 碳二亞胺化合物(d)； 且有機溶劑(e)的含量相對於黏接薄膜的質量為1～8質量%。An adhesive film, which is characterized by containing: Acid-modified polyolefin (a), Oligophenylene ether (b) with number average molecular weight below 3000, Epoxy resin (c), and Carbodiimide compound (d); And the content of the organic solvent (e) is 1-8% by mass relative to the mass of the adhesive film.

酸改性聚烯烴(a)的酸價宜為5～40mgKOH/g，數目平均分子量3000以下之寡聚伸苯基醚(b)宜具有通式(1)之結構單元及/或通式(2)之結構單元。又，有機溶劑(e)宜為選自於由甲乙酮、甲基環己烷及甲苯構成之群組中之1種以上之有機溶劑。 [化1]

Figure 02_image001
通式(1)中，R1 、R2 、R3 、R4 分別獨立地表示氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基。 [化2]
Figure 02_image004
通式(2)中，R11 、R12 、R13 、R14 、R15 、R16 、R17 、R18 分別獨立地表示氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基。A為碳數20以下之直鏈狀或分支狀或環狀之2價烴基、或氧原子。The acid value of the acid-modified polyolefin (a) is preferably 5-40 mgKOH/g, and the oligophenylene ether (b) with a number average molecular weight of 3000 or less preferably has the structural unit of the general formula (1) and/or the general formula ( 2) The structural unit. In addition, the organic solvent (e) is preferably one or more organic solvents selected from the group consisting of methyl ethyl ketone, methyl cyclohexane, and toluene. [化1]
Figure 02_image001
In the general formula (1), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and An aryl group that may be substituted, an aralkyl group that may also be substituted, or an alkoxy group that may also be substituted. [化2]
Figure 02_image004
In the general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted Alkenyl, alkynyl which may also be substituted, aryl which may also be substituted, aralkyl which may also be substituted or alkoxy which may be substituted. A is a linear, branched, or cyclic divalent hydrocarbon group with a carbon number of 20 or less, or an oxygen atom.

前述黏接薄膜中，相對於酸改性聚烯烴(a)100質量份，宜含有5～100質量份之數目平均分子量3000以下之寡聚伸苯基醚(b)、5～60質量份之環氧樹脂(c)及0.5～20質量份之碳二亞胺化合物(d)。又，硬化後的黏接薄膜，於1GHz的相對介電常數(εc )宜為3.0以下，介電損耗正切(tanδ)宜為0.02以下。The aforementioned adhesive film preferably contains 5-100 parts by mass of oligophenylene ether (b) with a number average molecular weight of 3000 or less and 5-60 parts by mass relative to 100 parts by mass of acid-modified polyolefin (a) Epoxy resin (c) and 0.5-20 parts by mass of carbodiimide compound (d). In addition, the relative dielectric constant (ε c ) of the cured adhesive film at 1 GHz is preferably 3.0 or less, and the dielectric loss tangent (tanδ) is preferably 0.02 or less.

一種疊層體，係使用前述黏接薄膜而形成。一種印刷配線板，含有前述疊層體作為構成元件。 [發明之效果]A laminated body is formed using the aforementioned adhesive film. A printed wiring board containing the aforementioned laminate as a constituent element. [Effects of Invention]

本發明之黏接薄膜具有對聚醯亞胺薄膜等各種樹脂基材及金屬基材雙方之良好的黏接性，且焊料耐熱性優良，此外，乾燥後的黏性、電路填埋性等薄膜操作性優良。The adhesive film of the present invention has good adhesion to various resin substrates such as polyimide films and metal substrates, and has excellent solder heat resistance. In addition, the adhesive film after drying, circuit embedding properties, etc. Excellent operability.

＜酸改性聚烯烴(a)＞ 本發明所使用的酸改性聚烯烴(a)(以下也簡稱(a)成分)並無限制，宜為藉由將α,β-不飽和羧酸及其酸酐中之至少1種接枝於聚烯烴樹脂而得者。聚烯烴樹脂係指乙烯、丙烯、丁烯、丁二烯、異戊二烯等所例示之烯烴單體的均聚物、或和其它單體之共聚物、及得到的聚合物之氫化物、鹵化物等以烴骨架作為主體之聚合物。亦即，酸改性聚烯烴宜為藉由將α,β-不飽和羧酸及其酸酐中之至少1種接枝於聚乙烯、聚丙烯及丙烯-α-烯烴共聚物中之至少1種而得者。＜Acid modified polyolefin (a)＞ The acid-modified polyolefin (a) used in the present invention (hereinafter also referred to as (a) component) is not limited, and it is preferable to graft at least one of α, β-unsaturated carboxylic acid and its anhydride on Derived from polyolefin resin. Polyolefin resin refers to homopolymers of olefin monomers exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., or copolymers with other monomers, and hydrogenated products of the resulting polymers, Halides and other polymers with a hydrocarbon skeleton as the main body. That is, the acid-modified polyolefin is preferably obtained by grafting at least one of α, β-unsaturated carboxylic acid and its anhydride to at least one of polyethylene, polypropylene, and propylene-α-olefin copolymer. And the winner.

丙烯-α-烯烴共聚物係以丙烯作為主體，並將α-烯烴共聚合於其上而成者。α-烯烴例如可使用乙烯、1-丁烯、1-庚烯、1-辛烯、4-甲基-1-戊烯、乙酸乙烯酯等中之1種或數種。這些α-烯烴之中，宜為乙烯、1-丁烯。丙烯-α-烯烴共聚物的丙烯成分與α-烯烴成分之比率並無限制，但丙烯成分宜為50莫耳%以上，為70莫耳%以上更佳。The propylene-α-olefin copolymer is formed by copolymerizing α-olefin with propylene as the main body. For the α-olefin, for example, one or more of ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, vinyl acetate, and the like can be used. Among these α-olefins, ethylene and 1-butene are preferable. The ratio of the propylene component to the α-olefin component of the propylene-α-olefin copolymer is not limited, but the propylene component is preferably 50 mol% or more, more preferably 70 mol% or more.

α,β-不飽和羧酸及其酸酐中之至少1種可列舉例如：馬來酸、伊康酸、檸康酸及它們的酸酐。它們之中，宜為酸酐，為馬來酸酐更佳。具體而言，可列舉：馬來酸酐改性聚丙烯、馬來酸酐改性丙烯-乙烯共聚物、馬來酸酐改性丙烯-丁烯共聚物、馬來酸酐改性丙烯-乙烯-丁烯共聚物等，這些酸改性聚烯烴可使用1種或組合使用2種以上。Examples of at least one of α,β-unsaturated carboxylic acids and their anhydrides include maleic acid, itaconic acid, citraconic acid, and their anhydrides. Among them, acid anhydride is preferable, and maleic anhydride is more preferable. Specifically, examples include: maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, maleic anhydride-modified propylene-ethylene-butene copolymer These acid-modified polyolefins can be used singly or in combination of two or more.

酸改性聚烯烴(a)的酸價，考慮耐熱性及和樹脂基材、金屬基材之黏接性的觀點，下限宜為5mgKOH/g以上，為6mgKOH/g以上更佳，為7mgKOH/g以上再更佳。藉由設定為前述下限值以上，和環氧樹脂(c)之相容性可變良好，且可展現優良的黏接強度。而且，交聯密度高且焊料耐熱性變良好。上限宜為40mgKOH/g以下，為30mgKOH/g以下更佳，為20mgKOH/g以下再更佳。藉由設定為前述上限值以下，黏接性會變良好。The acid value of the acid-modified polyolefin (a), considering the heat resistance and adhesion to the resin substrate and metal substrate, the lower limit is preferably 5 mgKOH/g or more, more preferably 6 mgKOH/g or more, and 7 mgKOH/ Above g is even better. By setting it to be higher than the aforementioned lower limit, the compatibility with the epoxy resin (c) can be improved and excellent bonding strength can be exhibited. Furthermore, the crosslink density is high and the solder heat resistance becomes good. The upper limit is preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g or less, and even more preferably 20 mgKOH/g or less. By setting it below the aforementioned upper limit, the adhesiveness becomes better.

酸改性聚烯烴(a)的數目平均分子量(Mn)宜為10,000～50,000之範圍。為15,000～45,000之範圍更佳，為20,000～40000之範圍再更佳，為22,000～38,000之範圍特佳。藉由設定為前述下限值以上，凝聚力可變良好，且可展現優良的黏接性。又，藉由設定為前述上限值以下，流動性優良，且黏接時之操作性良好。The number average molecular weight (Mn) of the acid-modified polyolefin (a) is preferably in the range of 10,000 to 50,000. The range of 15,000-45,000 is more preferable, the range of 20,000-40000 is even more preferable, and the range of 22,000-38,000 is especially preferable. By setting it to be higher than the aforementioned lower limit, the cohesive force can be improved and excellent adhesiveness can be exhibited. In addition, by setting it to the upper limit or less, the fluidity is excellent, and the workability at the time of bonding is good.

酸改性聚烯烴(a)宜為結晶性酸改性聚烯烴。本發明中所稱結晶性係指使用差示掃描型熱量計(DSC)，以20℃/分鐘條件從-100℃昇溫至250℃，並於該昇溫過程中展現明確的熔解峰部者。The acid-modified polyolefin (a) is preferably a crystalline acid-modified polyolefin. The crystallinity referred to in the present invention refers to the use of a differential scanning calorimeter (DSC), the temperature is raised from -100°C to 250°C at a condition of 20°C/min, and a clear melting peak is exhibited during the heating process.

酸改性聚烯烴(a)的熔點(Tm)宜為50℃～120℃之範圍。為60℃～100℃之範圍更佳，為70℃～90℃之範圍最佳。藉由設定為前述下限值以上，源自結晶的凝聚力可變良好，且可展現優良的黏接性、焊料耐熱性。又，藉由設定為前述上限值以下，溶液安定性、流動性優良，且黏接時之操作性良好。The melting point (Tm) of the acid-modified polyolefin (a) is preferably in the range of 50°C to 120°C. The range of 60°C to 100°C is more preferable, and the range of 70°C to 90°C is most preferable. By setting it to the aforementioned lower limit or more, the cohesive force derived from crystals can be improved, and excellent adhesiveness and solder heat resistance can be exhibited. In addition, by setting it to the upper limit or less, the solution has excellent stability and fluidity, and the workability at the time of bonding is good.

酸改性聚烯烴(a)的熔解熱(ΔH)宜為5J/g～60J/g之範圍。為10J/g～50J/g之範圍更佳，為20J/g～40J/g之範圍最佳。藉由設定為前述下限值以上，源自結晶的凝聚力可變良好，且可展現優良的黏接性、焊料耐熱性。又，藉由設定為前述上限值以下，溶液安定性、流動性優良，且黏接時之操作性良好。The heat of fusion (ΔH) of the acid-modified polyolefin (a) is preferably in the range of 5J/g to 60J/g. The range of 10J/g～50J/g is more preferable, and the range of 20J/g～40J/g is the best. By setting it to the aforementioned lower limit or more, the cohesive force derived from crystals can be improved, and excellent adhesiveness and solder heat resistance can be exhibited. In addition, by setting it to the upper limit or less, the solution has excellent stability and fluidity, and the workability at the time of bonding is good.

酸改性聚烯烴(a)的製造方法並無特別限制，可列舉例如：自由基接枝反應(亦即對係為主鏈之聚合物生成自由基物種，並以該自由基物種作為聚合開始點使不飽和羧酸及酸酐進行接枝聚合之反應)等。The production method of acid-modified polyolefin (a) is not particularly limited. Examples include: radical grafting reaction (that is, a radical species is generated on the polymer of the main chain, and the radical species is used as the polymerization start Point to graft polymerization reaction of unsaturated carboxylic acid and acid anhydride) and so on.

自由基產生劑並無特別限制，但宜使用有機過氧化物。有機過氧化物並無特別限制，可列舉：過氧化苯二甲酸二(三級丁酯)、三級丁基過氧化氫、過氧化二異丙苯、過氧化苯甲醯、過氧化苯甲酸三級丁酯、過氧化-2-乙基己酸三級丁酯、過氧化三甲基乙酸三級丁酯、過氧化甲乙酮、二(三級丁基)過氧化物、過氧化月桂醯等過氧化物；偶氮雙異丁腈、偶氮雙異丙腈等偶氮腈類等。The radical generator is not particularly limited, but organic peroxides are preferably used. Organic peroxides are not particularly limited. Examples include: di(tertiary butyl) peroxyphthalate, tertiary butyl hydroperoxide, dicumyl peroxide, benzyl peroxide, and benzoic acid peroxide. Tertiary butyl ester, tertiary butyl peroxide-2-ethylhexanoate, tertiary butyl peroxide trimethyl acetate, methyl ethyl ketone peroxide, di(tertiary butyl) peroxide, lauryl peroxide, etc. Peroxides; azo nitriles such as azobisisobutyronitrile, azobisisopropionitrile, etc.

＜寡聚伸苯基醚(b)＞ 本發明所使用的寡聚伸苯基醚(b)(以下也簡稱(b)成分)係數目平均分子量(Mn)為3000以下者，理想可使用具有下述通式(1)表示之結構單元及/或通式(2)之結構單元的化合物。＜oligomeric phenylene ether (b)＞ The oligophenylene ether (b) used in the present invention (hereinafter also referred to as the (b) component) has a number average molecular weight (Mn) of 3000 or less, and it is desirable to use a structural unit represented by the following general formula (1) And/or the compound of the structural unit of general formula (2).

[化1]

Figure 02_image001
通式(1)中，R1 、R2 、R3 、R4 宜分別獨立為氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基。也可經取代之烷基之「烷基」例如為碳數1以上且6以下，宜為碳數1以上且3以下之直鏈狀或支鏈狀之烷基。更具體而言，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、己基等，為甲基或乙基更佳。也可經取代之烯基之「烯基」可列舉例如：乙烯基、1-丙烯基、2-丙烯基、3-丁烯基、戊烯基、己烯基等，為乙烯基或1-丙烯基更佳。也可經取代之炔基之「炔基」可列舉例如：乙炔基、1-丙炔基、2-丙炔基(炔丙基)、3-丁炔基、戊炔基、己炔基等，為乙炔基、1-丙炔基或2-丙炔基(炔丙基)更佳。也可經取代之芳基之「芳基」可列舉例如：苯基、萘基等，為苯基更佳。也可經取代之芳烷基之「芳烷基」可列舉例如：苄基、苯乙基、2-甲基苄基、4-甲基苄基、α-甲基苄基、2-乙烯基苯乙基、4-乙烯基苯乙基等，為苄基更佳。也可經取代之烷氧基之「烷氧基」例如為碳數1以上且6以下，宜為碳數1以上且3以下之直鏈狀或支鏈狀之烷氧基。可列舉例如：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、二級丁氧基、三級丁氧基、戊氧基、己氧基等，為甲氧基或乙氧基更佳。上述烷基、芳基、烯基、炔基、芳烷基、及烷氧基有被取代時，可具有1個或2個以上之取代基。如此的取代基可列舉例如：鹵素原子(例如氟原子、氯原子、溴原子)、碳數1～6之烷基(例如甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、己基)、芳基(例如苯基、萘基)、烯基(例如乙烯基、1-丙烯基、2-丙烯基)、炔基(例如乙炔基、1-丙炔基、2-丙炔基)、芳烷基(例如苄基、苯乙基)、烷氧基(例如甲氧基、乙氧基)等。其中，宜為R1 及R4 係甲基，且R2 及R3 係氫原子。[化1]
Figure 02_image001
In the general formula (1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or An aryl group that may be substituted, an aralkyl group that may also be substituted, or an alkoxy group that may also be substituted. The "alkyl group" of the alkyl group which may be substituted is, for example, a C 1 or more and 6 or less, and preferably a C 1 or more and 3 or less linear or branched alkyl group. More specifically, examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, hexyl, etc., which are methyl or ethyl Better. The "alkenyl" of the alkenyl group that may be substituted includes, for example, vinyl, 1-propenyl, 2-propenyl, 3-butenyl, pentenyl, hexenyl, etc., which are vinyl or 1- Acrylic is better. The "alkynyl" of the alkynyl group that may be substituted includes, for example, ethynyl, 1-propynyl, 2-propynyl (propargyl), 3-butynyl, pentynyl, hexynyl, etc. , More preferably ethynyl, 1-propynyl or 2-propynyl (propargyl). Examples of the "aryl group" of the aryl group that may be substituted include phenyl, naphthyl, etc., and phenyl is more preferred. The "aralkyl group" of the aralkyl group that may be substituted includes, for example, benzyl, phenethyl, 2-methylbenzyl, 4-methylbenzyl, α-methylbenzyl, 2-vinyl Phenylethyl, 4-vinylphenethyl, etc., benzyl is more preferred. The "alkoxy group" of the alkoxy group which may be substituted is, for example, a C 1 or more and 6 or less, preferably a C 1 or more and 3 or less linear or branched alkoxy group. Examples include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, secondary butoxy, tertiary butoxy, pentoxy, hexyloxy, etc., which are methoxy Or ethoxy is more preferable. When the alkyl group, aryl group, alkenyl group, alkynyl group, aralkyl group, and alkoxy group are substituted, they may have one or two or more substituents. Examples of such substituents include halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms), alkyl groups having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl). Group, secondary butyl, tertiary butyl, pentyl, hexyl), aryl (e.g. phenyl, naphthyl), alkenyl (e.g. vinyl, 1-propenyl, 2-propenyl), alkynyl ( For example, ethynyl, 1-propynyl, 2-propynyl), aralkyl (e.g., benzyl, phenethyl), alkoxy (e.g., methoxy, ethoxy), and the like. Among them, R 1 and R 4 are preferably methyl groups, and R 2 and R 3 are hydrogen atoms.

[化2]

Figure 02_image004
通式(2)中，R11 、R12 、R13 、R14 、R15 、R16 、R17 、R18 宜分別獨立為氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基。另外，各取代基的定義如前所述。烷基可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、戊基、己基等，宜為甲基。其中，宜為R13 、R14 、R17 及R18 係甲基，且R11 、R12 、R15 及R16 係氫原子。又，-A-宜為碳數20以下之直鏈狀或分支狀或環狀之2價烴基、或氧原子。A的碳數為1以上且15以下更佳，為2以上且10以下再更佳。又，A之2價烴基可列舉：亞甲基、伸乙基、伸正丙基、伸正丁基、伸環己基、伸苯基等，其中，宜為伸苯基。為氧原子特佳。[化2]
Figure 02_image004
In the general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 are each independently a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted Alkenyl, alkynyl which may also be substituted, aryl which may also be substituted, aralkyl which may also be substituted or alkoxy which may be substituted. In addition, the definition of each substituent is as described above. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, hexyl, etc., and methyl is preferred. Among them, R 13 , R 14 , R 17 and R 18 are preferably methyl groups, and R 11 , R 12 , R 15 and R 16 are hydrogen atoms. Furthermore, -A- is preferably a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms, or an oxygen atom. The carbon number of A is more preferably 1 or more and 15 or less, and even more preferably 2 or more and 10 or less. In addition, the divalent hydrocarbon group of A includes methylene, ethylene, n-propyl, n-butyl, cyclohexylene, phenylene, etc. Among them, phenylene is preferred. It is particularly good for oxygen atoms.

(b)成分中，也可將一部分或全部以乙烯基苄基等乙烯性不飽和基、環氧基、胺基、羥基、巰基、羧基、及矽基等製成經官能基化之改性寡聚伸苯基醚。此外，兩末端宜具有羥基、環氧基、或乙烯性不飽和基。乙烯性不飽和基可列舉：乙烯基、烯丙基、甲基丙烯酸基、丙烯基、丁烯基、己烯基、辛烯基等烯基；環戊烯基、環己烯基等環烯基；乙烯基苄基、乙烯基萘基等烯基芳基。又，兩末端可為相同的官能基，也可為不同的官能基。考慮高程度地控制低介電損耗正切及樹脂殘渣之減少之平衡的觀點，兩末端宜為羥基、或乙烯基苄基，兩末端均為羥基、或乙烯基苄基更佳。(b) In the component, part or all of it can be modified by functionalization with ethylenically unsaturated groups such as vinylbenzyl, epoxy, amino, hydroxyl, mercapto, carboxyl, and silyl groups. Oligomer phenylene ether. In addition, it is preferable to have a hydroxyl group, an epoxy group, or an ethylenically unsaturated group at both ends. Examples of ethylenically unsaturated groups include: vinyl, allyl, methacryl, propenyl, butenyl, hexenyl, octenyl and other alkenyl groups; cyclopentenyl, cyclohexenyl and other cycloalkenes Group; alkenyl aryl groups such as vinyl benzyl and vinyl naphthyl. In addition, both ends may have the same functional group or different functional groups. Considering the viewpoint of controlling the balance of low dielectric loss tangent and resin residue reduction to a high degree, both ends are preferably hydroxyl groups or vinylbenzyl groups, and both ends are preferably hydroxyl groups or vinylbenzyl groups.

具有通式(1)表示之結構單元的化合物為通式(3)之化合物特佳。 [化3]

Figure 02_image008
通式(3)中，n宜為3以上，為5以上更佳，且宜為23以下，為21以下更佳，為19以下再更佳。The compound having the structural unit represented by the general formula (1) is particularly preferably the compound of the general formula (3). [化3]
Figure 02_image008
In the general formula (3), n is preferably 3 or more, more preferably 5 or more, and preferably 23 or less, more preferably 21 or less, and even more preferably 19 or less.

又，具有通式(2)表示之結構單元的化合物為通式(4)之化合物特佳。 [化4]

Figure 02_image010
通式(4)中，n宜為2以上，為4以上更佳，且宜為23以下，為20以下更佳，為18以下再更佳。In addition, the compound having the structural unit represented by the general formula (2) is particularly preferably the compound of the general formula (4). [化4]
Figure 02_image010
In the general formula (4), n is preferably 2 or more, more preferably 4 or more, and preferably 23 or less, more preferably 20 or less, and even more preferably 18 or less.

(b)成分的數目平均分子量需要為3000以下，為2700以下更佳，為2500以下再更佳。又，(b)成分的數目平均分子量宜為500以上，為700以上更佳。藉由將(b)成分的數目平均分子量設定為下限值以上，可使黏接薄膜之可撓性良好。另一方面，藉由將(b)成分的數目平均分子量設定為上限值以下，可使其對有機溶劑之溶解性良好。(b) The number average molecular weight of the component needs to be 3000 or less, more preferably 2700 or less, and even more preferably 2500 or less. In addition, the number average molecular weight of the component (b) is preferably 500 or more, and more preferably 700 or more. By setting the number average molecular weight of the component (b) to be more than the lower limit, the flexibility of the adhesive film can be improved. On the other hand, by setting the number average molecular weight of the component (b) to be equal to or less than the upper limit, the solubility in organic solvents can be improved.

(b)成分的含量相對於(a)成分100質量份，宜為5質量份以上，為7質量份以上更佳，為10質量份以上再更佳。又，宜為100質量份以下，為80質量份以下更佳，為60質量份以下再更佳，為50質量份以下特佳。藉由設定為上述範圍內，可獲得黏接性及焊料耐熱性、電路填埋性優良的黏接薄膜。The content of the (b) component is preferably 5 parts by mass or more with respect to 100 parts by mass of the (a) component, more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more. Furthermore, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less. By setting it within the above range, an adhesive film with excellent adhesiveness, solder heat resistance, and circuit embedding properties can be obtained.

＜環氧樹脂(c)＞ 本發明所使用的環氧樹脂(c)(以下也簡稱(c)成分)若為分子中具有環氧基者，則無特別限制，宜為分子中具有2個以上之環氧丙基者。具體而言，可使用選自於由聯苯型環氧樹脂、萘型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、脂環族環氧樹脂、雙環戊二烯型環氧樹脂、四環氧丙基二胺基二苯基甲烷、三環氧丙基對胺基苯酚、四環氧丙基雙胺基甲基環己酮、N,N,N’,N’-四環氧丙基間二甲苯二胺、及環氧改性聚丁二烯構成之群組中之至少1種，但並非特別限定。宜為聯苯型環氧樹脂、酚醛清漆型環氧樹脂、雙環戊二烯型環氧樹脂或環氧改性聚丁二烯。為雙環戊二烯型環氧樹脂更佳。＜Epoxy resin (c)＞ The epoxy resin (c) used in the present invention (hereinafter also referred to as the (c) component) is not particularly limited as long as it has an epoxy group in the molecule, and it is preferably one having two or more glycidyl groups in the molecule. Specifically, it can be selected from the group consisting of biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, alicyclic ring Oxygen resin, dicyclopentadiene epoxy resin, tetraglycidyl diamino diphenyl methane, triglycidyl p-amino phenol, tetraglycidyl diamino methyl cyclohexanone, N ,N,N',N'-tetraepoxypropyl m-xylene diamine and epoxy-modified polybutadiene at least one of the group, but it is not particularly limited. It is preferably biphenyl type epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin or epoxy modified polybutadiene. It is more preferably a dicyclopentadiene type epoxy resin.

環氧樹脂(c)的環氧當量宜為50g/eq以上，為100g/eq以上更佳，為150g/eq以上再更佳。又，宜為400g/eq以下，為350g/eq以下更佳，為300g/eq以下再更佳。藉由設定為前述範圍內，可展現優良的焊料耐熱性。The epoxy equivalent of the epoxy resin (c) is preferably 50 g/eq or more, more preferably 100 g/eq or more, and even more preferably 150 g/eq or more. Furthermore, it is preferably 400 g/eq or less, more preferably 350 g/eq or less, and even more preferably 300 g/eq or less. By setting it within the aforementioned range, excellent solder heat resistance can be exhibited.

(c)成分的含量相對於(a)成分100質量份，宜為5質量份以上，為10質量份以上更佳，為15質量份以上再更佳。又，宜為60質量份以下，為50質量份以下更佳，為45質量份以下再更佳。藉由設定為上述範圍內，可獲得可得到充分的硬化效果、黏接性及焊料耐熱性良好、更具有優良的低介電特性之黏接薄膜。The content of the component (c) is preferably 5 parts by mass or more with respect to 100 parts by mass of the component (a), more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more. Furthermore, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. By setting it within the above range, an adhesive film can be obtained that can obtain a sufficient curing effect, has good adhesiveness and solder heat resistance, and has excellent low-dielectric properties.

＜碳二亞胺化合物(d)＞ 本發明所使用的碳二亞胺化合物(d)(以下也簡稱(d)成分)若為分子內具有碳二亞胺基者，則無特別限制。宜為分子內具有2個以上之碳二亞胺基之聚碳二亞胺。藉由使用聚碳二亞胺，酸改性聚烯烴(a)的羧基與碳二亞胺基會進行反應，可提高黏接劑組成物與基材的交互作用，並改善黏接性。＜Carbodiimide compound (d)＞ The carbodiimide compound (d) (hereinafter also referred to as the (d) component) used in the present invention is not particularly limited as long as it has a carbodiimide group in the molecule. Preferably, it is a polycarbodiimide having two or more carbodiimide groups in the molecule. By using polycarbodiimide, the carboxyl group and carbodiimide group of the acid-modified polyolefin (a) will react, which can increase the interaction between the adhesive composition and the substrate and improve the adhesion.

(d)成分的含量相對於(a)成分100質量份，宜為0.5質量份以上，為1質量份以上更佳，為2質量份以上再更佳。藉由設定為前述下限值以上，會展現和基材的交互作用，黏接性會變良好。又，宜為20質量份以下，為15質量份以下更佳，為10質量份以下再更佳。藉由設定為前述上限值以下，可展現優良的介電特性。亦即，藉由設定為上述範圍內，可獲得除了具有黏接性及焊料耐熱性之外，更具有優良的低介電特性之黏接薄膜。The content of the (d) component relative to 100 parts by mass of the (a) component is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. By setting it above the aforementioned lower limit, interaction with the substrate will be exhibited, and the adhesion will become better. Furthermore, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. By setting it below the aforementioned upper limit value, excellent dielectric properties can be exhibited. That is, by setting it within the above range, it is possible to obtain an adhesive film having excellent low-dielectric properties in addition to adhesiveness and solder heat resistance.

＜有機溶劑(e)＞ 本發明之黏接薄膜必須於該薄膜中含有1～8質量%之有機溶劑(e)。考量電路填埋性良好的情況，宜為2質量%以上，為3質量%以上更佳。又，考量黏性性、焊料耐熱性及電特性良好的情況，宜為7質量%以下，為6質量%以下更佳。亦即，藉由設定為上述範圍內，可獲得焊料耐熱性、薄膜操作性(電路填埋性及黏性性)、電特性優良的黏接薄膜。有機溶劑的含量取決於有機溶劑之種類、膜厚、乾燥溫度、乾燥時間而適當地調整。＜Organic solvent (e)＞ The adhesive film of the present invention must contain 1-8% by mass of organic solvent (e) in the film. In consideration of good circuit landfillability, it is preferably 2% by mass or more, and more preferably 3% by mass or more. In addition, in consideration of good viscosity, solder heat resistance, and electrical properties, it is preferably 7 mass% or less, and more preferably 6 mass% or less. That is, by setting it within the above range, an adhesive film with excellent solder heat resistance, film handling properties (circuit embedding properties and adhesiveness), and electrical properties can be obtained. The content of the organic solvent is appropriately adjusted depending on the type of organic solvent, film thickness, drying temperature, and drying time.

有機溶劑(e)宜為使酸改性聚烯烴(a)、寡聚伸苯基醚(b)、環氧樹脂(c)及碳二亞胺化合物(d)溶解者。具體而言，可使用例如：苯、甲苯、二甲苯等芳香族烴；己烷、庚烷、辛烷、癸烷等脂肪族系烴；環己烷、環己烯、甲基環己烷、乙基環己烷等脂環族烴；三氯乙烯、二氯乙烯、氯苯、氯仿等鹵化烴；甲醇、乙醇、異丙醇、丁醇、戊醇、己醇、丙烷二醇、苯酚等醇系溶劑；丙酮、甲基異丁基酮、甲乙酮、戊酮、己酮、環己酮、異佛爾酮、苯乙酮等酮系溶劑；甲基賽璐蘇、乙基賽璐蘇等賽璐蘇類；乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、甲酸丁酯等酯系溶劑；乙二醇單正丁醚、乙二醇單異丁醚、乙二醇單三級丁醚、二乙二醇單正丁醚、二乙二醇單異丁醚、三乙二醇單正丁醚、四乙二醇單正丁醚等二醇醚系溶劑等，它們可使用1種或合併使用2種以上。尤其考量作業環境性、乾燥性，宜為選自於由甲乙酮、甲基環己烷及甲苯構成之群組中之1種以上。The organic solvent (e) is preferably one that dissolves acid-modified polyolefin (a), oligophenylene ether (b), epoxy resin (c) and carbodiimide compound (d). Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; cyclohexane, cyclohexene, methylcyclohexane, Alicyclic hydrocarbons such as ethyl cyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, chloroform; methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propanediol, phenol, etc. Alcohol solvents; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, acetophenone, etc.; methyl cellophane, ethyl cellophane, etc. Cellulose; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc.; ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono Glycol ether solvents such as tertiary butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol mono-n-butyl ether, etc., they can Use 1 type or combine 2 or more types. In particular, considering working environment and drying properties, it is preferably one or more selected from the group consisting of methyl ethyl ketone, methyl cyclohexane, and toluene.

黏接薄膜中之有機溶劑(e)的含量可如下般進行計算。首先，稱量黏接薄膜的質量(A)。然後，使用乾燥器以200℃使該黏接薄膜乾燥10分鐘，再稱量乾燥後的質量(B)。可由下式計算出有機溶劑(e)量。 有機溶劑(e)(質量%)=(1-B/A)×100The content of organic solvent (e) in the adhesive film can be calculated as follows. First, weigh the quality of the adhesive film (A). Then, the adhesive film was dried at 200°C for 10 minutes using a desiccator, and the dried mass (B) was measured. The amount of organic solvent (e) can be calculated by the following formula. Organic solvent (e) (mass%)=(1-B/A)×100

黏接薄膜所含有的有機溶劑(e)為製作黏接薄膜時的清漆所含之有機溶劑的殘留物亦無妨，為製得黏接薄膜後添加的有機溶劑亦無妨。宜為清漆所含之有機溶劑的殘留物。The organic solvent (e) contained in the adhesive film does not matter if it is the residue of the organic solvent contained in the varnish when the adhesive film is made, and it does not matter if the organic solvent is added after the adhesive film is made. It should be the residue of the organic solvent contained in the varnish.

＜黏接薄膜＞ 本發明之黏接薄膜係含有酸改性聚烯烴(a)、數目平均分子量3000以下之寡聚伸苯基醚(b)、環氧樹脂(c)、及碳二亞胺化合物(d)，且含有1～8質量%之有機溶劑(e)的黏接性薄膜。藉由含有前述(a)成分～(e)成分，可展現和聚醯亞胺薄膜、液晶聚合物(LCP)等低極性樹脂基材、金屬基材之優良的黏接性、焊料耐熱性、電特性(低介電特性)、及薄膜操作性。＜Adhesive film＞ The adhesive film of the present invention contains acid-modified polyolefin (a), oligophenylene ether (b) with a number average molecular weight of 3000 or less, epoxy resin (c), and carbodiimide compound (d), An adhesive film containing 1-8% by mass of organic solvent (e). By containing the aforementioned components (a) to (e), it can exhibit excellent adhesion, solder heat resistance, Electrical properties (low dielectric properties), and film handling.

黏接薄膜可藉由將係為黏接薄膜之源的清漆(以下也簡稱清漆)塗佈於基材並乾燥，再將前述基材剝離而得。清漆係指將前述(a)成分～(d)成分以有機溶劑溶解或分散而成者。清漆所含的有機溶劑相對於酸改性聚烯烴(a)100質量份，宜為100～1000質量份之範圍，為200～900質量份之範圍更佳，為300～800質量份之範圍最佳。藉由設定為前述範圍內，則塗覆安定性良好，就成本方面亦為有利。清漆所含的有機溶劑宜和前述有機溶劑(e)相同。The adhesive film can be obtained by applying a varnish (hereinafter also referred to as varnish), which is the source of the adhesive film, on the substrate and drying, and then peeling off the substrate. The varnish refers to the one obtained by dissolving or dispersing the aforementioned (a) component to (d) component in an organic solvent. The organic solvent contained in the varnish is preferably in the range of 100 to 1000 parts by mass, more preferably in the range of 200 to 900 parts by mass, with respect to 100 parts by mass of the acid-modified polyolefin (a), preferably in the range of 300 to 800 parts by mass. good. By setting it within the aforementioned range, coating stability is good, which is also advantageous in terms of cost. The organic solvent contained in the varnish is preferably the same as the aforementioned organic solvent (e).

黏接薄膜的厚度並無特別限制，宜為5～200μm。考量改善黏接強度的情況，為10μm以上更佳，為15μm以上再更佳，為20μm以上特佳。又，考量更容易控制乾燥步驟之有機溶劑(e)的含量之情況，為150μm以下更佳，為100μm以下再更佳，為50μm以下特佳。The thickness of the adhesive film is not particularly limited, but is preferably 5 to 200 μm. Considering the improvement of the bonding strength, 10 μm or more is more preferable, 15 μm or more is even more preferable, and 20 μm or more is particularly preferable. In addition, considering that it is easier to control the content of the organic solvent (e) in the drying step, it is more preferably 150 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less.

就本發明之黏接薄膜而言，該黏接薄膜在硬化後於頻率1GHz的相對介電常數(εc )宜為3.0以下。為2.6以下更佳，為2.3以下再更佳。下限並無特別限制，於實用上為2.0。又，於頻率1GHz～30GHz之全區域的介電常數(ε)宜為3.0以下，為2.6以下更佳，為2.3以下再更佳。For the adhesive film of the present invention, the relative dielectric constant (ε c ) of the adhesive film at a frequency of 1 GHz after curing is preferably 3.0 or less. It is more preferably 2.6 or less, and even more preferably 2.3 or less. The lower limit is not particularly limited, but it is 2.0 in practice. In addition, the dielectric constant (ε) in the entire frequency range of 1 GHz to 30 GHz is preferably 3.0 or less, more preferably 2.6 or less, and even more preferably 2.3 or less.

就本發明之黏接薄膜而言，該黏接薄膜在硬化後於頻率1GHz的介電損耗正切(tanδ)宜為0.02以下。為0.01以下更佳，為0.008以下再更佳。下限並無特別限制，於實用上為0.0001。又，於頻率1GHz～30GHz之全區域的介電損耗正切(tanδ)宜為0.02以下，為0.01以下更佳，為0.05以下再更佳。For the adhesive film of the present invention, the dielectric loss tangent (tanδ) of the adhesive film at a frequency of 1 GHz after curing is preferably 0.02 or less. It is more preferably 0.01 or less, and even more preferably 0.008 or less. The lower limit is not particularly limited, but it is 0.0001 in practice. In addition, the dielectric loss tangent (tan δ) in the entire frequency range of 1 GHz to 30 GHz is preferably 0.02 or less, more preferably 0.01 or less, and even more preferably 0.05 or less.

本發明中，相對介電常數(εc )及介電損耗正切(tanδ)可如下進行測定。亦即，將黏接薄膜於約140℃進行熱處理約4小時並使其硬化(以下也簡稱硬化處理)，並測定硬化後之黏接薄膜於頻率1GHz的相對介電常數(εc )。具體而言，可利用蒸鍍、濺鍍法等薄膜法、或導電性糊劑之塗佈等方法於黏接薄膜的雙面形成金屬層並製成電容器，測定靜電電容並由厚度與面積計算出相對介電常數(εc )及介電損耗正切(tanδ)。又，黏接薄膜係和基材(脫模基材)成為疊層體時，可於基材剝離後僅對黏接薄膜進行硬化處理，也可直接對疊層體進行硬化處理後，再將基材剝離。In the present invention, the relative dielectric constant (ε c ) and the dielectric loss tangent (tan δ) can be measured as follows. That is, the adhesive film is heat-treated at about 140° C. for about 4 hours and cured (hereinafter also referred to as curing treatment), and the relative dielectric constant (ε c ) of the cured adhesive film at a frequency of 1 GHz is measured. Specifically, thin film methods such as vapor deposition, sputtering, or conductive paste coating can be used to form a metal layer on both sides of the adhesive film to form a capacitor. The electrostatic capacitance can be measured and calculated from the thickness and area. Relative permittivity (ε c ) and dielectric loss tangent (tanδ). In addition, when the adhesive film system and the base material (release base material) become a laminate, the adhesive film can be cured only after the base material is peeled off, or the laminate can be directly cured before the The substrate peels off.

又，本發明之黏接薄膜也可因應需要更含有其它成分。如此的成分之具體例可列舉：阻燃劑、賦黏劑、填料、矽烷偶聯劑。黏接薄膜含有前述其它成分時，宜事先使其含於係為黏接薄膜之源的清漆中。In addition, the adhesive film of the present invention can also contain other ingredients as needed. Specific examples of such components include flame retardants, tackifiers, fillers, and silane coupling agents. When the adhesive film contains the aforementioned other ingredients, it is preferable to preliminarily contain it in the varnish that is the source of the adhesive film.

＜阻燃劑＞ 本發明之黏接薄膜也可因應需要摻合阻燃劑。阻燃劑可列舉：溴系、磷系、氮系、氫氧化金屬化合物等。其中，宜為磷系阻燃劑，可使用：磷酸酯(例如磷酸三甲酯、磷酸三苯酯、磷酸三甲酚酯等)、磷酸鹽(例如次磷酸鋁等)、膦氮烯等公知的磷系阻燃劑。它們可單獨使用，也可任意組合使用2種以上。含有阻燃劑時，相對於(a)～(d)成分之合計100質量份，阻燃劑的含量宜為1～200質量份之範圍，為5～150質量份之範圍更佳，為10～100質量份之範圍最佳。藉由設定為前述範圍內，可維持黏接性、焊料耐熱性及電特性，同時可展現阻燃性。＜Flame Retardant＞ The adhesive film of the present invention can also be blended with flame retardants as needed. Examples of flame retardants include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds. Among them, phosphorus-based flame retardants are preferable, and well-known phosphoric acid esters (such as trimethyl phosphate, triphenyl phosphate, tricresol phosphate, etc.), phosphates (such as aluminum hypophosphite, etc.), phosphazene, etc. can be used. Phosphorus flame retardant. These may be used alone or in any combination of two or more kinds. When a flame retardant is contained, the content of the flame retardant is preferably in the range of 1 to 200 parts by mass, and more preferably in the range of 5 to 150 parts by mass, relative to 100 parts by mass of the total of components (a) to (d), 10 The range of ～100 parts by mass is the best. By setting it within the aforementioned range, adhesion, solder heat resistance, and electrical properties can be maintained, while flame retardancy can be exhibited.

＜賦黏劑＞ 本發明之黏接薄膜也可因應需要摻合賦黏劑。賦黏劑可列舉：聚萜烯樹脂、松香系樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、共聚合系石油樹脂、苯乙烯樹脂及氫化石油樹脂等，可為了使黏接強度改善而使用。它們可單獨使用，也可任意組合使用2種以上。含有賦黏劑時，相對於(a)～(d)成分之合計100質量份，賦黏劑含量宜為1～200質量份之範圍，為5～150質量份之範圍更佳，為10～100質量份之範圍最佳。藉由設定為前述範圍內，可維持黏接性、焊料耐熱性及電特性，同時可展現賦黏劑的效果。＜Tackifier＞ The adhesive film of the present invention can also be blended with a tackifier as needed. Examples of tackifiers include polyterpene resins, rosin-based resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymerized petroleum resins, styrene resins, hydrogenated petroleum resins, etc., which can be used to improve bonding strength And use. These may be used alone or in any combination of two or more kinds. When a tackifier is contained, the content of the tackifier is preferably in the range of 1 to 200 parts by mass, more preferably in the range of 5 to 150 parts by mass, and more preferably in the range of 10 to 100 parts by mass of the total of components (a) to (d). The range of 100 parts by mass is the best. By setting it within the aforementioned range, the adhesiveness, solder heat resistance, and electrical properties can be maintained while exhibiting the effect of the tackifier.

＜填料＞ 本發明之黏接薄膜也可因應需要摻合二氧化矽等填料。藉由摻合二氧化矽，會改善耐熱性之特性，故非常理想。二氧化矽通常已知有疏水性二氧化矽、及親水性二氧化矽，在此就賦予耐吸濕性方面，以二甲基二氯矽烷、或六甲基二矽氮烷、辛基矽烷等實施處理後之疏水性二氧化矽較佳。摻合二氧化矽時，其摻合量相對於(a)～(d)成分之合計100質量份，宜為0.05～30質量份之摻合量。藉由設定為前述下限值以上，可展現更進一步的耐熱性。又，藉由設定為前述上限值以下，會抑制清漆因二氧化矽而分散不良、或溶液黏度變得過高，並使作業性良好。＜Filling＞ The adhesive film of the present invention can also be blended with fillers such as silica as needed. By blending silicon dioxide, it will improve the characteristics of heat resistance, so it is very ideal. Silicon dioxide is generally known as hydrophobic silicon dioxide and hydrophilic silicon dioxide. In terms of moisture absorption resistance, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. The hydrophobic silica after treatment is preferred. When silicon dioxide is blended, the blending amount is preferably 0.05-30 parts by mass relative to 100 parts by mass of the total of components (a) to (d). By setting it to above the aforementioned lower limit value, further heat resistance can be exhibited. In addition, by setting it to the upper limit or less, it is possible to suppress poor dispersion of the varnish due to silica, or excessively high solution viscosity, and to improve workability.

＜矽烷偶聯劑＞ 本發明之黏接薄膜也可因應需要摻合矽烷偶聯劑。藉由摻合矽烷偶聯劑，會改善對金屬之黏接性、或耐熱性之特性，故非常理想。矽烷偶聯劑並無特別限制，可列舉：具有不飽和基者、具有環氧丙基者、具有胺基者等。它們之中，考慮耐熱性之觀點，為γ-環氧丙氧基丙基三甲氧基矽烷、或β-(3,4-環氧環己基)乙基三甲氧基矽烷、或β-(3,4-環氧環己基)乙基三乙氧基矽烷等具有環氧丙基之矽烷偶聯劑再更佳。摻合矽烷偶聯劑時，其摻合量相對於(a)～(d)成分之合計100質量份，宜為0.5～20質量份之摻合量。藉由設定為前述範圍內，可使焊料耐熱性、黏接性改善。＜Silane Coupling Agent＞ The adhesive film of the present invention can also be blended with a silane coupling agent as needed. By blending the silane coupling agent, the adhesion to metal or the characteristics of heat resistance will be improved, so it is very ideal. The silane coupling agent is not particularly limited, and examples thereof include those having unsaturated groups, those having glycidyl groups, and those having amine groups. Among them, considering the viewpoint of heat resistance, γ-glycidoxypropyltrimethoxysilane, or β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or β-(3 , 4-epoxycyclohexyl) ethyl triethoxy silane and other silane coupling agents with glycidyl groups are even more preferable. When the silane coupling agent is blended, the blending amount is preferably 0.5-20 parts by mass relative to 100 parts by mass of the total of components (a) to (d). By setting it within the aforementioned range, the solder heat resistance and adhesiveness can be improved.

＜疊層體＞ 本發明之疊層體係於基材疊層黏接薄膜而成者(基材/黏接薄膜之2層疊層體)、或更進一步貼合基材而成者(基材/黏接薄膜/基材之3層疊層體)。藉由將本發明之係為黏接薄膜之源的清漆，依循常法塗佈於各種基材並進行乾燥，以及更進一步疊層其它基材，可獲得本發明之疊層體。又，也可藉由將黏接薄膜貼合於基材並進行疊層而獲得。＜Laminated body＞ The laminated system of the present invention is formed by laminating an adhesive film on a substrate (a two-layer laminate of substrate/adhesive film), or a substrate formed by laminating a substrate (substrate/adhesive film/base) Material of 3 laminates). The laminate of the present invention can be obtained by applying the varnish of the present invention, which is the source of the adhesive film, to various substrates according to the usual method and drying, and further laminating other substrates. Moreover, it can also be obtained by laminating|stacking an adhesive film to a base material.

＜基材＞ 本發明中基材若為可貼合本發明之黏接薄膜並進行疊層者、或可塗佈係為黏接薄膜之源的清漆並進行乾燥而形成黏接薄膜層者，則無特別限制，可列舉：薄膜狀樹脂等樹脂基材、金屬板或金屬箔等金屬基材、紙類等。＜Substrate＞ In the present invention, if the substrate can be laminated with the adhesive film of the present invention and laminated, or can be coated with a varnish that is the source of the adhesive film and dried to form an adhesive film layer, there is no particular limitation Examples include resin substrates such as film-like resins, metal substrates such as metal plates or metal foils, papers, and the like.

樹脂基材可例示：聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂、及氟系樹脂等。宜為薄膜狀樹脂(以下也稱為基材薄膜層)。Examples of resin substrates include polyester resins, polyamide resins, polyimide resins, polyimide resins, liquid crystal polymers, polyphenylene sulfide, parapolystyrene, polyolefin resins, and Fluorine resin etc. It is preferably a film-like resin (hereinafter also referred to as a base film layer).

金屬基材可使用能使用於電路基板之任意的習知導電性材料。材料可例示：SUS、銅、鋁、鐵、鋼、鋅、鎳等各種金屬、及以各別的合金、鍍敷物、鋅或鉻化合物等其它金屬處理後之金屬等。宜為金屬箔，為銅箔更佳。金屬箔的厚度並無特別限制，宜為1μm以上，為3μm以上更佳，為10μm以上再更佳。又，宜為50μm以下，為30μm以下更佳，為20μm以下再更佳。厚度過薄時，有時會有電路不易獲得充分的電氣性能之情況，另一方面，厚度過厚時，有時會有製作電路時之加工效率等降低的情況。金屬箔通常係以輥狀的形態予以提供。製造本發明之印刷配線板時所使用的金屬箔之形態並無特別限制。使用條帶狀之形態的金屬箔時，其長度並無特別限制。又，其寬亦無特別限制，宜為約250～500cm。Any conventional conductive material that can be used for circuit substrates can be used for the metal substrate. Examples of materials include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, and metals treated with various alloys, platings, and other metals such as zinc or chromium compounds. It is preferably a metal foil, and more preferably a copper foil. The thickness of the metal foil is not particularly limited, and is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 10 μm or more. Moreover, it is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. When the thickness is too thin, it may be difficult for the circuit to obtain sufficient electrical performance. On the other hand, when the thickness is too thick, the processing efficiency when making the circuit may be reduced. Metal foil is usually provided in the form of a roll. The form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited. When using the metal foil in the form of a strip, its length is not particularly limited. In addition, the width is not particularly limited, but it is preferably about 250 to 500 cm.

紙類可例示：優質紙、牛皮紙、紙捲、玻璃紙等。又，複合材料可例示：玻璃環氧樹脂等。Examples of paper: high-quality paper, kraft paper, paper rolls, cellophane, etc. In addition, the composite material can be exemplified by glass epoxy resin and the like.

考量和黏接薄膜之黏接力、耐久性，基材宜為聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂、氟系樹脂、SUS鋼板、銅箔、鋁箔、或玻璃環氧樹脂。Considering the adhesion and durability of the adhesive film, the base material should be polyester resin, polyamide resin, polyimide resin, polyimide resin, liquid crystal polymer, polyphenylene sulfide, and parallel Polystyrene, polyolefin resin, fluorine resin, SUS steel plate, copper foil, aluminum foil, or glass epoxy resin.

＜黏接片＞ 本發明中，黏接片係將前述疊層體及脫模基材藉由黏接薄膜而進行疊層者。具體的構成態樣可列舉：疊層體/黏接薄膜層/脫模基材、或脫模基材/黏接薄膜層/疊層體/黏接薄膜層/脫模基材。藉由疊層脫模基材，會作為基材的保護層而發揮功能。又，藉由使用脫模基材，可將脫模基材從黏接片予以脫模，再將黏接薄膜層轉印於另一基材。＜Adhesive sheet＞ In the present invention, the adhesive sheet is obtained by laminating the aforementioned laminated body and the release substrate by an adhesive film. Specific structural aspects include: laminate/adhesive film layer/release substrate, or release substrate/adhesive film layer/layer laminate/adhesive film layer/release substrate. By laminating the release base material, it functions as a protective layer of the base material. In addition, by using a release substrate, the release substrate can be released from the adhesive sheet, and then the adhesive film layer can be transferred to another substrate.

可藉由將本發明之疊層體和基材進行貼合，也可藉由將係為黏接薄膜之源的清漆依循常法塗佈於各種疊層體並進行乾燥來獲得本發明之黏接片。又，於乾燥後，將脫模基材貼附於黏接薄膜層的話，能在不造成背印至基材的情況下進行捲繞，作業性優良，同時黏接薄膜層受到保護，故保存性優良，使用也容易。又，若塗佈於脫模基材並進行乾燥後，因應需要再貼附於另一脫模基材，則也可將黏接薄膜層自身轉印於其它基材。The laminate of the present invention can be laminated to the substrate, or the varnish, which is the source of the adhesive film, can be applied to various laminates in a usual manner and dried to obtain the adhesive of the present invention. Splice. In addition, if the release base material is attached to the adhesive film layer after drying, it can be wound without causing back printing to the base material. The workability is excellent, and the adhesive film layer is protected, so it is stored Excellent performance and easy to use. In addition, if it is applied to a release substrate and dried, and then attached to another release substrate as needed, the adhesive film layer itself can also be transferred to another substrate.

＜脫模基材＞ 脫模基材並無特別限制，可列舉例如於優質紙、牛皮紙、紙捲、玻璃紙等紙的雙面設置黏土、聚乙烯、聚丙烯等填平劑之塗佈層，再於該各塗佈層之上塗佈聚矽氧系、氟系、醇酸系之脫模劑而成者。又，也可列舉：聚乙烯、聚丙烯、乙烯-α-烯烴共聚物、丙烯-α-烯烴共聚物等單獨之各種烯烴薄膜；以及於聚對苯二甲酸乙二酯等薄膜上塗佈上述脫模劑而成者。考量脫模基材與黏接劑層之脫模力、聚矽氧會對電特性造成不良影響等理由，宜為於優質紙之雙面進行聚丙烯填平處理，並於其上使用醇酸系脫模劑而成者、或於聚對苯二甲酸乙二酯上使用醇酸系脫模劑而成者。＜Release base material＞ The release substrate is not particularly limited. For example, a coating layer of clay, polyethylene, polypropylene and other fillers is provided on both sides of high-quality paper, kraft paper, paper roll, cellophane, etc., and then applied to each It is formed by coating silicone, fluorine, and alkyd release agents on the layer. In addition, various olefin films such as polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and the like; and coating the above-mentioned films on polyethylene terephthalate, etc. Those made of release agent. Considering the demolding force of the mold release substrate and the adhesive layer, and the adverse effects of polysiloxane on the electrical properties, etc., it is advisable to fill in polypropylene on both sides of high-quality paper and use alkyd on it. It is made of a mold release agent, or a polyethylene terephthalate is made of an alkyd mold release agent.

另外，將本發明中係為黏接薄膜之源的清漆塗佈於基材上之方法塗佈於基材上之方法並無特別限制，可列舉：逗塗、逆輥塗等。或也可因應需要於作為構成印刷配線板之材料的壓延銅箔、或於聚醯亞胺薄膜直接設置黏接薄膜層或以轉印法設置黏接薄膜層。乾燥後之黏接劑層的厚度係因應需要而適當地變化，宜為5～200μm之範圍。藉由將黏接薄膜厚設定為5μm以上，可獲得充分的黏接強度。又，藉由設定為200μm以下，可輕易控制乾燥步驟的殘留溶劑量。乾燥條件若為適當地調整俾使有機溶劑(e)的含量成為1～8質量%，則無特別限制。In addition, the method of applying the varnish, which is the source of the adhesive film in the present invention, to the substrate is not particularly limited. The method of applying the varnish to the substrate is not particularly limited, and examples thereof include: coating, reverse roll coating, and the like. Or, according to needs, an adhesive film layer can be directly provided on the rolled copper foil, which is a material constituting a printed wiring board, or a polyimide film, or an adhesive film layer can be provided by a transfer method. The thickness of the adhesive layer after drying is appropriately changed according to needs, and is preferably in the range of 5 to 200 μm. By setting the thickness of the bonding film to 5μm or more, sufficient bonding strength can be obtained. In addition, by setting it to 200 μm or less, the amount of residual solvent in the drying step can be easily controlled. The drying conditions are not particularly limited as long as they are appropriately adjusted so that the content of the organic solvent (e) becomes 1 to 8% by mass.

＜印刷配線板＞ 本發明中的「印刷配線板」含有由形成導體電路之金屬箔與樹脂基材形成的疊層體作為構成元件。印刷配線板例如使用覆金屬疊層體並利用減去法等習知的方法來製造。因應需要將利用金屬箔形成的導體電路使用覆蓋薄膜、網版印刷印墨等部分地或全面地予以被覆而成之所謂統稱撓性電路板(FPC)、扁平纜線、捲帶式自動接合(TAB)用之電路板等。＜Printed wiring board＞ The "printed wiring board" in the present invention contains a laminate composed of a metal foil forming a conductor circuit and a resin substrate as a constituent element. The printed wiring board is manufactured by a conventional method such as a subtraction method using a metal-clad laminate, for example. According to the needs, the conductor circuit formed by the metal foil is partially or completely coated with a cover film, screen printing ink, etc., which is collectively referred to as a flexible circuit board (FPC), flat cable, and tape-type automatic bonding ( TAB) used circuit boards, etc.

本發明之印刷配線板可製成能被採用作為印刷配線板之任意疊層構成。例如可製成由基材薄膜層、金屬箔層、黏接薄膜層、及覆蓋薄膜層之4層構成的印刷配線板。又，例如可製成由基材薄膜層、黏接薄膜層、金屬箔層、黏接薄膜層、及覆蓋薄膜層之5層構成的印刷配線板。The printed wiring board of the present invention can be made into any laminated structure that can be used as a printed wiring board. For example, it can be made into a printed wiring board composed of four layers of a base film layer, a metal foil layer, an adhesive film layer, and a cover film layer. In addition, for example, a printed wiring board composed of five layers of a base film layer, an adhesive film layer, a metal foil layer, an adhesive film layer, and a cover film layer can be produced.

此外，也可因應需要製成將2個或3個以上之上述印刷配線板疊層而成的構成。In addition, it can also be made into a structure in which two or three or more of the above-mentioned printed wiring boards are laminated as required.

本發明之黏接薄膜可理想地使用於印刷配線板之黏接層。尤其使用本發明之黏接薄膜的話，不僅和構成印刷配線板之習知的聚醯亞胺、聚酯薄膜、銅箔，也和LCP等低極性之樹脂基材具有高黏接性，且可獲得耐焊料回焊性，黏接層本身為低介電特性優良。因此，適合作為覆蓋層薄膜、疊層板、及設有樹脂之銅箔所使用的黏接薄膜。The adhesive film of the present invention can be ideally used in the adhesive layer of a printed wiring board. In particular, when the adhesive film of the present invention is used, it not only has high adhesion to the conventional polyimide, polyester film, and copper foil constituting printed wiring boards, but also low-polarity resin substrates such as LCP. The solder reflow resistance is obtained, and the adhesive layer itself has excellent low dielectric properties. Therefore, it is suitable as an adhesive film for cover film, laminated board, and copper foil provided with resin.

本發明之印刷配線板中，基材薄膜可使用自以往即已被使用作為印刷配線板之基材的任意樹脂薄膜。基材薄膜之樹脂可例示：聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂、及氟系樹脂等。尤其對於液晶聚合物、聚苯硫醚、對排聚苯乙烯、聚烯烴系樹脂等低極性基材亦具有優良的黏接性。In the printed wiring board of the present invention, any resin film that has been used as a substrate of a printed wiring board from the past can be used as the base film. The resin of the substrate film can be exemplified: polyester resin, polyamide resin, polyimide resin, polyimide resin, liquid crystal polymer, polyphenylene sulfide, parapolystyrene, polyolefin resin , And fluorine-based resins, etc. In particular, it has excellent adhesion to low-polarity substrates such as liquid crystal polymer, polyphenylene sulfide, para-polystyrene, and polyolefin resin.

＜覆蓋薄膜＞ 覆蓋薄膜可使用習知作為印刷配線板用之絕緣薄膜的任意絕緣薄膜。例如可使用由聚醯亞胺、聚酯、聚苯硫醚、聚醚碸、聚醚醚酮、芳香族聚醯胺、聚碳酸酯、聚芳酯、聚醯胺醯亞胺、液晶聚合物、對排聚苯乙烯、聚烯烴系樹脂等各種聚合物製造而得的薄膜。為聚醯亞胺薄膜或液晶聚合物薄膜更佳。＜Cover film＞ As the cover film, any insulating film conventionally used as an insulating film for printed wiring boards can be used. For example, polyimide, polyester, polyphenylene sulfide, polyether ether, polyether ether ketone, aromatic polyamide, polycarbonate, polyarylate, polyamide imide, liquid crystal polymer can be used , Parallel polystyrene, polyolefin resin and other polymers made of films. It is more preferably a polyimide film or a liquid crystal polymer film.

本發明之印刷配線板除了使用上述各層之材料以外，也可使用習知之任意製程來製造。The printed wiring board of the present invention can be manufactured using any conventional manufacturing process in addition to the materials of the above-mentioned layers.

理想的實施態樣係製造將黏接薄膜層疊層於覆蓋薄膜層而成的半成品(以下稱為「覆蓋薄膜側半成品」)。另外，製造將金屬箔層疊層於基材薄膜層並形成期望的電路圖案之半成品(以下稱為「基材薄膜側2層半成品」)或將黏接薄膜層疊層於基材薄膜層，並於其上疊層金屬箔層後形成期望的電路圖案之半成品(以下稱為「基材薄膜側3層半成品」)(以下將基材薄膜側2層半成品及基材薄膜側3層半成品合稱為「基材薄膜側半成品」)。藉由將以此方式得到的覆蓋薄膜側半成品與基材薄膜側半成品進行貼合，可獲得4層或5層之印刷配線板。An ideal embodiment is to manufacture a semi-finished product in which an adhesive film is laminated on a cover film layer (hereinafter referred to as "cover film-side semi-finished product"). In addition, a semi-finished product in which a metal foil is laminated on the base film layer and a desired circuit pattern is formed (hereinafter referred to as "the two-layer semi-finished product on the base film side") or an adhesive film is laminated on the base film layer, and used A semi-finished product (hereinafter referred to as "3-layer semi-finished product on the base film side") on which a metal foil layer is laminated to form the desired circuit pattern (hereinafter referred to as the two-layer semi-finished product on the substrate film side and the 3-layer semi-finished product on the substrate film side are collectively referred to as "Substrate film side semi-finished products"). By laminating the semi-finished product on the cover film side and the semi-finished product on the base film side obtained in this way, a 4-layer or 5-layer printed wiring board can be obtained.

基材薄膜側半成品例如可利用包含(A)將成為基材薄膜之樹脂溶液塗佈於前述金屬箔，並使塗膜進行初期乾燥之步驟、及(B)對(A)得到的金屬箔與初始乾燥塗膜的疊層物進行熱處理、乾燥之步驟(以下稱為「熱處理-脫溶劑步驟」)之製造法獲得。The semi-finished product on the substrate film side can be, for example, a step of applying (A) a resin solution that becomes a substrate film to the aforementioned metal foil and subjecting the coating film to initial drying, and (B) the metal foil obtained from (A) and The laminate of the initially dried coating film is obtained by a manufacturing method of heat treatment and drying steps (hereinafter referred to as "heat treatment-solvent removal step").

金屬箔層中的電路之形成可使用習知的方法。可使用加成法，也可使用減去法。宜為減去法。A conventional method can be used to form the circuit in the metal foil layer. Additive or subtractive methods can be used. It should be the subtraction method.

得到的基材薄膜側半成品可直接使用於和覆蓋薄膜側半成品之貼合，也可貼合脫模薄膜予以保存後，再使用於和覆蓋薄膜側半成品之貼合。The obtained base film side semi-finished product can be directly used for bonding with the cover film side semi-finished product, or it can be pasted with a release film for storage, and then used for bonding with the cover film side semi-finished product.

覆蓋薄膜側半成品例如將係為黏接薄膜之源的清漆塗佈於覆蓋薄膜來製造。因應需要可實施黏接薄膜層之硬化。在理想的實施態樣中，係使黏接薄膜層半硬化。The semi-finished product on the cover film side, for example, is manufactured by applying a varnish that is the source of the adhesive film to the cover film. The hardening of the adhesive film layer can be implemented according to the needs. In an ideal embodiment, the adhesive film layer is semi-hardened.

得到的覆蓋薄膜側半成品可直接使用於和基材薄膜側半成品之貼合，也可貼合脫模薄膜予以保存後，再使用於和基材薄膜側半成品之貼合。The obtained cover film side semi-finished product can be directly used for bonding with the base film side semi-finished product, or it can be pasted with a release film for storage, and then used for bonding with the base film side semi-finished product.

基材薄膜側半成品及覆蓋薄膜側半成品係分別例如以輥的形態予以保存後，再進行貼合來製造印刷配線板。貼合方法可使用任意的方法，例如可使用壓製或輥等來使其貼合。又，也可利用加熱壓製、或使用加熱輥裝置等方法邊實施加熱邊使兩者貼合。The semi-finished product on the base film side and the semi-finished product on the cover film side are respectively stored in the form of a roll, for example, and then laminated to manufacture a printed wiring board. Any method may be used for the bonding method, and for example, pressing or a roll may be used for bonding. In addition, it is also possible to bond the two while applying heating by a method such as heating and pressing or using a heating roller device.

補強材側半成品例如在聚醯亞胺薄膜之類柔軟可捲繞之補強材的情況，宜將係為黏接薄膜之源的清漆塗佈於補強材來製造。又，例如在SUS、鋁等金屬板、利用環氧樹脂使玻璃纖維硬化而成的板等之類硬而不可捲繞之補強板的情況，宜藉由事先轉印塗佈設有脫模基材之黏接薄膜來製造。又，因應需要可實施黏接薄膜層之硬化。在理想的實施態樣中，係使黏接薄膜層半硬化。The semi-finished product on the side of the reinforcing material, for example, in the case of a flexible and windable reinforcing material such as a polyimide film, is preferably manufactured by applying a varnish that is the source of the adhesive film to the reinforcing material. In addition, for example, in the case of SUS, aluminum and other metal plates, plates made by curing glass fiber with epoxy resin, etc., which are hard and unwindable, it is advisable to set a mold release base by transfer coating in advance. It is made by bonding film of materials. In addition, curing of the adhesive film layer can be implemented according to needs. In an ideal embodiment, the adhesive film layer is semi-hardened.

得到的補強材側半成品可直接使用於和印刷配線板背面之貼合，也可貼合脫模薄膜予以保存後，再使用於和基材薄膜側半成品之貼合。The obtained reinforcing material side semi-finished product can be directly used for bonding to the back of the printed wiring board, or it can be pasted with a release film for storage, and then used for bonding to the base film side semi-finished product.

基材薄膜側半成品、覆蓋薄膜側半成品、補強材側半成品均為本發明中的印刷配線板用疊層體。The semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the reinforcing material side are all laminates for printed wiring boards in the present invention.

＜實施例＞ 以下，舉實施例更詳細地說明本發明。惟，本發明不受實施例限制。實施例中及比較例中略以份表示質量份。<Example> Hereinafter, the present invention will be explained in more detail with examples. However, the present invention is not limited by the embodiments. In the examples and comparative examples, the parts by mass are abbreviated as parts.

(物性評價方法)(Physical property evaluation method)

[酸價(a)成分：酸改性聚烯烴] 本發明中的酸價(mgKOH/g)係將酸改性聚烯烴溶解於甲苯，並以酚酞作為指示劑滴定甲醇鈉之甲醇溶液。[Acid value (a) component: acid-modified polyolefin] The acid value (mgKOH/g) in the present invention is that the acid-modified polyolefin is dissolved in toluene, and the methanol solution of sodium methoxide is titrated with phenolphthalein as an indicator.

[數目平均分子量(Mn)] 本發明中的數目平均分子量係利用島津製作所(股)製凝膠滲透層析儀(以下稱GPC，標準物質：聚苯乙烯樹脂，移動相：四氫呋喃，管柱：Shodex KF-802 + KF-804L + KF-806L，管柱溫度：30℃，流速：1.0ml/分鐘，檢測器：RI檢測器)測得的值。[Number average molecular weight (Mn)] The number average molecular weight in the present invention uses a gel permeation chromatograph manufactured by Shimadzu Corporation (hereinafter referred to as GPC, standard material: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 + KF-804L) + KF-806L, column temperature: 30°C, flow rate: 1.0ml/min, detector: RI detector).

[熔點、熔解熱之測定] 本發明中的熔點、熔解熱係使用差示掃描熱量計(以下稱DSC，TA Instruments Japan製，Q-2000)，以20℃/分鐘之速度進行昇溫熔解，並予以冷卻樹脂化後，由再度昇溫熔解時之熔解峰部的峰值溫度及面積測得的值。[Determination of melting point and heat of fusion] The melting point and heat of fusion in the present invention are based on a differential scanning calorimeter (hereinafter referred to as DSC, manufactured by TA Instruments Japan, Q-2000). The temperature is raised and melted at a rate of 20°C/min, and the resin is cooled and then converted into a resin. The value measured at the peak temperature and area of the melting peak at the time of heating and melting.

(1)乾燥後之黏性 將後述係為黏接薄膜之源的清漆塗佈於厚度12.5μm之聚醯亞胺薄膜(Kaneka股份有限公司製，APICAL(註冊商標))並實施乾燥，使薄膜厚度成為25μm，且成為預定的殘留溶劑量。調整至25℃後，將厚度12.5μm之聚醯亞胺薄膜(Kaneka股份有限公司製，APICAL(註冊商標))輕輕壓抵於得到的設有基材之黏接薄膜的黏接薄膜面，評價貼附情況。評價基準如下所述。 ＜評價基準＞ ◎：無貼附 ○：有一部分貼附 △：有許多貼附 ×：貼附強，不易剝離(1) Viscosity after drying The varnish, which is the source of the adhesive film described later, is applied to a polyimide film (manufactured by Kaneka Co., Ltd., APICAL (registered trademark)) with a thickness of 12.5 μm and dried to make the film thickness 25 μm and become a predetermined The amount of residual solvent. After adjusting to 25°C, a polyimide film (manufactured by Kaneka Co., Ltd., APICAL (registered trademark)) with a thickness of 12.5 μm was gently pressed against the adhesive film surface of the obtained adhesive film with a substrate. Evaluate the attachment situation. The evaluation criteria are as follows. <Evaluation criteria> ◎: No attachment ○: There is a part attached △: There are many stickers ×: strong adhesion, not easy to peel off

(2)電路填埋性 將後述係為黏接薄膜之源的清漆塗佈於厚度12.5μm之聚醯亞胺薄膜(Kaneka股份有限公司製，APICAL(註冊商標))並實施乾燥，使薄膜厚度成為25μm，且成為預定的殘留溶劑量。將得到的設有基材之黏接薄膜和已形成有梳齒圖案之微細電路的單面覆銅疊層板(銅厚12μm，聚醯亞胺薄膜厚25μm，L(線：配線寬)/S(間距：間隔寬)=10/10μm)貼合。貼合係以5kgf/cm2 、80℃、1分鐘、1Torr之條件進行加熱層合，然後利用熱板壓製機以10kgf/cm2 、90℃、1分鐘之條件進行整平。層合後空氣進入線與間距之邊界部分，隔著載體薄膜於100處確認樹脂層中是否有產生氣泡(空隙)。評價基準如下所述。 ＜評價基準＞ ◎：未確認到空隙。 ○：確認有1～2處之空隙。 △：確認有3～5處之空隙。 ×：確認有6處以上之空隙。(2) Circuit burying property. Apply the varnish, which is the source of the adhesive film described later, to a polyimide film (manufactured by Kaneka Co., Ltd., APICAL (registered trademark)) with a thickness of 12.5 μm and dry to make the film thickness It becomes 25 μm, and becomes a predetermined amount of residual solvent. The obtained adhesive film provided with a substrate and a single-sided copper-clad laminate (copper thickness of 12μm, polyimide film thickness of 25μm, L (line: wiring width)/ S (pitch: interval width)=10/10μm) bonding. Laminating is performed by heating and laminating under the conditions of 5kgf/cm 2 , 80°C, 1 minute, and 1 Torr, and then leveling using a hot plate press under the conditions of 10kgf/cm 2 , 90°C, and 1 minute. After lamination, air enters the boundary between the line and the space, and confirm whether there are bubbles (voids) in the resin layer at 100 places through the carrier film. The evaluation criteria are as follows. <Evaluation Criteria> ◎: No voids were confirmed. ○: Confirm that there are 1 to 2 gaps. △: 3 to 5 gaps are confirmed. ×: Confirm that there are more than 6 gaps.

(3)剝離強度(黏接性) 將後述係為黏接薄膜之源的清漆塗佈於厚度12.5μm之聚醯亞胺薄膜(Kaneka股份有限公司製，APICAL(註冊商標))並實施乾燥，使薄膜厚度成為25μm，且成為預定的殘留溶劑量。將得到的設有基材之黏接薄膜和厚度18μm之壓延銅箔(JX金屬股份有限公司製，BHY系列)進行貼合。貼合係以壓延銅箔之光澤面和黏接薄膜接觸的方式來進行，並於160℃、40kgf/cm2 之加壓下壓製30秒鐘進行黏接。然後以140℃熱處理4小時使其硬化，獲得剝離強度評價用樣本。剝離強度係於25℃拉伸聚醯亞胺薄膜，以拉伸速度50mm/min實施90°剝離試驗，並測定剝離強度。該試驗係表示於常溫的黏接強度。 ＜評價基準＞ ◎：1.0N/mm以上 ○：0.8N/mm以上且未達1.0N/mm △：0.5N/mm以上且未達0.8N/mm ×：未達0.5N/mm(3) Peel strength (adhesiveness) The varnish, which is the source of the adhesive film described later, is applied to a polyimide film (manufactured by Kaneka Co., Ltd., APICAL (registered trademark)) with a thickness of 12.5 μm and dried. The thickness of the film is 25 μm, and the amount of residual solvent is predetermined. The obtained adhesive film provided with a substrate and a rolled copper foil (manufactured by JX Metal Co., Ltd., BHY series) with a thickness of 18 μm were bonded together. The bonding is carried out by rolling the glossy surface of the copper foil in contact with the adhesive film, and pressing it at 160°C under a pressure of 40kgf/cm 2 for 30 seconds for bonding. Then, it was heat-treated at 140° C. for 4 hours to be hardened, and a sample for peeling strength evaluation was obtained. For the peel strength, the polyimide film was stretched at 25°C, a 90° peel test was performed at a stretching speed of 50 mm/min, and the peel strength was measured. This test indicates the bonding strength at room temperature. <Evaluation criteria> ◎: 1.0N/mm or more ○: 0.8N/mm or more and less than 1.0N/mm △: 0.5N/mm or more and less than 0.8N/mm ×: less than 0.5N/mm

(4)焊料耐熱性 以和上述剝離強度試驗相同的方法製得樣本，將2.0cm×2.0cm之樣本片於23℃實施2天熟成處理，再使其漂浮於已在280℃熔融的焊料浴中10秒，並確認是否有膨起等外觀變化。 ＜評價基準＞ ◎：無膨起 ○：有一部分膨起 △：有許多膨起 ×：有膨起且變色(4) Solder heat resistance The sample was prepared by the same method as the above peel strength test. The 2.0cm×2.0cm sample piece was aged at 23°C for 2 days, and then floated in a solder bath melted at 280°C for 10 seconds, and confirmed Whether there are changes in appearance such as swelling. <Evaluation criteria> ◎: No swelling ○: Some swelling △: There is a lot of bulging ×: swelling and discoloration

(5)相對介電常數(εc )及介電損耗正切(tanδ) 將後述黏接劑組成物塗佈於厚度100μm之鐵氟龍(註冊商標)片材並實施乾燥，使乾燥硬化後的厚度成為25μm，且成為預定的殘留溶劑量。然後，於140℃熱處理4小時使其硬化後，將鐵氟龍(註冊商標)片材剝離，獲得試驗用之黏接劑樹脂片材(黏接薄膜)。裁切樣本使得到的試驗用黏接劑樹脂片材成為8cm×3mm之條狀，獲得試驗用樣本。介電常數(εc )及介電損耗正切(tanδ)係使用Network Analyzer(Anritsu公司製)，以共振腔擾動法(resonant cavity perturbation method)，於溫度23℃、頻率1GHz之條件進行測定。針對得到的相對介電常數、介電損耗正切係如下般進行評價。 ＜相對介電常數之評價基準＞ ◎：2.3以下 ○：超過2.3且為2.6以下 △：超過2.6且為3.0以下 ×：超過3.0 ＜介電損耗正切之評價基準＞ ◎：0.008以下 ○：超過0.008且為0.01以下 △：超過0.01且為0.02以下 ×：超過0.02(5) Relative permittivity (ε c ) and dielectric loss tangent (tanδ) The adhesive composition described below is applied to a Teflon (registered trademark) sheet with a thickness of 100 μm and dried to dry and harden the The thickness becomes 25 μm and becomes a predetermined amount of residual solvent. Then, after heat treatment at 140°C for 4 hours to harden, the Teflon (registered trademark) sheet was peeled off to obtain an adhesive resin sheet (adhesive film) for testing. The sample was cut so that the obtained test adhesive resin sheet became a strip of 8 cm×3 mm to obtain a test sample. The dielectric constant (ε c ) and the dielectric loss tangent (tan δ) were measured using a Network Analyzer (manufactured by Anritsu) by the resonant cavity perturbation method at a temperature of 23° C. and a frequency of 1 GHz. The obtained relative permittivity and dielectric loss tangent system were evaluated as follows. <Evaluation criteria of relative permittivity> ◎: 2.3 or less ○: more than 2.3 and less than 2.6 △: more than 2.6 and less than 3.0 ×: more than 3.0 <evaluation criteria of dielectric loss tangent> ◎: less than 0.008 ○: more than 0.008 And less than 0.01 △: more than 0.01 and less than 0.02 ×: more than 0.02

[實施例1] 摻合80質量份之CO-1、20質量份之OPE-2St 1200、17質量份之環氧樹脂HP-7200、5質量份之聚碳二亞胺V-09GB、288質量份之甲基環己烷，39質量份之甲乙酮、11質量份之甲苯，再追加94質量份之甲基環己烷作為追加溶劑並使其均勻溶解，藉此製得係為黏接薄膜之源的清漆。支持體薄膜使用厚度12.5μm之聚醯亞胺薄膜的APICAL12.5NPI(Kaneka股份有限公司製，商品名)，塗佈清漆並進行乾燥。以薄膜厚度成為25μm，且殘留溶劑量成為3質量%的方式實施塗佈、乾燥，獲得設有基材之黏接薄膜。乾燥後之黏性、電路填埋性、黏接強度、焊料耐熱性、電特性如表1所示。[Example 1] Blended with 80 parts by mass of CO-1, 20 parts by mass of OPE-2St 1200, 17 parts by mass of epoxy resin HP-7200, 5 parts by mass of polycarbodiimide V-09GB, 288 parts by mass of methyl ring Hexane, 39 parts by mass of methyl ethyl ketone, 11 parts by mass of toluene, and 94 parts by mass of methylcyclohexane were added as an additional solvent and uniformly dissolved to prepare a varnish that is the source of the adhesive film. As the support film, APICAL 12.5NPI (manufactured by Kaneka Co., Ltd., trade name) of a polyimide film with a thickness of 12.5 μm was used, and varnish was applied and dried. Coating and drying were performed so that the film thickness became 25 μm and the amount of residual solvent became 3% by mass to obtain an adhesive film provided with a substrate. After drying, the viscosity, circuit embedding, bonding strength, solder heat resistance, and electrical properties are shown in Table 1.

[實施例2～15] 如表1所示般進行變更，以和實施例1同樣的方法進行實施例2～15。乾燥後之黏性、電路填埋性、黏接強度、焊料耐熱性、電特性如表1所示。[Examples 2-15] The changes were made as shown in Table 1, and Examples 2 to 15 were performed in the same manner as in Example 1. After drying, the viscosity, circuit embedding, bonding strength, solder heat resistance, and electrical properties are shown in Table 1.

[比較例1～7] 如表1所示般進行變更，以和實施例1同樣的方法進行比較例1～7。乾燥後之黏性、電路填埋性、黏接強度、焊料耐熱性、電特性如表1所示。[Comparative Examples 1-7] The changes were made as shown in Table 1, and Comparative Examples 1 to 7 were performed in the same manner as in Example 1. After drying, the viscosity, circuit embedding, bonding strength, solder heat resistance, and electrical properties are shown in Table 1.

[表1] 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 比較例 比較例 比較例 比較例 比較例 比較例 比較例 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 2 3 4 5 6 7 酸改性聚烯烴(a) (質量份) CO-1 (Tm80℃) 80 CO-2 (Tm78℃) 80 CO-3 (Tm80℃) 80 80 70 80 80 80 80 80 80 80 60 90 100 80 100 80 80 80 CO-4 (Tm82℃) 80 寡聚伸苯基醚(b) (質量份) OPE-2St 1200 20 OPE-2St 2200 20 20 20 20 30 20 20 20 20 20 20 20 40 10 20 100 20 20 20 PPO粉末 20 環氧樹脂(c) (質量份) HP-7200 17 17 17 17 17 16 34 17 17 17 17 17 17 HP-7200H 17 22 17 17 17 17 17 17 碳二亞胺化合物(d) (質量份) V-09GB 5 5 5 5 5 5 5 5 5 2 20 5 5 5 5 5 5 5 5 5 V-03 5 溶劑 (質量份) 甲基環己烷 288 288 288 288 288 252 288 288 288 288 288 288 288 216 324 360 288 0 360 288 288 288 甲乙酮 39 39 39 39 39 35 47 39 41 39 39 39 39 31 43 47 39 7 40 39 39 39 甲苯 11 11 11 11 11 17 11 11 11 11 11 11 11 23 6 0 11 56 11 11 11 11 合計固體量 (質量份) 122 122 122 122 122 121 139 122 127 119 137 122 122 122 122 122 117 122 125 122 122 122 合計溶劑量 (質量份) 339 339 339 339 339 304 346 339 341 339 339 339 339 270 373 407 339 64 411 339 339 339 調整前之固體成分濃度 (質量wt%) 26.5 26.5 26.5 26.5 26.5 28.5 28.7 26.5 27.2 26.0 28.8 26.5 26.5 31.1 24.7 23.0 25.7 65.8 23.3 26.5 26.5 26.5 溶劑追加成分 (質量份) 甲基環己烷 94.0 94.0 94.0 94.0 94.0 125.3 147.0 94.0 109.6 83.4 147.2 94.0 94.0 162.8 59.6 25.3 76.3 369.0 31.9 94.0 94.0 94.0 調整後之固體成分濃度 (質量wt%) 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 殘留溶劑(e) (質量wt%) 3 3 3 3 3 3 3 3 3 3 3 3 6 3 3 3 3 3 3 3 0.5 10 乾燥後之黏性 評價 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ◎ △ ○ ○ ○ ○ 溶解不良故無法測定 ◎ × 電路填埋性 評價 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ◎ ○ ○ × ○ × ◎ 黏接強度 (PI/Ad/Cu) 評價 △ ◎ △ ○ △ ◎ △ △ △ △ ◎ △ △ ◎ △ ◎ × × △ △ △ 焊料耐熱性 (PI/Ad/Cu) 評價 △ ◎ ○ ◎ △ ◎ △ △ △ △ △ △ △ ◎ △ × △ △ × ○ × 電特性 介電常數 ○ ◎ ◎ ◎ ○ △ ○ ○ ○ ○ × ○ △ △ ◎ ◎ ◎ ○ ◎ ◎ × 介電損耗正切 ○ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ × ○ △ △ ◎ ◎ ◎ ○ ◎ ◎ × [Table 1] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 2 3 4 5 6 7 Acid-modified polyolefin (a) (parts by mass) CO-1 (Tm80℃) 80 CO-2 (Tm78℃) 80 CO-3 (Tm80℃) 80 80 70 80 80 80 80 80 80 80 60 90 100 80 100 80 80 80 CO-4 (Tm82℃) 80 Oligophenylene ether (b) (parts by mass) OPE-2St 1200 20 OPE-2St 2200 20 20 20 20 30 20 20 20 20 20 20 20 40 10 20 100 20 20 20 PPO powder 20 Epoxy resin (c) (parts by mass) HP-7200 17 17 17 17 17 16 34 17 17 17 17 17 17 HP-7200H 17 twenty two 17 17 17 17 17 17 Carbodiimide compound (d) (parts by mass) V-09GB 5 5 5 5 5 5 5 5 5 2 20 5 5 5 5 5 5 5 5 5 V-03 5 Solvent (parts by mass) Methylcyclohexane 288 288 288 288 288 252 288 288 288 288 288 288 288 216 324 360 288 0 360 288 288 288 Methyl ethyl ketone 39 39 39 39 39 35 47 39 41 39 39 39 39 31 43 47 39 7 40 39 39 39 Toluene 11 11 11 11 11 17 11 11 11 11 11 11 11 twenty three 6 0 11 56 11 11 11 11 Total solid content (parts by mass) 122 122 122 122 122 121 139 122 127 119 137 122 122 122 122 122 117 122 125 122 122 122 Total solvent amount (parts by mass) 339 339 339 339 339 304 346 339 341 339 339 339 339 270 373 407 339 64 411 339 339 339 Solid content concentration before adjustment (mass wt%) 26.5 26.5 26.5 26.5 26.5 28.5 28.7 26.5 27.2 26.0 28.8 26.5 26.5 31.1 24.7 23.0 25.7 65.8 23.3 26.5 26.5 26.5 Additional solvent ingredients (parts by mass) Methylcyclohexane 94.0 94.0 94.0 94.0 94.0 125.3 147.0 94.0 109.6 83.4 147.2 94.0 94.0 162.8 59.6 25.3 76.3 369.0 31.9 94.0 94.0 94.0 Adjusted solid content concentration (mass wt%) twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two twenty two Residual solvent (e) (mass wt%) 3 3 3 3 3 3 3 3 3 3 3 3 6 3 3 3 3 3 3 3 0.5 10 Stickiness after drying Evaluation ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ◎ △ ○ ○ ○ ○ Poorly dissolves so it cannot be measured ◎ X Circuit landfill Evaluation ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ △ ◎ ○ ○ X ○ X ◎ Bonding strength (PI/Ad/Cu) Evaluation △ ◎ △ ○ △ ◎ △ △ △ △ ◎ △ △ ◎ △ ◎ X X △ △ △ Solder heat resistance (PI/Ad/Cu) Evaluation △ ◎ ○ ◎ △ ◎ △ △ △ △ △ △ △ ◎ △ X △ △ X ○ X Electrical characteristics Dielectric constant ○ ◎ ◎ ◎ ○ △ ○ ○ ○ ○ X ○ △ △ ◎ ◎ ◎ ○ ◎ ◎ X Dielectric loss tangent ○ ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ X ○ △ △ ◎ ◎ ◎ ○ ◎ ◎ X

表1所使用的酸改性聚烯烴(a)、寡聚伸苯基醚(b)、環氧樹脂(c)、碳二亞胺化合物(d)係如下者。 (寡聚伸苯基醚(b)) 寡聚伸苯基醚苯乙烯改性品：OPE-2St 1200(三菱瓦斯化學公司製 Mn1000之具有通式(4)之結構的化合物) 寡聚伸苯基醚苯乙烯改性品：OPE-2St 2200(三菱瓦斯化學公司製 Mn2000之具有通式(4)之結構的化合物) 寡聚伸苯基醚：PPO樹脂粉末(SABIC公司製 Mn20000之具有通式(3)之結構的化合物) (環氧樹脂(c)) 雙環戊二烯型環氧樹脂：HP-7200(DIC公司製 環氧當量 259g/eq) 雙環戊二烯型環氧樹脂：HP-7200H(DIC公司製 環氧當量 278g/eq) (碳二亞胺化合物(d)) 碳二亞胺樹脂：V-09GB(日清紡化學公司製 碳二亞胺當量 216g/eq) 碳二亞胺樹脂：V-03(日清紡化學公司製 碳二亞胺當量 209g/eq)The acid-modified polyolefin (a), oligophenylene ether (b), epoxy resin (c), and carbodiimide compound (d) used in Table 1 are as follows. (Oligophenylene ether (b)) Oligophenylene ether styrene modified product: OPE-2St 1200 (Mitsubishi Gas Chemical Corporation Mn1000 compound having the structure of general formula (4)) Oligophenylene ether styrene modified product: OPE-2St 2200 (Mn2000 manufactured by Mitsubishi Gas Chemical Company, a compound having a structure of general formula (4)) Oligomer phenylene ether: PPO resin powder (manufactured by SABIC Corporation Mn20000 compound with the structure of general formula (3)) (Epoxy resin (c)) Dicyclopentadiene epoxy resin: HP-7200 (manufactured by DIC, epoxy equivalent 259g/eq) Dicyclopentadiene epoxy resin: HP-7200H (manufactured by DIC, epoxy equivalent 278g/eq) (Carbodiimide compound (d)) Carbodiimide resin: V-09GB (manufactured by Nisshinbo Chemical Co., carbodiimide equivalent 216g/eq) Carbodiimide resin: V-03 (manufactured by Nisshinbo Chemical Co., carbodiimide equivalent 209g/eq)

(酸改性聚烯烴(a)) [製造例1] 於1L之高溫高壓釜(autoclave)中，添加100質量份之丙烯-丁烯共聚物(三井化學公司製「TAFMER(註冊商標)XM7080」)、150質量份之甲苯及19質量份之馬來酸酐、6質量份之二(三級丁基)過氧化物，昇溫至140℃後，再攪拌3小時。其後，將得到的反應液予以冷卻後，注入裝有大量甲乙酮之容器，使樹脂析出。其後，藉由將含有該樹脂之液體進行離心分離，而將接枝聚合有馬來酸酐之酸改性丙烯-丁烯共聚物、和(聚)馬來酸酐及低分子量物分離並進行純化。其後，藉由在減壓下以70℃乾燥5小時，獲得馬來酸酐改性丙烯-丁烯共聚物(CO-1，酸價19mgKOH/g，數目平均分子量25,000，Tm80℃，△H35J/g)。(Acid modified polyolefin (a)) [Manufacturing Example 1] In a 1L autoclave, 100 parts by mass of propylene-butene copolymer ("TAFMER (registered trademark) XM7080" manufactured by Mitsui Chemicals Co., Ltd.), 150 parts by mass of toluene, and 19 parts by mass of maleic anhydride were added , 6 parts by mass of two (tertiary butyl) peroxide, heated to 140° C., and then stirred for another 3 hours. After that, the obtained reaction liquid was cooled, and then poured into a container filled with a large amount of methyl ethyl ketone to precipitate the resin. Thereafter, by centrifuging the liquid containing the resin, the acid-modified propylene-butene copolymer graft-polymerized with maleic anhydride, (poly)maleic anhydride and low molecular weight substances are separated and purified. Thereafter, it was dried under reduced pressure at 70°C for 5 hours to obtain a maleic anhydride modified propylene-butene copolymer (CO-1, acid value 19mgKOH/g, number average molecular weight 25,000, Tm80°C, △H35J/ g).

[製造例2] 將馬來酸酐的進料量變更為14質量份，除此之外，和製造例1同樣地進行，藉此獲得馬來酸酐改性丙烯-丁烯共聚物(CO-2，酸價14mgKOH/g，數目平均分子量30,000，Tm78℃，△H25J/g)。[Manufacturing Example 2] Except that the feed amount of maleic anhydride was changed to 14 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a maleic anhydride-modified propylene-butene copolymer (CO-2, acid value 14mgKOH/ g, number average molecular weight 30,000, Tm78°C, △H25J/g).

[製造例3] 將馬來酸酐的進料量變更為11質量份，除此之外，和製造例1同樣地進行，藉此獲得馬來酸酐改性丙烯-丁烯共聚物(CO-3，酸價11mgKOH/g，數目平均分子量33,000，Tm80℃，△H25J/g)。[Manufacturing Example 3] Except that the feed amount of maleic anhydride was changed to 11 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a maleic anhydride-modified propylene-butene copolymer (CO-3, acid value 11mgKOH/ g, number average molecular weight 33,000, Tm80℃, △H25J/g).

[製造例4] 將馬來酸酐的進料量變更為6質量份，除此之外，和製造例1同樣地進行，藉此獲得馬來酸酐改性丙烯-丁烯共聚物(CO-4，酸價7mgKOH/g，數目平均分子量35,000，Tm82℃，△H25J/g)。[Manufacturing Example 4] Except that the feed amount of maleic anhydride was changed to 6 parts by mass, the same procedure as in Production Example 1 was carried out to obtain a maleic anhydride-modified propylene-butene copolymer (CO-4, acid value 7mgKOH/ g, number average molecular weight 35,000, Tm 82°C, △H25J/g).

由表1可知，實施例1～15中，就黏接薄膜而言，乾燥後之黏性、電路填埋性等薄膜操作性優良，和聚醯亞胺薄膜及和銅箔具有優良的黏接性、焊料耐熱性。又，實施例11中，碳二亞胺化合物(d)的摻合量多，故電特性差，但薄膜操作性、黏接性、焊料耐熱性良好。相對於此，比較例1中，未摻合寡聚伸苯基醚(b)，故焊料耐熱性差。比較例2中，未摻合碳二亞胺化合物(d)，故黏接性差。比較例3中，未摻合酸改性聚烯烴(a)，故黏接性及電路填埋性差。比較例4中，未摻合環氧樹脂(c)，故焊料耐熱性差。比較例5中，寡聚伸苯基醚的數目平均分子量大，故未溶解於有機溶劑，而無法製備黏接薄膜。比較例6中，溶劑(e)(殘留溶劑)的含量少，故電路填埋性差。比較例7中，溶劑(e)(殘留溶劑)的含量多，故乾燥後之黏性及焊料耐熱性差。 [產業上利用性]It can be seen from Table 1 that in Examples 1-15, as far as the adhesive film is concerned, the dry adhesiveness, circuit embedding and other film handling properties are excellent, and it has excellent adhesiveness with polyimide film and copper foil. , Solder heat resistance. In addition, in Example 11, the blending amount of the carbodiimide compound (d) was large, so the electrical properties were poor, but the film handling properties, adhesive properties, and solder heat resistance were good. In contrast, in Comparative Example 1, the oligophenylene ether (b) was not blended, so the solder had poor heat resistance. In Comparative Example 2, the carbodiimide compound (d) was not blended, so the adhesiveness was poor. In Comparative Example 3, the acid-modified polyolefin (a) was not blended, so the adhesiveness and circuit filling properties were poor. In Comparative Example 4, the epoxy resin (c) was not blended, so the solder had poor heat resistance. In Comparative Example 5, the number average molecular weight of the oligophenylene ether was large, so it was not dissolved in an organic solvent, and an adhesive film could not be prepared. In Comparative Example 6, the content of the solvent (e) (residual solvent) is small, and therefore, the circuit fillability is poor. In Comparative Example 7, the content of the solvent (e) (residual solvent) was large, so the viscosity after drying and the solder heat resistance were poor. [Industrial Utilization]

本發明之黏接薄膜具有和聚醯亞胺等樹脂基材及和銅箔等金屬基材之高黏接性，且可獲得高焊料耐熱性。又，藉由調整碳二亞胺化合物(d)之摻合量，可展現優良的低介電特性。此外，由於乾燥後之黏性、電路填埋性等薄膜操作優良，故生產性優良。本發明之黏接薄膜可獲得黏接片及使用該黏接片進行黏接而成的疊層體。由於上述特性，而在撓性印刷配線板用途，尤其在高頻區域要求低介電特性(低介電常數、低介電損耗正切)之FPC用途係為有效。The adhesive film of the present invention has high adhesiveness to resin substrates such as polyimide and metal substrates such as copper foil, and can obtain high solder heat resistance. In addition, by adjusting the blending amount of the carbodiimide compound (d), excellent low dielectric properties can be exhibited. In addition, due to the excellent film handling properties such as adhesiveness and circuit embedding after drying, the productivity is excellent. The adhesive film of the present invention can obtain an adhesive sheet and a laminated body formed by bonding using the adhesive sheet. Due to the above characteristics, it is effective for FPC applications in flexible printed wiring board applications, especially in high-frequency regions that require low dielectric characteristics (low dielectric constant, low dielectric loss tangent).

Figure 109141231-A0101-11-0001-1
Figure 109141231-A0101-11-0001-1

Claims (8)

一種黏接薄膜，其特徵為含有： 酸改性聚烯烴(a)， 數目平均分子量3000以下之寡聚伸苯基醚(b)， 環氧樹脂(c)，及 碳二亞胺化合物(d)； 且有機溶劑(e)的含量相對於黏接薄膜的質量為1～8質量%。An adhesive film, which is characterized by containing: Acid-modified polyolefin (a), Oligophenylene ether (b) with number average molecular weight below 3000, Epoxy resin (c), and Carbodiimide compound (d); And the content of the organic solvent (e) is 1-8% by mass relative to the mass of the adhesive film. 如請求項1之黏接薄膜，其中，酸改性聚烯烴(a)的酸價為5～40mgKOH/g。Such as the adhesive film of claim 1, wherein the acid value of the acid-modified polyolefin (a) is 5-40 mgKOH/g. 如請求項1或2之黏接薄膜，其中，數目平均分子量3000以下之寡聚伸苯基醚(b)具有通式(1)之結構單元及/或通式(2)之結構單元；
Figure 03_image001
通式(1)中，R1 、R2 、R3 、R4 分別獨立地表示氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基；
Figure 03_image004
通式(2)中，R11 、R12 、R13 、R14 、R15 、R16 、R17 、R18 分別獨立地表示氫原子、也可經取代之烷基、也可經取代之烯基、也可經取代之炔基、也可經取代之芳基、也可經取代之芳烷基或也可經取代之烷氧基；A為碳數20以下之直鏈狀或分支狀或環狀之2價烴基、或氧原子。The adhesive film of claim 1 or 2, wherein the oligophenylene ether (b) with a number average molecular weight of 3000 or less has a structural unit of the general formula (1) and/or a structural unit of the general formula (2);
Figure 03_image001
In the general formula (1), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and An aryl group that may be substituted, an aralkyl group that may also be substituted, or an alkoxy group that may also be substituted;
Figure 03_image004
In the general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted Alkenyl, substituted alkynyl, substituted aryl, substituted aralkyl, or substituted alkoxy; A is linear or branched with 20 carbon atoms or less Or a cyclic divalent hydrocarbon group, or an oxygen atom. 如請求項1或2之黏接薄膜，其中，相對於酸改性聚烯烴(a)100質量份，含有5～100質量份之數目平均分子量3000以下之寡聚伸苯基醚(b)、5～60質量份之環氧樹脂(c)及0.5～20質量份之碳二亞胺化合物(d)。The adhesive film of claim 1 or 2, which contains 5 to 100 parts by mass of oligophenylene ether (b) with a number average molecular weight of 3000 or less relative to 100 parts by mass of acid-modified polyolefin (a), 5-60 parts by mass of epoxy resin (c) and 0.5-20 parts by mass of carbodiimide compound (d). 如請求項1或2之黏接薄膜，其在硬化後於1GHz的相對介電常數(εc )為3.0以下，介電損耗正切(tanδ)為0.02以下。For example, the adhesive film of claim 1 or 2 has a relative permittivity (ε c ) of 3.0 or less at 1 GHz after curing, and a dielectric loss tangent (tanδ) of 0.02 or less. 如請求項1或2之黏接薄膜，其中，有機溶劑(e)為選自於由甲乙酮、甲基環己烷及甲苯構成之群組中之1種以上之有機溶劑。The adhesive film of claim 1 or 2, wherein the organic solvent (e) is one or more organic solvents selected from the group consisting of methyl ethyl ketone, methyl cyclohexane, and toluene. 一種疊層體，係使用如請求項1至6中任一項之黏接薄膜而形成。A laminated body is formed by using the adhesive film of any one of claims 1 to 6. 一種印刷配線板，含有如請求項7之疊層體作為構成元件。A printed wiring board containing a laminated body as in Claim 7 as a constituent element.
TW109141231A 2019-11-28 2020-11-25 Adhesive film, laminate, and printed wiring board TW202130766A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019215101 2019-11-28
JP2019-215101 2019-11-28

Publications (1)

Publication Number Publication Date
TW202130766A true TW202130766A (en) 2021-08-16

Family

ID=76130513

Family Applications (1)

Application Number Title Priority Date Filing Date
TW109141231A TW202130766A (en) 2019-11-28 2020-11-25 Adhesive film, laminate, and printed wiring board

Country Status (5)

Country Link
JP (1) JP6919776B1 (en)
KR (1) KR20220104685A (en)
CN (1) CN114555740B (en)
TW (1) TW202130766A (en)
WO (1) WO2021106847A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023054676A1 (en) * 2021-09-30 2023-04-06 リンテック株式会社 Curable adhesive sheet

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60197781A (en) * 1984-03-19 1985-10-07 Sumitomo Bakelite Co Ltd Adhesive and flexible printed circuit board
EP0800914B1 (en) * 1996-04-11 2002-07-03 Mitsui Chemicals, Inc. Laminated film and packaging material
US6387990B1 (en) * 1999-09-10 2002-05-14 General Electric Company Curable epoxy resin compositions with brominated triazine flame retardants
US6906120B1 (en) * 2000-06-20 2005-06-14 General Electric Poly(arylene ether) adhesive compositions
US20020072585A1 (en) * 2000-10-17 2002-06-13 Industrial Technology Research Institute PPE derivatives and resin composition having the same
JP2003292767A (en) * 2002-04-08 2003-10-15 Asahi Kasei Corp Polymer varnish
JP2004137411A (en) * 2002-10-18 2004-05-13 Sumitomo Bakelite Co Ltd Adhesive film for semiconductor, semiconductor device and method for producing semiconductor device
JP4411876B2 (en) * 2003-06-23 2010-02-10 東レ株式会社 Adhesive composition for semiconductor device, adhesive sheet and coverlay film using the same, and copper-clad polyimide film
JP4658735B2 (en) * 2005-08-18 2011-03-23 信越化学工業株式会社 Adhesive composition and adhesive film
JP4872295B2 (en) * 2005-09-30 2012-02-08 Ｄｉｃ株式会社 Moisture curable polyurethane hot melt adhesive
JP2008248141A (en) * 2007-03-30 2008-10-16 Nippon Steel Chem Co Ltd Flame retardant curable resin composition
JP2010275374A (en) * 2009-05-26 2010-12-09 Panasonic Electric Works Co Ltd Resin composition for flexible printed wiring board, resin film, prepreg, metal foil with resin, and flexible printed wiring board
JP2012116954A (en) * 2010-12-01 2012-06-21 Hitachi Cable Ltd Adhesive composition, adhesive film and wiring film using the same
JP5943461B2 (en) * 2012-02-21 2016-07-05 株式会社Adeka Insulating adhesive for polyimide
JP6022893B2 (en) * 2012-10-24 2016-11-09 ナミックス株式会社 Coverlay film, flexible printed wiring board using the same, and method for producing the same
CN105051111B (en) * 2013-03-22 2017-03-29 纳美仕有限公司 Resin combination and the adhesive film obtained using which, coverlay, layers cementing agent
JPWO2015033703A1 (en) * 2013-09-03 2017-03-02 東洋紡株式会社 Polyolefin adhesive composition
JP5743042B1 (en) * 2013-09-26 2015-07-01 東洋紡株式会社 Polyurethane resin composition, adhesive composition using the same, laminate and printed wiring board
CN106459703B (en) * 2014-06-11 2018-09-25 东洋纺株式会社 Polyolefins adhesive composition
KR102178215B1 (en) * 2014-08-27 2020-11-12 도요보 가부시키가이샤 Low dielectric adhesive composition
CN107075335B (en) * 2014-09-24 2020-02-14 东亚合成株式会社 Adhesive composition and adhesive layer-equipped laminate using same
JP6458985B2 (en) * 2014-10-22 2019-01-30 ナミックス株式会社 Resin composition, insulating film using the same, and semiconductor device
KR102160499B1 (en) * 2015-05-15 2020-09-28 도요보 가부시키가이샤 Laminate comprising low dielectric constant adhesive layer
JP6724916B2 (en) * 2015-07-03 2020-07-15 東洋紡株式会社 Polyolefin-based adhesive composition for automobile structural panel
JP2017031276A (en) * 2015-07-30 2017-02-09 パナソニックＩｐマネジメント株式会社 Thermosetting resin composition, resin varnish, metal foil with resin, resin film, metal clad laminated board and printed wiring board using the same
JP6074698B1 (en) * 2015-07-31 2017-02-08 東洋インキＳｃホールディングス株式会社 Thermosetting adhesive sheet and use thereof
JP6705456B2 (en) * 2015-08-19 2020-06-03 東洋紡株式会社 Low dielectric adhesive composition
WO2017033784A1 (en) * 2015-08-25 2017-03-02 三井金属鉱業株式会社 Metal foil with resin layer, metal-clad laminate, and method for producing printed wiring board
WO2017077912A1 (en) * 2015-11-02 2017-05-11 東洋紡株式会社 Low-dielectric flame-resistant adhesive composition
CN106190004B (en) * 2016-07-20 2020-05-15 律胜科技（苏州）有限公司 Adhesive composition with high-frequency characteristic and application thereof
WO2018030026A1 (en) * 2016-08-09 2018-02-15 東洋紡株式会社 Laminate containing low dielectric constant adhesive layer
CN110168017B (en) * 2017-01-10 2022-06-21 住友精化株式会社 Epoxy resin composition
KR102468900B1 (en) * 2017-05-31 2022-11-18 린텍 가부시키가이샤 Sheet-like adhesives, gas barrier laminates, and encapsulants
JP7106819B2 (en) * 2017-06-22 2022-07-27 昭和電工マテリアルズ株式会社 Resin varnish, resin composition, prepreg, laminate, multilayer printed wiring board, and storage method for resin varnish
CN107880530B (en) * 2017-12-25 2020-10-27 广东生益科技股份有限公司 Halogen-free resin composition, cover film and preparation method thereof
JP2019127501A (en) * 2018-01-22 2019-08-01 藤森工業株式会社 Thermosetting adhesive composition, adhesive film, coverlay film, and flexible printed wiring board

Also Published As

Publication number Publication date
JP6919776B1 (en) 2021-08-18
JPWO2021106847A1 (en) 2021-12-02
CN114555740A (en) 2022-05-27
WO2021106847A1 (en) 2021-06-03
KR20220104685A (en) 2022-07-26
CN114555740B (en) 2024-01-05

Similar Documents

Publication Publication Date Title
TWI812720B (en) Low Dielectric Adhesive Composition
CN106459704B (en) Low dielectric adhesive composition
TWI749038B (en) Laminated body with low dielectric adhesive layer
TW201702341A (en) Laminate comprising low dielectric constant adhesive layer
WO2021070606A1 (en) Polyolefin-based adhesive composition
WO2021045125A1 (en) Polyolefin-based adhesive composition
JP6919777B1 (en) Adhesive compositions, adhesive sheets, laminates and printed wiring boards
TW202130766A (en) Adhesive film, laminate, and printed wiring board
JP7120497B1 (en) Adhesive composition, and adhesive sheet, laminate and printed wiring board containing same
TW202214809A (en) Adhesive composition, adhesive sheet, multilayer body and printed wiring board
CN114080439B (en) Adhesive composition, adhesive sheet, laminate, and printed wiring board
JP7444319B1 (en) Adhesive composition, adhesive sheet, laminate, and printed wiring board containing the same
TW202120648A (en) Polyolefin-based adhesive composition
TW202337949A (en) Adhesive composition, adhesive sheet, electromagnetic-wave shielding film, laminate, and printed wiring board
CN116997627A (en) Adhesive composition, and adhesive sheet, laminate and printed wiring board each comprising same
TW202242060A (en) Adhesive composition, and bonding sheet, multilayer body and printed wiring board each containing same