JP2003221456A - Highly adhesive liquid crystal polymer film - Google Patents
Highly adhesive liquid crystal polymer filmInfo
- Publication number
- JP2003221456A JP2003221456A JP2002020508A JP2002020508A JP2003221456A JP 2003221456 A JP2003221456 A JP 2003221456A JP 2002020508 A JP2002020508 A JP 2002020508A JP 2002020508 A JP2002020508 A JP 2002020508A JP 2003221456 A JP2003221456 A JP 2003221456A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- polymer film
- highly adhesive
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49894—Materials of the insulating layers or coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
- H01L2924/097—Glass-ceramics, e.g. devitrified glass
- H01L2924/09701—Low temperature co-fired ceramic [LTCC]
-
- 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
- H05K1/0313—Organic insulating material
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は高接着性液晶ポリマ
ーフィルム及びそれを用いる回路基板、半導体パッケー
ジ並びに積層体に関するものである。TECHNICAL FIELD The present invention relates to a highly adhesive liquid crystal polymer film, a circuit board using the same, a semiconductor package and a laminate.
【0002】[0002]
【従来の技術】従来、高分子フィルムの表面特性を改良
する方法として、クロム酸混液処理、コロナ放電処理等
が用いられているが、化学的な安定度が高い液晶ポリマ
ーに対しては高い改質効果が得られない。一方、液晶ポ
リマーフィルムの表面特性を改良する方法として、特開
平10−316777号公報には、フィルムの表面に接
着促進コーティングを行う方法が、特開平1−2168
24号および特開平1−236246号の各公報には、
波長184.9nmの紫外線を照射する方法が、特開2
000−49002号公報には気体状の酸素原子含有化
合物の存在下で気体放電プラズマ処理を施す方法が提案
されている。特開平10−316777号公報に記載さ
れているフィルムの表面に接着促進コーティングを行う
方法は、コーティングされる材料自体が、アクリル、ポ
リエステル、ポリイミド、ポリウレタン、ポリアミドの
様に、基材となる液晶ポリマーより、耐熱性や吸水性な
どの面で劣っているため、液晶ポリマーの特性を生かせ
ない。また、コーティングするための工程が複雑なた
め、加工コストの上昇などの問題が発生する。特開平1
−216824号および特開平1−236246号の各
公報に記載されている波長184.9nmの紫外線を照
射する方法では、銅箔等との接着性は向上するものの、
メッキ、スパッタリングによりフィルム上に直接形成さ
れた金属層との接着力はあまり向上しない。同様にエポ
キシ樹脂等の接着剤や半導体封止用樹脂との接着力もあ
まり向上しない。特開2000−49002号公報には
表面の酸素濃度が内部の1.2倍になるように、気体状
の酸素原子含有化合物の存在下で気体放電プラズマ処理
を施す方法が提案されている。しかし、表面の酸素濃度
の増加により、銅箔等との接着性は向上するものの、や
はり、メッキ、スパッタリングによりフィルム上に直接
形成された金属層との接着力やエポキシ樹脂等の接着剤
や半導体封止用樹脂との接着力もあまり向上しない。2. Description of the Related Art Conventionally, chromic acid mixed liquid treatment, corona discharge treatment and the like have been used as a method for improving the surface characteristics of polymer films, but it is highly effective for liquid crystal polymers having high chemical stability. The quality effect cannot be obtained. On the other hand, as a method for improving the surface characteristics of a liquid crystal polymer film, JP-A-10-316777 discloses a method of applying an adhesion-promoting coating on the surface of the film.
No. 24 and JP-A-1-236246,
A method of irradiating ultraviolet rays having a wavelength of 184.9 nm is disclosed in Japanese Patent Application Laid-Open No.
No. 000-49002 proposes a method of performing gas discharge plasma treatment in the presence of a gaseous oxygen atom-containing compound. The method of performing adhesion-promoting coating on the surface of a film described in JP-A-10-316777 is a liquid crystal polymer that is a base material such as acrylic, polyester, polyimide, polyurethane, and polyamide. Therefore, since it is inferior in terms of heat resistance and water absorption, the characteristics of the liquid crystal polymer cannot be utilized. Further, since the coating process is complicated, problems such as an increase in processing cost occur. JP-A-1
In the method of irradiating with ultraviolet rays having a wavelength of 184.9 nm described in JP-A-216824 and JP-A-1-236246, although the adhesiveness with a copper foil or the like is improved,
The adhesive force with the metal layer formed directly on the film by plating or sputtering does not improve so much. Similarly, the adhesive strength with an adhesive such as an epoxy resin or a resin for semiconductor encapsulation is not improved so much. Japanese Unexamined Patent Publication No. 2000-49002 proposes a method of performing gas discharge plasma treatment in the presence of a gaseous oxygen atom-containing compound so that the oxygen concentration on the surface is 1.2 times that of the inside. However, due to the increase in oxygen concentration on the surface, the adhesiveness with copper foil, etc. is improved, but also the adhesiveness with the metal layer directly formed on the film by plating and sputtering, the adhesive such as epoxy resin, and the semiconductor. The adhesive strength with the sealing resin does not improve so much.
【0003】[0003]
【発明が解決しようとする課題】本発明は、高接着性を
有する液晶ポリマーフィルムを提供するとともに、該フ
ィルムを用いる回路基板、半導体パッケージ及び積層体
を提供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal polymer film having high adhesiveness, and to provide a circuit board, a semiconductor package and a laminate using the film.
【0004】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、以下に示す液晶ポリ
マーフィルム、回路基板、半導体パッケージ及び積層体
が提供される。
(1)液晶ポリマーからなるフィルムであって、その片
側又は両側の表面部に窒素原子が存在し、X線光電子分
光分析で測定した該窒素原子の濃度が2%以上であるこ
とを特徴とする高接着性液晶ポリマーフィルム。
(2)該窒素原子がアミノ基又はアミド基として存在す
る前記(1)に記載の高接着性液晶ポリマーフィルム。
(3)前記(1)又は(2)に記載の高接着性液晶ポリ
マーフィルムの該窒素原子が存在する高接着性表面上に
金属層が形成された積層体からなることを特徴とする回
路基板。
(4)該金属層が接着、融着、スパッタリング、無電解
メッキのいずれかの方法により形成されたことを特徴と
する前記(3)に記載の回路基板。
(5)該金属層が銅である前記(3)又は(4)に記載
の回路基板。
(6)封止樹脂により半導体が封止されている回路基板
を有する半導体パッケージにおいて、該回路基板が前記
(3)〜(5)のいずれかに記載の回路基板からなるこ
とを特徴とする半導体パッケージ。
(7)前記(1)又は(2)に記載の高接着性液晶ポリ
マーフィルムの該窒素原子が存在する高接着性表面上に
金属層が形成されたことを特徴とする高接着性液晶ポリ
マーフィルム/金属層積層体。
(8)液晶ポリマーフィルムの表面処理面をアンモニア
水溶液又はヒドラジン水溶液で濡らした後、該表面処理
面に308nmの波長を含む紫外線を照射することを特
徴とする液晶ポリマーフィルムの表面処理方法。
(9)液晶ポリマーフィルムの表面処理面にアンモニア
又はヒドラジンガス雰囲気中でプラズマを照射すること
を特徴とする液晶ポリマーフィルムの表面処理方法。
(10)前記(8)又は(9)に記載の表面処理方法で
処理されたことを特徴とする高接着性液晶ポリマーフィ
ルム。The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, the following liquid crystal polymer film, circuit board, semiconductor package, and laminate are provided. (1) A film made of a liquid crystal polymer, wherein nitrogen atoms are present on one or both surfaces of the film, and the concentration of the nitrogen atoms measured by X-ray photoelectron spectroscopy analysis is 2% or more. Highly adhesive liquid crystal polymer film. (2) The highly adhesive liquid crystal polymer film as described in (1) above, wherein the nitrogen atom is present as an amino group or an amide group. (3) A circuit board comprising a laminate having a metal layer formed on the highly adhesive surface of the highly adhesive liquid crystal polymer film as described in (1) or (2), in which the nitrogen atom is present. . (4) The circuit board as described in (3) above, wherein the metal layer is formed by any method of adhesion, fusion bonding, sputtering, and electroless plating. (5) The circuit board according to (3) or (4), wherein the metal layer is copper. (6) In a semiconductor package having a circuit board in which a semiconductor is sealed with a sealing resin, the circuit board is formed of the circuit board according to any one of (3) to (5). package. (7) A highly adhesive liquid crystal polymer film having a metal layer formed on the highly adhesive surface of the highly adhesive liquid crystal polymer film according to (1) or (2), in which the nitrogen atom is present. / Metal layer laminate. (8) A method for treating a surface of a liquid crystal polymer film, which comprises irradiating the surface-treated surface of the liquid crystal polymer film with an aqueous ammonia solution or an aqueous hydrazine solution, and then irradiating the surface-treated surface with ultraviolet rays having a wavelength of 308 nm. (9) A surface treatment method for a liquid crystal polymer film, which comprises irradiating plasma on the surface-treated surface of the liquid crystal polymer film in an atmosphere of ammonia or hydrazine gas. (10) A highly adhesive liquid crystal polymer film, which is treated by the surface treatment method according to (8) or (9).
【0005】[0005]
【発明の実施の形態】本発明で用いる基材フィルムは、
熱溶融型液晶ポリマーであり、芳香族系ポリエステル構
造を有する。その融点は、230〜380℃、好ましく
は250〜350℃である。このような液晶ポリマーに
は、従来公知のクランクシャフトユニットを持ったII
型やベントユニットを有するか又は直線構造を有したI
型の液晶ポリマーが包含される。液晶ポリマーフィルム
において、その融点が前記範囲より低くなると半田リフ
ローの熱に耐えられなくなり、一方、前記範囲より高く
なると押出し成形が難かしくなり、シート化に適さなく
なる。そのフィルムの分子配向は2軸配向が好ましく、
そのMD/TDの強度比が1/3〜3/1の間にあるも
のが好ましく、1/2〜2/1の間にあるものがより好
ましい。前記強度比が前記範囲に入らないものは、引き
裂けやすい上に、その線膨張係数(CTE)の異方性が
強くなるため、加工性、信頼性が低下してしまう。BEST MODE FOR CARRYING OUT THE INVENTION The base film used in the present invention is
It is a hot-melt liquid crystal polymer and has an aromatic polyester structure. Its melting point is 230-380 ° C, preferably 250-350 ° C. Such a liquid crystal polymer has a conventionally known crankshaft unit II
I with mold or vent unit or with linear structure
Included are types of liquid crystal polymers. If the melting point of the liquid crystal polymer film is lower than the above range, it cannot withstand the heat of solder reflow, while if it is higher than the above range, extrusion molding becomes difficult and it becomes unsuitable for sheet formation. The molecular orientation of the film is preferably biaxial orientation,
The MD / TD strength ratio is preferably between 1/3 and 3/1, and more preferably between 1/2 and 2/1. If the strength ratio does not fall within the above range, it is easy to tear and the anisotropy of the coefficient of linear expansion (CTE) becomes strong, so that workability and reliability are deteriorated.
【0006】本発明の高接着性液晶ポリマーフィルム
(以下、単にフィルムとも言う)は、前記液晶ポリマー
フィルムの片面又は両面に窒素化処理を施すことによっ
て製造することができる。この場合の窒素化処理は、液
晶ポリマーフィルムの表面部に窒素原子を固定化し得る
方法であればよく、このような方法には、NH結合を有
する常温で気体状又は液体状化合物を処理剤として用い
る各種の方法が包含される。例えば、処理剤を含む雰囲
気中で液晶ポリマーフィルム表面に紫外線を照射する方
法や、液状の処理剤を液晶ポリマーフィルム表面に塗布
し、紫外線を照射する方法、処理剤のガス中で液晶ポリ
マーフィルムをプラズマ放電加工する方法等が好ましく
採用される。これらの方法を用いる際に、前処理として
あらかじめ液晶ポリマーフィルムの表面処理面に紫外線
を照射すると、液晶ポリマーフィルムの接着性をさらに
向上させることができる。紫外線照射を行う場合、その
紫外線は、好ましくは308nm以下、より好ましくは
254nm以下の波長を主成分とするものが用いられ
る。紫外線の波長が前記範囲を超えると、液晶ポリマー
フィルムの接着性を向上させる効果が十分に得られな
い。また、照度は中心波長で1mW/cm2以上が好ま
しく、照射時間は1秒以上が好ましい。照度や照射時間
が不十分であると液晶ポリマーフィルムの接着性を向上
させる効果が十分に得られない。照射時間は長いほど接
着改良効果があるが、製造コストを考慮すると、一般的
には工業的に生産可能な時間は60分以下と考えられ
る。また、ランプと液晶ポリマーフィルムとの間の距離
は5mm以上、500mm以下が好ましい。距離が短す
ぎるとランプの熱によりフィルムが変形してしまい、距
離が遠すぎると液晶ポリマーフィルムの接着性を向上さ
せる効果が十分に得られない。The highly adhesive liquid crystal polymer film of the present invention (hereinafter, also simply referred to as a film) can be produced by subjecting one side or both sides of the liquid crystal polymer film to a nitrogen treatment. The nitriding treatment in this case may be a method capable of immobilizing nitrogen atoms on the surface portion of the liquid crystal polymer film. In such a method, a gaseous or liquid compound having an NH bond at room temperature as a treating agent is used. The various methods used are included. For example, a method of irradiating the liquid crystal polymer film surface with ultraviolet rays in an atmosphere containing a treatment agent, a method of applying a liquid treatment agent to the surface of the liquid crystal polymer film and irradiating it with ultraviolet rays, A method such as plasma electric discharge machining is preferably adopted. When using these methods, if the surface-treated surface of the liquid crystal polymer film is previously irradiated with ultraviolet rays as a pretreatment, the adhesiveness of the liquid crystal polymer film can be further improved. When UV irradiation is performed, UV rays having a wavelength of preferably 308 nm or less, more preferably 254 nm or less, as a main component are used. When the wavelength of ultraviolet rays exceeds the above range, the effect of improving the adhesiveness of the liquid crystal polymer film cannot be sufficiently obtained. The illuminance is preferably 1 mW / cm 2 or more at the central wavelength, and the irradiation time is preferably 1 second or more. If the illuminance or irradiation time is insufficient, the effect of improving the adhesiveness of the liquid crystal polymer film cannot be sufficiently obtained. The longer the irradiation time is, the better the adhesion improving effect is. However, considering the manufacturing cost, it is generally considered that the industrially producible time is 60 minutes or less. The distance between the lamp and the liquid crystal polymer film is preferably 5 mm or more and 500 mm or less. If the distance is too short, the film will be deformed by the heat of the lamp, and if the distance is too long, the effect of improving the adhesiveness of the liquid crystal polymer film cannot be sufficiently obtained.
【0007】前記NH結合を有する化合物としては、ア
ンモニア、ヒドラジン、ヒドロキシルアミン等が特に好
ましく用いられる。As the compound having the NH bond, ammonia, hydrazine, hydroxylamine and the like are particularly preferably used.
【0008】液晶ポリマーフィルムを処理剤と接触させ
る場合、その処理剤の濃度は、液中では1〜100%、
好ましくは10〜50%の範囲、ガス中では1〜100
モル%、好ましくは10〜100モル%の範囲に規定す
るのがよい。液晶ポリマーフィルム中に固定化される窒
素原子は、アミノ基及び/又はアミド基の形態であるこ
とが好ましいが、より好ましくはCNH結合(アミノ
基)の形態である。When the liquid crystal polymer film is brought into contact with a treating agent, the concentration of the treating agent is 1 to 100% in the liquid,
Preferably in the range of 10-50%, in gas 1-100
It is preferable to define the amount in the range of mol%, preferably 10 to 100 mol%. The nitrogen atom immobilized in the liquid crystal polymer film is preferably in the form of an amino group and / or an amide group, more preferably in the form of a CNH bond (amino group).
【0009】本発明においては、前記窒素化処理は、フ
ィルムの表面部の窒素原子濃度が、2%(重量%)以
上、好ましくは3%以上になるように行う。その窒素原
子濃度の上限値は特に制約されないが、通常15%程度
である。In the present invention, the nitriding treatment is carried out so that the nitrogen atom concentration on the surface portion of the film is 2% (% by weight) or more, preferably 3% or more. The upper limit of the nitrogen atom concentration is not particularly limited, but is usually about 15%.
【0010】なお、フィルム表面部の窒素原子濃度は、
X線光電子分光分析で、ワイドスキャン測定して得られ
るスペクトルから、元素を固定後C(Is)及びO(I
s)のナロースキャン測定をし、高分解性測定結果に基
づいて求めたものである。また、照射X線としてはAl
Kαを用いた。この場合のフィルム表面部とは、前記窒
素原子濃度の測定法からもわかるように、フィルムの表
面から約50〜100オングストロームの深さまでを意
味するものである。The nitrogen atom concentration on the film surface is
In X-ray photoelectron spectroscopy, C (Is) and O (I
It is obtained by performing the narrow scan measurement of s) and based on the measurement result of high resolution. In addition, the irradiation X-ray is Al
K α was used. In this case, the film surface portion means a depth of about 50 to 100 angstroms from the surface of the film, as can be seen from the method for measuring the nitrogen atom concentration.
【0011】本発明による高接着性フィルムは、金属や
プラスチックフィルム、熱硬化性樹脂等と強固に接着さ
せることができる。本発明の好ましい1つの製品形態
は、該フィルムに金属層を積層したフィルム/金属層積
層体である。このような積層体は、以下の方法により製
造することができる。
(1)熱融着法
この方法は、金属箔とフィルムとを熱融着することによ
り積層体を得る方法である。金属箔としては、各種の金
属のもの、例えば、銅箔、アルミ箔、金箔等が挙げられ
る。その厚さは、通常0.01〜200μm、好ましく
は0.1〜50μmである。熱融着は、一般的な熱プレ
スやダブルベルトプレス等の方法により行うことができ
る。熱融着する際の加工条件は、金属薄の種類や厚み、
液晶ポリマーフィルムの融点や厚み等の条件から適宜選
択すればよいが、一般的に温度は180〜400℃、圧
力は0.3〜10MPa/cm2の範囲である。
(2)スパッタリング法
この方法は、電子回路基板や光学材料製造の分野では公
知の方法であり、金属をフィルム上にスパッタリングす
ることにより積層体を得る方法である。スパッタリング
用金属としては、例えば、銅、アルミニウム、金、す
ず、クロム等が挙げられる。
(3)無電解メッキ法
この方法は、プラスチックやセラミック等の非導電性材
料を用いためっき製品の製造分野で公知の方法であり、
金属イオンを含む溶液からフィルム上に金属を析出させ
ることにより積層体を得る方法である。金属としては、
銅、ニッケル、コバルト、金、すず、クロム等が挙げら
れる。
(4)接着剤を用いる方法
この方法は、フィルムと金属フィルムとを接着剤を用い
て接着することにより積層体を得る方法である。接着剤
としては、エポキシ系、アクリル系、シアネート系等の
各種のものを用いることができる。The highly adhesive film according to the present invention can be firmly adhered to a metal, a plastic film, a thermosetting resin or the like. One preferable product form of the present invention is a film / metal layer laminate in which a metal layer is laminated on the film. Such a laminated body can be manufactured by the following method. (1) Heat-fusion method This method is a method for obtaining a laminate by heat-sealing a metal foil and a film. Examples of the metal foil include various metal foils such as copper foil, aluminum foil, and gold foil. The thickness is usually 0.01 to 200 μm, preferably 0.1 to 50 μm. The heat fusion can be performed by a method such as a general heat press or a double belt press. The processing conditions for heat fusion are the type and thickness of thin metal,
The temperature may be 180 to 400 ° C. and the pressure may be 0.3 to 10 MPa / cm 2 , although the temperature may be appropriately selected depending on the conditions such as the melting point and the thickness of the liquid crystal polymer film. (2) Sputtering method This method is a known method in the field of manufacturing electronic circuit boards and optical materials, and is a method of obtaining a laminate by sputtering a metal on a film. Examples of the metal for sputtering include copper, aluminum, gold, tin and chromium. (3) Electroless plating method This method is a known method in the field of manufacturing plated products using non-conductive materials such as plastics and ceramics,
It is a method of obtaining a laminate by depositing a metal on a film from a solution containing metal ions. As a metal,
Examples include copper, nickel, cobalt, gold, tin, and chromium. (4) Method using an adhesive This method is a method for obtaining a laminate by bonding a film and a metal film with an adhesive. As the adhesive, various types such as epoxy type, acrylic type and cyanate type can be used.
【0012】前記フィルム/金属層積層体において、そ
のフィルムの厚さは10〜500μm、好ましくは25
〜200μmである。金属層の厚さは0.01〜200
μm、好ましくは0.1〜50μmである。In the film / metal layer laminate, the thickness of the film is 10 to 500 μm, preferably 25.
Is about 200 μm. The thickness of the metal layer is 0.01 to 200
μm, preferably 0.1 to 50 μm.
【0013】本発明によれば、前記フィルム/金属層積
層体からなる回路基板が提供される。この場合、金属と
しては、銅、アルミニウム、金、すず、クロム等が好ま
しく用いられる。フィルムの厚さは10〜200μm、
好ましくは25〜125μmであり、金属層の厚さは3
〜100μm、好ましくは5〜50μmである。本発明
の回路基板は、その回路基板を構成するフィルムが機械
的強度及び耐熱性に優れ、かつ吸湿性の極めて小さい液
晶ポリマーからなり、しかもそのフィルムと金属層との
間の接着強度も高いことから、耐久性、耐熱性及び使用
安定性に優れた高品質のものである。According to the present invention, there is provided a circuit board comprising the film / metal layer laminate. In this case, as the metal, copper, aluminum, gold, tin, chromium or the like is preferably used. The thickness of the film is 10-200 μm,
The thickness is preferably 25 to 125 μm, and the thickness of the metal layer is 3
˜100 μm, preferably 5˜50 μm. In the circuit board of the present invention, the film forming the circuit board is made of a liquid crystal polymer having excellent mechanical strength and heat resistance and extremely low hygroscopicity, and further, the adhesive strength between the film and the metal layer is high. Therefore, it is a high quality product having excellent durability, heat resistance and use stability.
【0014】本発明によれば、前記回路基板上に半導体
を封止樹脂で封止した半導体パッケージが提供される。
この場合、封止樹脂としては、ビスフェノール型、クレ
ゾールノボラック型、ビフェニル型、ジシクロペンタジ
エン型、ナフタレン型、スチルベン型等のエポキシ樹脂
に無機フィラーを混合したもの等が挙げられる。本発明
の半導体パッケージは、前記回路基板を用いたことか
ら、耐久性、耐熱性及び使用安定性に優れた高品質のも
のである。According to the present invention, there is provided a semiconductor package in which a semiconductor is sealed on the circuit board with a sealing resin.
In this case, examples of the sealing resin include epoxy resins of bisphenol type, cresol novolac type, biphenyl type, dicyclopentadiene type, naphthalene type, stilbene type and the like mixed with an inorganic filler. Since the semiconductor package of the present invention uses the circuit board, it is of high quality and excellent in durability, heat resistance and use stability.
【0015】[0015]
【実施例】次に本発明を実施例によりさらに詳述する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【0016】実施例1
10%濃度のヒドラジン水溶液を液晶ポリマーフィルム
(ジャパンゴアテックス社製、製品名「BIAC BA
50F」)上に滴下し、その表面上に4mm厚の合成石
英板を重ねてフィルム上に水溶液を拡散した後、その石
英板を介してセン特殊光源社製の低圧水銀ランプPL3
0−200を用い、254nmの波長を中心とした紫外
線を120秒間照射した。照射距離はランプから4cm
とし、この際の照射強度を測定したところ15mW/c
m2(254nm)であった。Example 1 A 10% aqueous solution of hydrazine was added to a liquid crystal polymer film (manufactured by Japan Gore-Tex, product name "BIAC BA").
50F "), a synthetic quartz plate having a thickness of 4 mm is superposed on the surface thereof to diffuse the aqueous solution on the film, and then the low-pressure mercury lamp PL3 manufactured by Sen Special Light Source Co. is passed through the quartz plate.
UV light having a wavelength of 254 nm was irradiated for 120 seconds using 0-200. The irradiation distance is 4 cm from the lamp
And the irradiation intensity at this time was measured to be 15 mW / c
It was m 2 (254 nm).
【0017】実施例2
ベルジャー型プラズマ装置(サムコ社製、PD−10−
S)を用い、平行電極間に液晶ポリマーフィルム(ジャ
パンゴアテックス社製、製品名「BIAC BA50
F」)を固定し、アンモニアガスで装置内を置換した
後、0.1Torrに減圧し、13.56MHzの高周
波電圧を印加してプラズマを発生させ、プラズマ雰囲気
中で120秒間、フィルムの処理を行った。Example 2 Bell jar type plasma device (PD-10- manufactured by Samco)
S), and a liquid crystal polymer film (manufactured by Japan Gore-Tex, product name “BIAC BA50” between the parallel electrodes.
F ”) is fixed and the inside of the apparatus is replaced with ammonia gas, the pressure is reduced to 0.1 Torr, a high frequency voltage of 13.56 MHz is applied to generate plasma, and the film is processed in a plasma atmosphere for 120 seconds. went.
【0018】比較例1
セン特殊光源社製の低圧水銀ランプPL30−200を
用い、空気中で254nmの波長を中心とした紫外線を
液晶ポリマーフィルム(ジャパンゴアテックス社製、製
品名「BIAC BA50F」)に対して120秒間照
射した。照射距離はランプから4cmとし、この際の照
射強度を測定したところ15mW/cm 2(254n
m)であった。Comparative Example 1
Sen special light source company low pressure mercury lamp PL30-200
Using the ultraviolet light centered at a wavelength of 254 nm in the air
Liquid crystal polymer film (made by Japan GORE-TEX,
Illuminate the product name "BIAC BA50F") for 120 seconds.
Shot The irradiation distance should be 4 cm from the lamp and
When the radiation intensity is measured, it is 15 mW / cm 2(254n
m).
【0019】比較例2
ベルジャー型プラズマ装置(サムコ社製、PD−10−
S)を用い、平行電極間にフィルムを固定し、酸素ガス
で装置内を置換した後、0.1Torrに減圧し、1
3.56MHzの高周波電圧を印加してプラズマを発生
させ、プラズマ雰囲気中で120秒間、液晶ポリマーフ
ィルム(ジャパンゴアテックス社製、製品名「BIAC
BA50F」)の処理を行った。Comparative Example 2 Bell jar type plasma device (PD-10- manufactured by Samco)
S) was used to fix the film between the parallel electrodes, the inside of the device was replaced with oxygen gas, and the pressure was reduced to 0.1 Torr.
A high-frequency voltage of 3.56 MHz is applied to generate plasma, and a liquid crystal polymer film (manufactured by Japan Gore-Tex, product name "BIAC" is used for 120 seconds in a plasma atmosphere.
BA50F ") was performed.
【0020】前記実施例及び比較例で得られた液晶ポリ
マーフィルムについて、その性状を評価した。その結果
を表1に示す。The properties of the liquid crystal polymer films obtained in the above Examples and Comparative Examples were evaluated. The results are shown in Table 1.
【0021】[0021]
【表1】 [Table 1]
【0022】表1に示す通り、窒素の導入量が少ないと
無電解めっき、スパッタリング、封止樹脂との接着性が
優れないことがわかる。As shown in Table 1, it is understood that when the introduction amount of nitrogen is small, the adhesiveness with electroless plating, sputtering and sealing resin is not excellent.
【0023】前記各性状の評価は、以下の方法により行
った。
(1)窒素量定量及び窒素原子の形態:Surface
Science Instruments社製、S−
Probe ESCA Model 2803を用い
て、ワイドスキャン測定して得られるスペクトルから、
元素を固定後C(Is)及びO(Is)のナロースキャ
ン測定をし、高分解性測定結果に基づいて求めたもので
ある。また、照射X線としてはAlKαを用いた。
(2)銅箔接着強度(N/cm):日本電解社製、US
LP−12箔(電解銅箔、厚み12μm、粗化面の表面
粗さ:Rz=1.5)を、真空プレス機を用いて325
℃、4MPa、5分間加圧のプレス条件で張り合わせ、
180°ピール試験を行った。ピール試験条件は表2の
通りである。The evaluation of the above properties was carried out by the following methods. (1) Determination of nitrogen content and form of nitrogen atom: Surface
Product made by Science Instruments, S-
From the spectrum obtained by wide scan measurement using Probe ESCA Model 2803,
After fixing the element, the narrow scan measurement of C (Is) and O (Is) was performed, and it was obtained based on the high-decomposition measurement result. AlK α was used as the irradiation X-ray. (2) Copper foil adhesive strength (N / cm): manufactured by Nippon Denki Co., Ltd., US
LP-12 foil (electrolytic copper foil, thickness 12 μm, surface roughness of roughened surface: Rz = 1.5) was used for 325 using a vacuum press.
Laminated under press conditions of pressure, 4 MPa, 5 MPa,
A 180 ° peel test was conducted. Table 2 shows the peel test conditions.
【0024】[0024]
【表2】 [Table 2]
【0025】(3)無電解めっき接着強度(N/c
m):下記の表3の条件を用いて、0.5μm厚の銅の
無電解めっき層を形成した後、さらにめっき層が9μm
厚になるまで、表4の条件で2.5A/dm2の電流密
度で銅の電解めっきを行い、180°ピール試験を行っ
た。なお、表3中で、化学物質名以外で示している薬品
はATOTECH社の製品名である。(3) Electroless plating adhesive strength (N / c
m): Using the conditions in Table 3 below, after forming an electroless plating layer of copper having a thickness of 0.5 μm, the plating layer further has a thickness of 9 μm.
Copper was electrolytically plated at a current density of 2.5 A / dm 2 under the conditions shown in Table 4 to a thickness, and a 180 ° peel test was performed. In addition, in Table 3, chemicals other than chemical substance names are product names of ATOTECH.
【0026】[0026]
【表3】 [Table 3]
【0027】[0027]
【表4】
(4)スパッタリング銅接着強度(N/cm):フィル
ム表面に0.1μm厚の銅の層をスパッタリングで形成
した後、めっき層が9μm厚になるまでさらに銅の電解
めっきを行い、180°ピール試験を行った。
(5)封止樹脂接着強度(MPa):クレゾールノボラ
ック型エポキシ樹脂に、硬化剤としてノボラックフェノ
ール、フィラーとして溶融シリカを配合したコンパウン
ドを作製し、フィルム上にトランスファーモールドで成
形後、硬化させ、せん断破壊強度を測定した。モールド
用コンパウンドの配合は下記の表5の通りであり、トラ
ンスファーモールドの条件は表6の通りである。また、
せん断強度の測定条件は表7の通りである。[Table 4] (4) Sputtering copper adhesion strength (N / cm): After forming a 0.1 μm-thick copper layer on the film surface by sputtering, copper electroplating was further performed until the plating layer became 9 μm thick, and 180 ° peeling was performed. The test was conducted. (5) Sealing resin adhesive strength (MPa): A compound was prepared by mixing cresol novolac type epoxy resin with novolac phenol as a curing agent and fused silica as a filler, molded on a film by transfer molding, and then cured and sheared. The breaking strength was measured. The composition of the molding compound is shown in Table 5 below, and the transfer molding conditions are shown in Table 6. Also,
The conditions for measuring the shear strength are as shown in Table 7.
【0028】[0028]
【表5】 [Table 5]
【0029】[0029]
【表6】 [Table 6]
【0030】[0030]
【表7】 [Table 7]
【0031】[0031]
【発明の効果】本発明の高接着性液晶ポリマーフィルム
は、その表面接着性が著しく向上したものであることか
ら、他の材料(金属、プラスチック、セラミックス、ガ
ラス等)に対して強固に接着させることができる。本発
明のフィルムに金属層を形成したフィルム/金属層積層
体は、耐久性、耐熱性及び使用安定性に優れた高品質の
ものである。従って、本発明の積層体を用いることによ
り、耐久性、耐熱性及び使用安定性に優れ、信頼性の高
い高品質の回路基板及び半導体パッケージを得ることが
できる。Since the highly adhesive liquid crystal polymer film of the present invention has remarkably improved surface adhesiveness, it is firmly adhered to other materials (metal, plastic, ceramics, glass, etc.). be able to. The film / metal layer laminate in which the metal layer is formed on the film of the present invention is of high quality having excellent durability, heat resistance and use stability. Therefore, by using the laminate of the present invention, it is possible to obtain a high-quality circuit board and a semiconductor package which are excellent in durability, heat resistance, and use stability and have high reliability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) H01L 23/14 H05K 1/03 610N H05K 1/03 610 C08L 101:02 // C08L 101:02 H01L 23/14 R Fターム(参考) 4F071 AA04 AA48 AA78 AF12 AF58 AG01 AG15 AG16 AH13 BC01 4F073 AA01 BA25 BB01 CA01 CA45 EA01 EA11 EA43 EA44 4F100 AB01B AB17B AB33B AK41A AS00A AT00A BA02 EC03 EC18 EH66B EJ54 EJ58 EJ61 GB43 JJ03 JL11 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01L 23/14 H05K 1/03 610N H05K 1/03 610 C08L 101: 02 // C08L 101: 02 H01L 23 / 14 RF term (reference) 4F071 AA04 AA48 AA78 AF12 AF58 AG01 AG15 AG16 AH13 BC01 4F073 AA01 BA25 BB01 CA01 CA45 EA01 EA11 EA43 EA44 4F100 AB01B AB17B AB33B AK41A AS00A AT00A BA02 EC03 J61EJ43EJ58B58 EC03 EC54 E4366
Claims (10)
て、その片側又は両側の表面部に窒素原子が存在し、X
線光電子分光分析で測定した該窒素原子の濃度が2%以
上であることを特徴とする高接着性液晶ポリマーフィル
ム。1. A film comprising a liquid crystal polymer, wherein nitrogen atoms are present on one or both surface portions of the film, and X
A highly adhesive liquid crystal polymer film having a concentration of the nitrogen atom of 2% or more measured by a line photoelectron spectroscopy analysis.
て存在する請求項1に記載の高接着性液晶ポリマーフィ
ルム。2. The highly adhesive liquid crystal polymer film according to claim 1, wherein the nitrogen atom is present as an amino group or an amide group.
リマーフィルムの該窒素原子が存在する高接着性表面上
に金属層が形成された積層体からなることを特徴とする
回路基板。3. A circuit board comprising a laminate having a metal layer formed on the highly adhesive surface of the highly adhesive liquid crystal polymer film according to claim 1 or 2, wherein the nitrogen atom is present.
グ、無電解メッキのいずれかの方法により形成されたこ
とを特徴とする請求項3に記載の回路基板。4. The circuit board according to claim 3, wherein the metal layer is formed by any one of adhesion, fusion bonding, sputtering, and electroless plating.
載の回路基板。5. The circuit board according to claim 3, wherein the metal layer is copper.
回路基板を有する半導体パッケージにおいて、該回路基
板が請求項3〜5のいずれかに記載の回路基板からなる
ことを特徴とする半導体パッケージ。6. A semiconductor package having a circuit board in which a semiconductor is encapsulated by an encapsulating resin, wherein the circuit board comprises the circuit board according to any one of claims 3 to 5. .
リマーフィルムの該窒素原子が存在する高接着性表面上
に金属層が形成されたことを特徴とする高接着性液晶ポ
リマーフィルム/金属層積層体。7. A highly adhesive liquid crystal polymer film having a metal layer formed on the highly adhesive surface of the highly adhesive liquid crystal polymer film according to claim 1, wherein the nitrogen atom is present. Metal layer laminate.
ンモニア水溶液又はヒドラジン水溶液で濡らした後、該
表面処理面に308nmの波長を含む紫外線を照射する
ことを特徴とする液晶ポリマーフィルムの表面処理方
法。8. A method for treating a surface of a liquid crystal polymer film, which comprises immersing the surface-treated surface of the liquid crystal polymer film in an aqueous ammonia solution or an aqueous solution of hydrazine, and then irradiating the surface-treated surface with ultraviolet rays having a wavelength of 308 nm.
ンモニア又はヒドラジンガス雰囲気中でプラズマを照射
することを特徴とする液晶ポリマーフィルムの表面処理
方法。9. A surface treatment method for a liquid crystal polymer film, which comprises irradiating plasma on the surface-treated surface of the liquid crystal polymer film in an atmosphere of ammonia or hydrazine gas.
で処理されたことを特徴とする高接着性液晶ポリマーフ
ィルム。10. A highly adhesive liquid crystal polymer film treated by the surface treatment method according to claim 8 or 9.
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2003
- 2003-01-29 WO PCT/JP2003/000850 patent/WO2003064506A1/en active Application Filing
- 2003-01-29 TW TW092102015A patent/TW200302245A/en unknown
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TW200302245A (en) | 2003-08-01 |
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