JPH07145362A - Adhesive for bonding metal to fluororesin substrate - Google Patents
Adhesive for bonding metal to fluororesin substrateInfo
- Publication number
- JPH07145362A JPH07145362A JP5319109A JP31910993A JPH07145362A JP H07145362 A JPH07145362 A JP H07145362A JP 5319109 A JP5319109 A JP 5319109A JP 31910993 A JP31910993 A JP 31910993A JP H07145362 A JPH07145362 A JP H07145362A
- Authority
- JP
- Japan
- Prior art keywords
- terpolymer
- tetrafluoroethylene
- perfluoro
- group
- lower alkyl
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
-
- 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
- C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09J127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
-
- 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
- B32B2327/00—Polyvinylhalogenides
- B32B2327/12—Polyvinylhalogenides containing fluorine
- B32B2327/18—PTFE, i.e. polytetrafluoroethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/015—Fluoropolymer, e.g. polytetrafluoroethylene [PTFE]
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フッ素樹脂基質と金属
との接着剤に関する。更に詳しくは、高周波用プリント
配線板などの製造時に有効に用いられるフッ素樹脂基質
と金属との接着剤に関する。FIELD OF THE INVENTION The present invention relates to an adhesive between a fluororesin substrate and a metal. More specifically, the present invention relates to an adhesive between a fluororesin substrate and a metal, which is effectively used in the production of a printed wiring board for high frequencies.
【０００２】[0002]
【従来の技術】従来からガラス布基材にエポキシ樹脂あ
るいはポリイミド樹脂またはポリアミドイミド樹脂を含
浸させた樹脂含浸基板を積層成形して、プリント配線板
用の積層板が成形されているが、この積層板の誘電率
は、ガラス/エポキシ樹脂基板の場合で約4.5、ガラス/
ポリイミド樹脂系基板の場合で4.0と比較的大きく、そ
のため高周波に対する特性が不十分で、実際的にも用途
上、設計上の制約が大きいという欠点がみられる。2. Description of the Related Art Conventionally, a resin-impregnated substrate in which a glass cloth base material is impregnated with an epoxy resin, a polyimide resin or a polyamideimide resin is laminated and molded to form a laminated board for a printed wiring board. The dielectric constant of the plate is about 4.5 for glass / epoxy resin substrate,
In the case of a polyimide resin-based substrate, it is relatively large at 4.0, so the characteristics for high frequencies are insufficient, and there are drawbacks in that there are practical restrictions on design in terms of applications.
【０００３】そこで、高周波に対する特性を向上させる
ため、フッ素樹脂絶縁シート/熱溶融性フッ素樹脂/金属
シートを加熱加圧して接着させる方法が開発されてきて
いる(米国特許第5,198,053号明細書、特開昭62-109827
号公報)。しかるに、フッ素樹脂は本来接着力(密着力)
が低く、その上接着条件も厳しいため、金属表面のサン
ドブラスター処理が要求されたり、また多くの工程を組
み合わせたときの寸法安定性の問題や剥離現象などがひ
き起こされるため、特殊な目的の場合のみに少量用いら
れるだけである。Therefore, in order to improve the characteristics against high frequencies, a method of heating and pressing a fluororesin insulating sheet / heat-meltable fluororesin / metal sheet to bond them has been developed (US Pat. No. 5,198,053, Japanese Patent No. 5,198,053). Kaisho 62-109827
Issue). However, fluororesins are originally adhesive (adhesive)
Is low and the adhesion conditions are strict, so it is necessary to perform sandblasting on the metal surface, and it may cause problems such as dimensional stability and peeling phenomenon when combining many processes. It is only used in small quantities in some cases.
【０００４】更に、フッ素樹脂接着剤として、側鎖にス
ルホニルフロライド基-SO2Fを導入したものも知られて
いるが(米国特許第4,916,020号明細書)、この場合には
金属面をエポキシ樹脂などで表面処理したものを用いな
ければならず、このような金属面の表面処理は、工程上
からも、また電気特性面からも大きなデメリットであ
る。Further, a fluororesin adhesive having a sulfonyl fluoride group-SO 2 F introduced into its side chain is also known (US Pat. No. 4,916,020). In this case, the metal surface is epoxy. It is necessary to use a resin surface-treated, and such a surface treatment of a metal surface is a great disadvantage from the viewpoint of the process as well as the electric characteristics.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、フッ
素樹脂基質と金属とを接着させる熱溶融性のフッ素樹脂
よりなる接着剤であって、金属面に特別の表面処理を施
さなくとも良好な接着性を示すものを提供することにあ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composed of a heat-melting fluororesin for adhering a fluororesin substrate and a metal, which does not require any special surface treatment on the metal surface. To provide a material that exhibits excellent adhesiveness.
【０００６】[0006]
【課題を解決するための手段】かかる本発明の目的は、
テトラフルオロエチレン、パーフルオロ(低級アルキル
ビニルエーテル)および一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO3H で表わされるスルホン酸基含有パーフルオロビニルエー
テルまたはその塩の3元共重合体よりなるフッ素樹脂基
質と金属との接着剤によって達成される。The object of the present invention is as follows.
A ternary compound of tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) and a sulfonic acid group-containing perfluorovinyl ether represented by the general formula CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 3 H or a salt thereof. This is achieved by an adhesive between a fluororesin substrate made of a polymer and a metal.
【０００７】上記3元共重合体は、一般にテトラフルオ
ロエチレン約80〜96重量%、パーフルオロ(低級アルキル
ビニルエーテル)約10〜2重量%およびスルホン酸(塩)含
有パーフルオロビニルエーテル約10〜2重量%の共重合組
成を有するものが用いられる。スルホン酸(塩)含有パー
フルオロビニルエーテルの共重合割合がこれより少ない
と、所望の接着効果が得られず、一方これより多い割合
で共重合されたものが用いられると、接着時に発泡が発
生するようになり好ましくない。The terpolymer is generally about 80 to 96% by weight of tetrafluoroethylene, about 10 to 2% by weight of perfluoro (lower alkyl vinyl ether) and about 10 to 2% by weight of perfluorovinyl ether containing sulfonic acid (salt). Those having a copolymerization composition of 10% are used. If the copolymerization ratio of the sulfonic acid (salt) -containing perfluorovinyl ether is lower than this, the desired adhesive effect cannot be obtained, while if a copolymerized ratio higher than this is used, foaming occurs during bonding. This is not desirable.
【０００８】3元共重合体中には、耐熱性、電気的特
性、接着性などの求められる特性を実質的に損なわない
範囲内、例えば約10重量%以下の範囲内で、エチレン、
プロピレン、イソブチレン、ヘキサフルオロプロピレ
ン、ヘキサフルオロイソブチレン、クロロトリフルオロ
エチレン等を更に共重合させることができる。In the terpolymer, ethylene, within a range that does not substantially impair the required properties such as heat resistance, electrical properties and adhesiveness, for example, within a range of about 10% by weight or less,
Propylene, isobutylene, hexafluoropropylene, hexafluoroisobutylene, chlorotrifluoroethylene and the like can be further copolymerized.
【０００９】かかる3元共重合体は、テトラフルオロエ
チレン、パーフルオロ(低級アルキルビニルエーテル)お
よび一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO2X で表わされる、スルホニルハライド基、一般にはスルホ
ニルフロライド基を含有するパーフルオロビニルエーテ
ルの3元共重合体に、アルカリ金属水酸化物、アンモニ
ア、アミンなどを反応させ、スルホン酸のアルカリ金属
塩、アンモニウム塩、アミン塩などを形成させた後、無
機酸と反応させる一連の工程によって製造される。Such a terpolymer is a sulfonyl halide represented by tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) and the general formula CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 2 X. Group, generally a perfluorovinyl ether terpolymer containing a sulfonyl fluoride group, is reacted with an alkali metal hydroxide, ammonia, an amine, etc. to give an alkali metal salt of sulfonic acid, an ammonium salt, an amine salt, etc. After being formed, it is produced by a series of steps of reacting with an inorganic acid.
【００１０】接着剤として用いられる3元共重合体は、
一般に厚さが約0.05〜0.3mm程度のフィルムとして用い
られることが多い。そのため、上記一連の反応も、フィ
ルム状態で行うことができる。即ち、テトラフルオロエ
チレン、パーフルオロ(低級アルキルビニルエーテル)お
よびスルホニルハライド基含有パーフルオロビニルエー
テルの3元共重合体が、まずフィルム状に成形される。
この3元共重合体のフィルム成形は、約360〜380℃、約1
〜10kg/cm2、約1〜3分間の条件下で予熱した後、約360
〜380℃、約10〜20kg/cm2、約30〜60分間の条件下で加
圧プレスすることにより行われる。The terpolymer used as an adhesive is
Generally, it is often used as a film having a thickness of about 0.05 to 0.3 mm. Therefore, the above series of reactions can also be performed in a film state. That is, a terpolymer of tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) and sulfonyl halide group-containing perfluorovinyl ether is first formed into a film.
Film formation of this ternary copolymer is about 360 ~ 380 ℃, about 1
To 10 kg / cm 2, it was preheated under conditions of about 1-3 minutes, about 360
It is carried out by press-pressing under the conditions of ˜380 ° C., about 10-20 kg / cm 2 , about 30-60 minutes.
【００１１】得られたフィルムは、アルカリ金属水酸化
物、アンモニア、アミンなどと反応させて、3元共重合
体中の側鎖スルホニルハライド基をスルホン酸のアルカ
リ金属塩、アンモニウム塩、アミン塩などに変換させ
る。アルカリ金属塩は、水酸化ナトリウム、水酸化カリ
ウムなどのアルカリ金属水酸化物のアルコール水溶液中
に約60〜145℃で浸漬することにより形成される。アン
モニウム塩は、アンモニア水との反応により形成され
る。また、トリエチルアミン、トリエチレンジアミン、
トリエチレンテトラミン、1,8-ジアザビシクロ[5,4,0]
ウンデセン-7などのアミン塩は、これらアミンの水溶液
との反応により形成される。このようにして形成された
スルホン酸塩基含有3元共重合体のフィルムを、塩酸、
硫酸などの無機酸を溶解させたアルコール溶液中に、約
60〜90℃で浸漬することにより、遊離スルホン酸基を10
0%あるいは部分的に含有する3元共重合体のフィルムが
そこに形成される。遊離スルホン酸基を部分的に有する
共重合体は、スルホン酸塩基含有共重合体との混合物と
して用いることができる。The obtained film is reacted with an alkali metal hydroxide, ammonia, amine or the like to convert the side chain sulfonyl halide group in the terpolymer to the alkali metal salt, ammonium salt, amine salt of sulfonic acid, etc. Convert to. The alkali metal salt is formed by immersion in an aqueous alcohol solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at about 60 to 145 ° C. Ammonium salts are formed by reaction with aqueous ammonia. Also, triethylamine, triethylenediamine,
Triethylenetetramine, 1,8-diazabicyclo [5,4,0]
Amine salts such as undecene-7 are formed by reaction of these amines with aqueous solutions. The sulfonate group-containing terpolymer film thus formed was treated with hydrochloric acid,
In an alcohol solution in which an inorganic acid such as sulfuric acid is dissolved,
Free sulfonic acid groups can be
A film of terpolymer containing 0% or part of it is formed there. The copolymer partially having free sulfonic acid groups can be used as a mixture with a sulfonate group-containing copolymer.
【００１２】これらの側鎖にスルホン酸基またはスルホ
ン酸塩基を有する3元共重合体のフィルムを、フッ素樹
脂基質と金属との間に介在させた状態で加熱加圧する
と、これら両者間に良好な接着状態が形成される。When a film of a terpolymer having a sulfonic acid group or a sulfonate group on these side chains is heated and pressed while being interposed between the fluororesin substrate and the metal, good results are obtained between the two. An excellent adhesion state is formed.
【００１３】一方の被接着物たるフッ素樹脂基質として
は、ポリテトラフルオロエチレン、テトラフルオロエチ
レン-ヘキサフルオロプロペン共重合体、テトラフルオ
ロエチレン-パーフルオロ(低級アルキルビニルエーテ
ル)共重合体、テトラフルオロエチレン-エチレン共重合
体等のフィルム乃至シート、成形品等が挙げられる。こ
れらの各種重合体の中では、加熱加圧接着の観点から、
接着剤樹脂の軟化、流動温度よりも軟化、変形温度の高
いポリテトラフルオロエチレン、テトラフルオロエチレ
ン-パーフルオロ(低級アルキルビニルエーテル)共重合
体が好んで用いられる。また、接着性を更に強固にする
ために、フッ素樹脂基質の表面を、ナトリウム処理、プ
ラズマ処理、スパッタエッチング処理などして用いるこ
とが更に好ましい。On the other hand, as a fluororesin substrate as an adherend, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropene copolymer, tetrafluoroethylene-perfluoro (lower alkyl vinyl ether) copolymer, tetrafluoroethylene- Examples thereof include films and sheets of ethylene copolymer and the like, molded products and the like. Among these various polymers, from the viewpoint of heat and pressure adhesion,
Polytetrafluoroethylene and tetrafluoroethylene-perfluoro (lower alkyl vinyl ether) copolymers, which have higher softening and deformation temperatures than the adhesive resin, are preferably used. Further, in order to further strengthen the adhesiveness, it is more preferable to use the surface of the fluororesin substrate after sodium treatment, plasma treatment, sputter etching treatment or the like.
【００１４】また、他方の被接着物たる金属としては、
銅、ニッケル、アルミニウム、真ちゅう、鉄、ステンレ
ス鋼、けい素銅等の板状体乃至箔等が用いられる。As the other metal to be adhered,
Plates or foils of copper, nickel, aluminum, brass, iron, stainless steel, silicon copper or the like are used.
【００１５】加熱加圧接着は、フッ素樹脂基質と金属と
の間に、一般にフィルム状の3元共重合体を介在させ、
原則的にはフッ素樹脂基質の融点[例えば、ポリテトラ
フルオロエチレンでは327℃、テトラフルオロエチレン-
パーフルオロ(低級アルキルビニルエーテル)共重合体で
は308℃]以下でかつ約200℃以上の温度で、約5〜20kg/c
m2、約2〜30分間の条件下で加熱加圧することにより行
われる。勿論、これ以上の温度、例えば約380℃で加熱
加圧することもでき、この場合により、より短時間での
接着を可能とする。In heating and pressure bonding, a film-like terpolymer is generally interposed between a fluororesin substrate and a metal,
In principle, the melting point of the fluororesin substrate [eg 327 ° C for polytetrafluoroethylene, tetrafluoroethylene-
For perfluoro (lower alkyl vinyl ether) copolymer, it is about 5 ~ 20kg / c at the temperature below 308 ℃ and above about 200 ℃.
It is carried out by heating and pressurizing under the condition of m 2 , about 2 to 30 minutes. Of course, it is also possible to heat and pressurize at a temperature higher than this, for example, about 380 ° C., and in this case, bonding can be performed in a shorter time.
【００１６】[0016]
【発明の効果】フッ素樹脂基質と金属とを接着させる熱
溶融性のフッ素樹脂として、イオン性の官能基であるス
ルホン酸(塩)基を導入したものを用い、接着強度を上げ
ることにより、金属面に特別の表面処理を施さなくと
も、フッ素樹脂基質との間に良好な接着状態が形成され
る。従って、本発明に係る接着剤は、高周波用プリント
配線板などの製造時に有効に用いることができる。EFFECT OF THE INVENTION As a heat-melting fluororesin for adhering a fluororesin substrate and a metal, a sulfonic acid (salt) group, which is an ionic functional group, is introduced, and the adhesive strength is increased to improve the metal Even if the surface is not subjected to any special surface treatment, a good adhesion state is formed with the fluororesin substrate. Therefore, the adhesive according to the present invention can be effectively used when manufacturing a high-frequency printed wiring board or the like.
【００１７】[0017]
【実施例】次に、実施例について本発明を説明する。EXAMPLES The present invention will now be described with reference to examples.
【００１８】実施例 脱気した容量3Ｌの撹拌機付きステンレス鋼製オートク
レーブに、 脱塩脱酸素水 754.0g パーフルオロ(2-ブチルテトラヒドロフラン) 713.3g パーフルオロ(プロピルビニルエーテル) 56.0g パーフルオロ(3.6-ジオキサ-4-メチル-7-オクテン スルホニルフロライド) CF2＝CFOCF2CF(CF3)O(CF2)2SO2F [PSVE] 70.0g メタノール 105.0g をそれぞれ仕込み、50℃迄昇温させた後、圧力が9.0kg/
cm2になる迄テトラフルオロエチレンを仕込んだ。Example In a degassed 3 L stainless steel autoclave equipped with a stirrer, desalted and deoxidized water 754.0 g perfluoro (2-butyltetrahydrofuran) 713.3 g perfluoro (propyl vinyl ether) 56.0 g perfluoro (3.6- Dioxa-4-methyl-7-octene sulfonyl fluoride) CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 2 F [PSVE] 70.0 g Methanol 105.0 g are charged respectively and heated to 50 ° C. After the pressure is 9.0kg /
Tetrafluoroethylene was charged until it reached cm 2 .
【００１９】次いで、5重量%濃度のビス-パーフルオロ
ブチリルペルオキシド C3F7COOOCOC3F7のR-113(1,2,2-
トリクロロ-1,1,2-トリフルオロエタン)溶液7.4gを添加
して重合反応を開始させ、反応の進行と共に圧力が低下
するので、テトラフルオロエチレンを追加供給して、重
合圧力を維持した。反応の途中では、テトラフルオロエ
チレン仕込量が74gになった時点で、PSVE 30gを追加し
て添加し、また最初に用いた量の半分以下の重合開始剤
溶液を、数回に分けて添加した。Then, a 5 wt% concentration of bis-perfluorobutyryl peroxide C 3 F 7 COOOCOC 3 F 7 R-113 (1,2,2-
A polymerization reaction was started by adding 7.4 g of a (trichloro-1,1,2-trifluoroethane) solution, and the pressure decreased as the reaction proceeded. Therefore, tetrafluoroethylene was additionally supplied to maintain the polymerization pressure. In the middle of the reaction, when the amount of tetrafluoroethylene charged reached 74 g, PSVE 30 g was additionally added, and a polymerization initiator solution of less than half of the amount initially used was added in several times. .
【００２０】テトラフルオロエチレンの全仕込量が180g
になった時点(重合開始から144分後)で、テトラフルオ
ロエチレンの供給を停止し、未反応ガスをパージして、
オートクレーブから重合物を取り出した。この重合物を
減圧乾燥、水洗、ロ過およびオーブン乾燥して、3元共
重合体を208.3g(収率45.7%)得た。The total amount of tetrafluoroethylene charged is 180 g
At the point of time (144 minutes after the start of polymerization), the supply of tetrafluoroethylene was stopped, unreacted gas was purged,
The polymer was taken out from the autoclave. This polymer was dried under reduced pressure, washed with water, filtered and oven dried to obtain 208.3 g (yield 45.7%) of a terpolymer.
【００２１】この3元共重合体を、380℃、2kg/cm2、30
秒間の条件下で予熱し、次いで380℃、10kg/cm2、60秒
間の条件下で加圧プレスして、厚さ約0.1mmのフィルム
を得た。This terpolymer was treated at 380 ° C., 2 kg / cm 2 , 30
It was preheated under the condition of second, and then pressed under the condition of 380 ° C., 10 kg / cm 2 and 60 seconds to obtain a film having a thickness of about 0.1 mm.
【００２２】得られた3元共重合体フィルムを、50%メタ
ノール水溶液中に2.5N濃度となる量の水酸化ナトリウム
を溶解させた溶液中に、60℃で16時間浸漬すると、赤外
線吸収スペクトルでスルホニルフロライド基の1470cm-1
の吸収が殆んど消滅し、その代わりに1060cm-1付近にス
ルホン酸ナトリウム基の吸収が現われた。The obtained terpolymer film was immersed in a solution of sodium hydroxide in an amount of 2.5 N in a 50% aqueous methanol solution at a concentration of 2.5 N for 16 hours at 60 ° C. to obtain an infrared absorption spectrum. Sulfonyl fluoride group 1470 cm -1
The absorption of sodium sulfonate almost disappeared, and instead, the absorption of sodium sulfonate group appeared around 1060 cm -1 .
【００２３】次いで、メタノール中に1N濃度となる量の
塩化水素を溶解させた溶液中に、90℃で8.5時間浸漬す
ると、EPMA(Electron Probe Micro Analyzer)でNaピー
クの大幅な減少が認められることから、フィルム表面の
スルホン酸ナトリウム基はスルホン酸基へと変換してい
ることが確認された。Then, when immersed in a solution of 1N hydrogen chloride in methanol at 90 ° C. for 8.5 hours, EPMA (Electron Probe Micro Analyzer) shows a significant decrease in Na peak. From this, it was confirmed that the sodium sulfonate group on the film surface was converted into a sulfonate group.
【００２４】[接着試験]クロム処理銅板(厚さ0.035mm)
の上に、上記スルホン酸基含有3元共重合体フィルムお
よびフッ素樹脂フィルム[Na-ナフタリン錯体のテトラヒ
ドロフラン溶液中に浸漬して表面処理を行ったテトラフ
ルオロエチレン-パーフルオロアルキルビニルエーテル
(モル比約97：3)共重合体フィルム、厚さ0.05mm]を順次
重ね、360℃または380℃、2kg/cm2、2分間の条件下で予
熱した後、360℃または380℃、20kg/cm2、20分間の条件
下で加圧プレスした。このとき、厚さ0.26mmのポリイミ
ドフィルムがスペーサーとして用いられた。[Adhesion test] Chromium treated copper plate (thickness 0.035 mm)
On the above, the terpolymer copolymer film containing a sulfonic acid group and a fluororesin film [tetrafluoroethylene-perfluoroalkyl vinyl ether surface-treated by immersing in a tetrahydrofuran solution of Na-naphthalene complex]
(Molar ratio about 97: 3) Copolymer films, thickness 0.05mm] are sequentially stacked and preheated under the conditions of 360 ℃ or 380 ℃, 2kg / cm 2 for 2 minutes, and then 360 ℃ or 380 ℃, 20kg / pressed under the condition of / cm 2 for 20 minutes. At this time, a 0.26 mm-thick polyimide film was used as a spacer.
【００２５】フッ素樹脂フィルムと銅板間の接着強度
を、JIS C-6481に準じて、クロスヘッド速度50mm/分、2
4±2℃により測定すると、360℃の場合には0.60kg/cm、
また380℃の場合には0.65kg/cmの値がそれぞれ得られ
た。Adhesive strength between the fluororesin film and the copper plate was measured according to JIS C-6481 with a crosshead speed of 50 mm / min, 2
When measured at 4 ± 2 ℃, 0.60kg / cm at 360 ℃,
At 380 ° C, a value of 0.65 kg / cm was obtained.
【００２６】比較例 実施例の接着試験において、スルホン酸基含有3元共重
合体フィルムの代わりに、テトラフルオロエチレン-ヘ
キサフルオロプロピレン(重量比約88：12)共重合体フィ
ルム(厚さ約0.1mm)を用いて接着強度を測定すると、360
℃の場合には0.36kg/cm2、また380℃の場合には0.41kg/
cm2の値がそれぞれ得られたにすぎなかった。Comparative Example In the adhesion test of the example, a tetrafluoroethylene-hexafluoropropylene (weight ratio of about 88:12) copolymer film (thickness of about 0.1 was used instead of the sulfonic acid group-containing terpolymer film). mm) to measure the adhesive strength
0.36kg / cm 2 at ℃, 0.41kg / cm at 380 ℃
Only cm 2 values were obtained respectively.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年８月２６日[Submission date] August 26, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２６[Correction target item name] 0026
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２６】比較例 実施例の接着試験において、スルホン酸基含有３元共重
合体フィルムの代わりに、テトラフルオロエチレン−ヘ
キサフルオロプロピレン（重量比約８８：１２）共重体
フィルム（厚さ約０．１ｍｍ）を用いて接着強度を測定
すると、３６０℃の場合には０．３６ｋｇ／ｃｍ、また
３８０℃の場合には０．４１ｋｇ／ｃｍの値がそれぞれ
得られたにすぎなかった。 ─────────────────────────────────────────────────────
Comparative Example In the adhesion test of the example, a tetrafluoroethylene-hexafluoropropylene (weight ratio of about 88:12) copolymer polymer film (thickness of about 0. When the adhesive strength was measured using 1 mm), a value of 0.36 kg / cm 3 at 360 ° C. and a value of 0.41 kg / cm 3 at 380 ° C. were only obtained. ─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年９月１日[Submission date] September 1, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】 得られたフィルムは、アルカリ金属水酸
化物、アンモニアアミンなどと反応させて、３元共重合
体中の側鎖スルホニルハライド基をスルホン酸のアルカ
リ金属塩、アンモニウム塩、アミン塩などに変換させ
る。アルカリ金属塩は、水酸化ナトリウム、水酸化カリ
ウムなどのアルカリ金属水酸化物のアルコール水溶液中
に約６０〜１４５℃で浸漬することにより形成される。
アンモニウム塩は、アンモニア水との反応により形成さ
れる。また、トリエチルアミン、トリエチレンジアミ
ン、トリエチレンテトラミン、１，８−ジアザビシクロ
［５，４，０］ウンデセン−７などのアミン塩は、これ
らアミンの水溶液との反応により形成される。このよう
にして形成されたスルホン酸塩基含有３元共重合体のフ
ィルムを、塩酸、硫酸などの無機酸を溶解させたアルコ
ール溶液中に、約６０〜９０℃で浸漬することにより、
フィルム表面で遊離スルホン酸基を１００％あるいは部
分的に含有す３元共重合体のフィルムがそこに形成され
る。遊離スルホン酸基を部分的に有する共重合体は、ス
ルホン酸塩基含有共重合体との混合物として用いること
ができる。The obtained film is reacted with an alkali metal hydroxide, ammonia amine or the like to convert the side chain sulfonyl halide group in the terpolymer into an alkali metal salt, ammonium salt or amine salt of sulfonic acid. Convert it. The alkali metal salt is formed by immersing the alkali metal salt in an aqueous alcohol solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide at about 60 to 145 ° C.
Ammonium salts are formed by reaction with aqueous ammonia. Further, amine salts such as triethylamine, triethylenediamine, triethylenetetramine, 1,8-diazabicyclo [5,4,0] undecene-7 are formed by the reaction of these amines with an aqueous solution. By immersing the sulfonate group-containing terpolymer film thus formed in an alcohol solution in which an inorganic acid such as hydrochloric acid or sulfuric acid is dissolved at about 60 to 90 ° C.,
A film of a terpolymer containing 100% or partially free sulfonic acid groups on the film surface is formed there. The copolymer partially having free sulfonic acid groups can be used as a mixture with a sulfonate group-containing copolymer.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】 加熱加圧接着は、フッ素樹脂基質と金属
との間に、一般にフィルム状の３元共重合体を介在さ
せ、原則的にはフッ素樹脂基質の融点［例えは、ポリテ
トラフルオロエチレンでは３２７℃、テトラフルオロエ
チレン−パーフルオロ（プロピルビニルエーテル）共重
合体では３０８℃］以下でかつ約２００℃以上の温度
で、約５〜２０ｋｇ／ｃｍ２、約２〜３０分間の条件下
で加熱加圧することにより行われる。勿論、これ以上の
温度、例えば３８０℃で加熱加圧することもでき、この
場合により、より短時間での接着を可能とする。In heating and pressure bonding, a film-shaped terpolymer is generally interposed between a fluororesin substrate and a metal, and in principle, the melting point of the fluororesin substrate [for example, in polytetrafluoroethylene, 327 [deg.] C., tetrafluoroethylene-perfluoro ( propyl vinyl ether) copolymer is 308 [deg.] C. or lower and about 200 [deg.] C. or higher at about 5 to 20 kg / cm < 2 > for about 2 to 30 minutes. It is performed by pressing. Of course, it is also possible to heat and pressurize at a temperature higher than this, for example, 380 ° C., and in this case, bonding can be performed in a shorter time.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Name of item to be corrected] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】［接着試験］クロム処理銅板（厚さ０．０
３５ｍｍ）の上に、上記スルホン酸基含有３元共重合体
フィルムおよびフッ素樹脂フィルム［Ｎａ−ナフタリン
錯体のテトラヒドロフラン溶液中に浸漬して表面処理を
行ったテトラフルオロエチレン−パーフルオロ（プロピ
ルビニルエーテル）（モル比約９７：３）共重合体フィ
ルム、厚さ０．０５ｍｍ］を順次重ね、３６０℃または
３８０℃、２ｋｇ／ｃｍ２、２分間の条件下で予熱した
後、３６０℃または３８０℃、２０ｋｇ／ｃｍ２、２０
分間の条件下で加圧プレスした。このとき、厚さ０．２
６ｍｍのポリイミドフィルムがスペーサーとして用いら
れた。[Adhesion test] Chromium treated copper plate (thickness 0.0
35 mm), the above sulfonic acid group-containing ternary copolymer film and fluororesin film [tetrafluoroethylene-perfluoro (propionate treated by immersing in a tetrahydrofuran solution of Na-naphthalene complex]
Ruvinyl ether) (molar ratio about 97: 3) copolymer film, thickness of 0.05 mm] are sequentially stacked and preheated under the conditions of 360 ° C. or 380 ° C., 2 kg / cm 2 , 2 minutes, 360 ° C. or 380 ° C, 20 kg / cm 2 , 20
Pressing was performed under the condition of minute. At this time, thickness 0.2
A 6 mm polyimide film was used as a spacer.
Claims (5)
(低級アルキルビニルエーテル)および一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO3H で表わされるスルホン酸基含有パーフルオロビニルエー
テルまたはその塩の3元共重合体よりなるフッ素樹脂基
質と金属との接着剤。1. Tetrafluoroethylene, perfluoro
(Lower alkyl vinyl ether) and fluorinated resin composed of terpolymer of sulfonic acid group-containing perfluorovinyl ether represented by the general formula CF 2 = CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 3 H or a salt thereof Adhesive between substrate and metal.
脂基質と金属との間に介在させた状態で加熱加圧するこ
とを特徴とするフッ素樹脂基質と金属との接着方法。2. A method for adhering a fluororesin substrate and a metal, wherein the terpolymer according to claim 1 is heated and pressed while being interposed between the fluororesin substrate and the metal.
(低級アルキルビニルエーテル)および一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO2X (ここで、Xはハロゲン原子である)で表わされるスルホ
ニルハライド基含有パーフルオロビニルエーテルの3元
共重合体をアルカリ金属水酸化物、アンモニアまたはア
ミンと反応させることを特徴とする、テトラフルオロエ
チレン、パーフルオロ(低級アルキルビニルエーテル)お
よび一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO3M (ここで、Mはアルカリ金属、アンモニウム基またはアミ
ノ基である)で表わされるスルホン酸塩基含有パーフル
オロビニルエーテルの3元共重合体の製造法。3. Tetrafluoroethylene, perfluoro
(Lower alkyl vinyl ether) and the general formula CF 2 = CFOCF 2 CF (CF 3) O (CF 2) 2 SO 2 X ( wherein, X is halogen atom) 3 of sulfonyl halide group-containing perfluorovinyl ether represented by Tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) and the general formula CF 2 = CFOCF 2 CF (CF 3 ) O (CF, characterized by reacting the former copolymer with an alkali metal hydroxide, ammonia or an amine. 2 ) A method for producing a terpolymer containing a sulfonate group-containing perfluorovinyl ether represented by 2 SO 3 M (where M is an alkali metal, an ammonium group or an amino group).
チレン、パーフルオロ(低級アルキルビニルエーテル)お
よびスルホン酸塩基含有パーフルオロビニルエーテルの
3元共重合体を無機酸と反応させることを特徴とする、
テトラフルオロエチレン、パーフルオロ(低級アルキル
ビニルエーテル)および一般式 CF2＝CFOCF2CF(CF3)O(CF2)2SO3H で表わされるスルホン酸基含有パーフルオロビニルエー
テルの3元共重合体の製造法。4. A tetrafluoroethylene, a perfluoro (lower alkyl vinyl ether) and a sulfonate group-containing perfluorovinyl ether obtained in claim 3.
Characterized by reacting a terpolymer with an inorganic acid,
Of terpolymers of tetrafluoroethylene, perfluoro (lower alkyl vinyl ether) and sulfonic acid group-containing perfluorovinyl ether represented by the general formula CF 2 ═CFOCF 2 CF (CF 3 ) O (CF 2 ) 2 SO 3 H Manufacturing method.
で行われる3元共重合体の製造法。5. A method for producing a terpolymer, wherein the reaction according to claim 3 or 4 is carried out in a film state.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31910993A JP3334301B2 (en) | 1993-11-25 | 1993-11-25 | Adhesive between fluoroplastic substrate and metal |
| DE4437573A DE4437573B4 (en) | 1993-11-25 | 1994-10-20 | An adhesive for bonding a fluorohydrocarbon resin substrate to a metal, a process for its preparation in film form and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31910993A JP3334301B2 (en) | 1993-11-25 | 1993-11-25 | Adhesive between fluoroplastic substrate and metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07145362A true JPH07145362A (en) | 1995-06-06 |
| JP3334301B2 JP3334301B2 (en) | 2002-10-15 |
Family
ID=18106568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31910993A Expired - Fee Related JP3334301B2 (en) | 1993-11-25 | 1993-11-25 | Adhesive between fluoroplastic substrate and metal |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3334301B2 (en) |
| DE (1) | DE4437573B4 (en) |
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|---|---|---|---|---|
| US4285795A (en) * | 1973-08-09 | 1981-08-25 | Hooker Chemicals & Plastics Corp. | Electrolysis apparatus |
| JPS5959764A (en) * | 1982-09-29 | 1984-04-05 | Daikin Ind Ltd | Heat-sensitive adhesive |
| EP0290848B1 (en) * | 1987-04-25 | 1991-07-31 | Daikin Industries, Limited | Novel fluorovinyl ether |
-
1993
- 1993-11-25 JP JP31910993A patent/JP3334301B2/en not_active Expired - Fee Related
-
1994
- 1994-10-20 DE DE4437573A patent/DE4437573B4/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08208931A (en) * | 1995-02-02 | 1996-08-13 | Tokyo Gas Furoro Material Kk | Production of steel sheet laminated with patterned fluororesin film |
| WO1997021779A1 (en) * | 1995-12-08 | 1997-06-19 | Daikin Industries, Ltd. | Fluoroadhesive and adhesive film and laminate prepared therefrom |
| US6713183B2 (en) | 1995-12-08 | 2004-03-30 | Daikin Industries, Ltd. | Fluorine-containing adhesive and adhesive film and laminated article produced by using same |
| US6060828A (en) * | 1996-09-11 | 2000-05-09 | Patent-Treuhand-Gesellschaft Fuer Elektrische Gluehlampen Mbh | Electric radiation source and irradiation system with this radiation source |
| JP2002276819A (en) * | 2001-03-15 | 2002-09-25 | Mitsubishi Cable Ind Ltd | Oil seal |
| JP2004010744A (en) * | 2002-06-06 | 2004-01-15 | Japan Atom Energy Res Inst | Fluorine-based macromolecular copolymer having large ion-exchanging capacity and oxidation resistance, and method for producing the same |
| JP2009190212A (en) * | 2008-02-13 | 2009-08-27 | Toho Kasei Kk | Insulated substrate material for high-frequency band |
| US10505197B2 (en) | 2011-03-11 | 2019-12-10 | Audi Ag | Unitized electrode assembly with high equivalent weight ionomer |
| JP2016508168A (en) * | 2012-12-21 | 2016-03-17 | アウディ アクチェンゲゼルシャフトＡｕｄｉ Ａｇ | Manufacturing method of electrolyte material |
| JP2018510235A (en) * | 2015-02-12 | 2018-04-12 | スリーエム イノベイティブ プロパティズ カンパニー | Copolymer of tetrafluoroethylene and perfluorinated allyl ether |
| US10676555B2 (en) | 2015-02-12 | 2020-06-09 | 3M Innovative Properties Company | Tetrafluoroethylene copolymers having sulfonyl groups |
| US10717795B2 (en) | 2015-02-12 | 2020-07-21 | 3M Innovative Properties Company | Tetrafluoroethylene/hexafluoropropylene copolymers having pendant sulfonyl groups |
| US10844152B2 (en) | 2015-02-12 | 2020-11-24 | 3M Innovative Properties Company | Tetrafluoroethylene and perfluorinated allyl ether copolymers |
| CN115322279A (en) * | 2022-08-11 | 2022-11-11 | 乳源东阳光氟树脂有限公司 | 1, 1-difluoroethylene copolymer and preparation method and application thereof |
| CN115322279B (en) * | 2022-08-11 | 2024-01-26 | 乳源东阳光氟树脂有限公司 | 1, 1-difluoroethylene copolymer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4437573A1 (en) | 1995-06-01 |
| DE4437573B4 (en) | 2007-03-08 |
| JP3334301B2 (en) | 2002-10-15 |
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