JPH0616725A - Fluororesin composition - Google Patents
Fluororesin compositionInfo
- Publication number
- JPH0616725A JPH0616725A JP19454592A JP19454592A JPH0616725A JP H0616725 A JPH0616725 A JP H0616725A JP 19454592 A JP19454592 A JP 19454592A JP 19454592 A JP19454592 A JP 19454592A JP H0616725 A JPH0616725 A JP H0616725A
- Authority
- JP
- Japan
- Prior art keywords
- perfluoro
- dioxole
- dimethyl
- fluororesin composition
- coupling agent
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は主単量体がパーフルオロ
（−2,2-ジメチル−1,3-ジオキソール）であるフッ素樹
脂に関し、とくにガラス、金属、他の樹脂との密着性を
改良したフッ素樹脂組成物に関するものである。FIELD OF THE INVENTION The present invention relates to a fluororesin whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole), and particularly, has excellent adhesiveness to glass, metal and other resins. The present invention relates to an improved fluororesin composition.
【０００２】[0002]
【従来の技術】主単量体がパーフルオロ（−2,2-ジメチ
ル−1,3-ジオキソール）であるフッ素樹脂は、従来開発
されてきたフッ素樹脂と同様、耐熱性、耐薬品性、低屈
折率、電気絶縁性、低誘電率、撥水・撥油性といった優
れた特性を有している。さらに非晶質であるため透明で
あること、また特定のパーフルオロ溶媒のみに溶解する
といった従来のフッ素樹脂には見られない特性も有して
いることから、低誘電率を活かして半導体保護膜などの
エレクトロニクス分野に、また低屈折率、透明性を活か
して光ファイバの鞘材や反射防止膜といった光学分野へ
の利用が期待できる。2. Description of the Related Art Fluorocarbon resins whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole) have the same heat resistance, chemical resistance and low resistance as conventional fluorocarbon resins. It has excellent properties such as refractive index, electrical insulation, low dielectric constant, and water / oil repellency. Furthermore, because it is amorphous, it is transparent, and because it has characteristics not found in conventional fluororesins, such as being soluble only in a specific perfluoro solvent, it is a semiconductor protective film that takes advantage of its low dielectric constant. It can be expected to be applied to the electronics field such as, and to the optical field such as the sheath material of an optical fiber and the antireflection film by utilizing the low refractive index and transparency.
【０００３】[0003]
【発明が解決しようとする課題】しかし、一方で主単量
体がパーフルオロ（−2,2-ジメチル−1,3-ジオキソー
ル）であるフッ素樹脂も、他のフッ素樹脂と同様、表面
自由エネルギーが著しく低く、他の材料との密着性に乏
しいという欠点を有するため、その用途が制限されてい
た。On the other hand, on the other hand, a fluororesin whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole) is similar to other fluororesins in surface free energy. Is extremely low and has poor adhesion to other materials, so that its use was limited.
【０００４】[0004]
【課題を解決するための手段】そこで本発明者等は、種
々検討した結果、メルカプト基を有するシランカップリ
ング剤をパーフルオロ（−2,2-ジメチル−1,3-ジオキソ
ール）系重合体に配合することにより、ガラス、金属、
他の樹脂との密着性を改良し得ることを見いだした。Means for Solving the Problems The inventors of the present invention have made various studies and found that a silane coupling agent having a mercapto group was converted to a perfluoro (-2,2-dimethyl-1,3-dioxole) -based polymer. By blending, glass, metal,
It has been found that the adhesion with other resins can be improved.
【０００５】本発明に用いられるパーフルオロ（−2,2-
ジメチル−1,3-ジオキソール）は、米国特許３８６５８
４５号などに記載の方法によって合成することができ、
また単独重合または共重合ができる。パーフルオロ（−
2,2-ジメチル−1,3-ジオキソール）と共重合可能な１ま
たは２以上のコモノマとしては、米国特許３９７８０３
０号などに記載されたごとき、CF2=CF2, CF2=CFCl, CH2
=CF2, CF2=CFCF3,CHF=CF2, CF2=CFORf（Rf＝CnF2n+1 、
ｎ＝１〜３）, CH2=CHF, CH2=CHRf （Rf＝CnF2n+1 、ｎ
＝１〜８）, CF2=CFOQZ （式中、Ｑ＝パーフルオロアル
キルエーテル：エーテル酸素原子数０〜５、アルキル基
炭素原子とエーテル酸素原子の和が２〜10、Ｚ＝COOCnH
2n+1、ｎ＝１〜４、COF, SO2F, CN ）が挙げられるが、
これに限定されるものではない。The perfluoro (-2,2- used in the present invention
Dimethyl-1,3-dioxole is described in US Pat.
45 can be synthesized by the method described in
Further, homopolymerization or copolymerization is possible. Perfluoro (-
2,2-dimethyl-1,3-dioxole) as one or more comonomers copolymerizable with U.S. Pat.
As described in No. 0, CF 2 = CF 2 , CF 2 = CFCl, CH 2
= CF 2 , CF 2 = CFCF 3 , CHF = CF 2 , CF 2 = CFOR f (R f = C n F 2n + 1 ,
n = 1 to 3), CH 2 = CHF, CH 2 = CHR f (R f = C n F 2n + 1 , n
= 1 to 8), CF 2 = CFOQZ (in the formula, Q = perfluoroalkyl ether: the number of ether oxygen atoms is 0 to 5, the sum of alkyl group carbon atoms and ether oxygen atoms is 2 to 10, Z = COOC n H
2n + 1 , n = 1 to 4, COF, SO 2 F, CN),
It is not limited to this.
【０００６】また上の重合体は、特表平３−５００５４
７号公報等の記載から、末端に-COF基を有することが知
られており、この点を考慮して検討した結果、本発明に
おいてはとくに-COF基と反応し得るメルカプト基を有す
るシランカップリング剤がガラス、金属、他の樹脂との
密着性を向上させるのに有効であることを見いだした。
本発明で用いるシランカップリング剤は、HS-Y-Si-X3,
HS-Y-Si(R1)-X2, HS-Y-Si(R1)(R2)-X （式中、Ｙはアル
キレン基で途中に酸素原子、窒素原子、イオウ原子、リ
ン原子、ハロゲンを含んでいてもかまわない。R1、R2は
アルキル基を、Ｘは-Cl,-OCH3,-OC2H5, -OC2H40CH3,-OC
OCH3,-N(CH3)2 といった加水分解基）で表されるように
-COF基と反応しうるメルカプト基を有しているものであ
ればよく、加水分解基は１つでも２つでも３つでもよ
い。またメルカプト基は２つ以上有していても差し支え
ない。シランカップリング剤を配合する割合は、主単量
体がパーフルオロ（−2,2-ジメチル−1,3-ジオキソー
ル）であるフッ素樹脂に対して0.01wt％以上、１wt％以
下が好ましく、とくに0.05〜 0.5wt％程度が好ましい。
１wt％を超えて配合すれば透明性が損なわれ、0.01wt％
より少なければ密着性の効果が発現されない。Further, the above polymer has the characteristics of JP-A-3-50054.
It is known from the description of Japanese Patent Publication No. 7 etc. that it has a -COF group at the terminal, and as a result of studying in consideration of this point, in the present invention, in particular, a silane cup having a mercapto group capable of reacting with a -COF group. It was found that the ring agent is effective in improving the adhesion to glass, metal and other resins.
The silane coupling agent used in the present invention is HS-Y-Si-X 3 ,
HS-Y-Si (R 1 ) -X 2 , HS-Y-Si (R 1 ) (R 2 ) -X (In the formula, Y is an alkylene group, and an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom R 1 , R 2 are alkyl groups, and X is —Cl, —OCH 3 ,, OC 2 H 5 ,, OC 2 H 40 CH 3 ,, OC.
OCH 3 ,, -N (CH 3 ) 2 )
Any hydrolyzable group may be used as long as it has a mercapto group capable of reacting with the —COF group, and the number of hydrolyzable groups may be one, two or three. Further, it may have two or more mercapto groups. The proportion of the silane coupling agent to be blended is preferably 0.01 wt% or more and 1 wt% or less with respect to the fluororesin whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole). About 0.05 to 0.5 wt% is preferable.
If it exceeds 1wt%, the transparency will be impaired, and 0.01wt%
If it is less, the effect of adhesion will not be exhibited.
【０００７】［密着性の評価方法］密着性の評価はJIS
K 5400に記載の碁盤目テープ法にて行った。すなわち、
主単量体がパーフルオロ（−2,2-ジメチル−1,3-ジオキ
ソール）であるフッ素樹脂をパーフルオロ（−2-ブチル
テトラヒドロフラン）に溶解し、これにシランカップリ
ング剤を配合したものを、基材上に塗布し、乾燥後のフ
ィルムの厚さが約50μｍとなるようにロールコーティン
グした。これを試験片とし、カッターナイフにて１mm間
隔の切傷を縦横それぞれ11本つけると 100ケのます目が
できる。この上にセロハンテープを貼り、消しゴムでこ
すってテープを完全に付着させ、テープをはがしてはが
れたます目の数を剥離率と称することとし、密着性の評
価の基準とした。[Adhesion Evaluation Method] Adhesion is evaluated according to JIS
It was carried out by the cross-cut tape method described in K 5400. That is,
A fluororesin whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole) is dissolved in perfluoro (-2-butyltetrahydrofuran), and a silane coupling agent is added to this. , And was roll-coated so that the film thickness after drying was about 50 μm. Using this as a test piece, and making 11 cuts at 1 mm intervals in each of the vertical and horizontal directions with a cutter knife, 100 squares are created. A cellophane tape was adhered onto this, and the tape was completely adhered by rubbing with an eraser, and the number of peeled off tapes was called the peeling rate, which was used as a criterion for evaluation of adhesion.
【０００８】以下、実施例により本発明をさらに詳細に
説明する。Hereinafter, the present invention will be described in more detail with reference to Examples.
【０００９】[0009]
【実施例１】パーフルオロ（−2,2-ジメチル−1,3-ジオ
キソール）／テトラフルオロエチレン＝（65／35 mol
％）の共重合体10ｇをパーフルオロ（−2-ブチルテトラ
ヒドロフラン）40ｇに溶解し、HS(CH2)3Si(OC2H5)3を0.
05ｇ配合した。この溶液をガラス板上にロールコーティ
ングし、乾燥後、碁盤目テープ法による塗膜の密着性試
験を行ったところ剥離率は０％であった。Example 1 Perfluoro (-2,2-dimethyl-1,3-dioxole) / tetrafluoroethylene = (65/35 mol
%) Copolymer was dissolved in 40 g of perfluoro (-2-butyltetrahydrofuran), and HS (CH 2 ) 3 Si (OC 2 H 5 ) 3 was dissolved in 0.2 g.
05g was added. When this solution was roll-coated on a glass plate and dried, an adhesion test of the coating film was carried out by a cross-cut tape method. As a result, the peeling rate was 0%.
【００１０】[0010]
【比較例１】実施例１で用いたパーフルオロ（−2,2-ジ
メチル−1,3-ジオキソール）系重合体の溶液にHS(CH2)3
Si(OC2H5)3を配合しなかった溶液をガラス板上にコーテ
ィングした試験片の剥離率は 100％であった。Comparative Example 1 HS (CH 2 ) 3 was added to the solution of the perfluoro (-2,2-dimethyl-1,3-dioxole) polymer used in Example 1.
The peel rate of the test piece coated with the solution containing no Si (OC 2 H 5 ) 3 on the glass plate was 100%.
【００１１】[0011]
【実施例２】実施例１で用いたパーフルオロ（−2,2-ジ
メチル−1,3-ジオキソール）系重合体溶液50ｇにカップ
リング剤としてHS(CH2)3Si(OC2H5)3を0.01ｇおよび0.00
4g配合した組成物を作り、実施例１と同様にして塗膜を
作り、その剥離試験を行ったところそれぞれ５％、20％
であった。Example 2 50 g of the perfluoro (-2,2-dimethyl-1,3-dioxole) -based polymer solution used in Example 1 was mixed with HS (CH 2 ) 3 Si (OC 2 H 5 ) as a coupling agent. 0.01 for 3 and 0.00
A composition containing 4 g was prepared, a coating film was prepared in the same manner as in Example 1, and a peeling test was conducted, and the composition was 5% and 20%, respectively.
Met.
【００１２】[0012]
【実施例３】実施例１で用いたパーフルオロ（−2,2-ジ
メチル−1,3-ジオキソール）系重合体溶液50ｇにHS(C
H2)3Si(OC2H5)3を0.01ｇ配合した。溶液を鉄板、アルミ
ニウム板上にコーティングした。乾燥後のフィルムの剥
離率はいずれも０％であった。また上記方法においてシ
ランカップリング剤を配合しない溶液を用いて形成した
塗膜の剥離率はそれぞれ70％、85％であった。Example 3 HS (C) was added to 50 g of the perfluoro (-2,2-dimethyl-1,3-dioxole) polymer solution used in Example 1.
0.01 g of H 2 ) 3 Si (OC 2 H 5 ) 3 was added. The solution was coated on an iron plate and an aluminum plate. The peeling rate of the film after drying was 0% in all cases. Further, the peeling rates of the coating films formed by using the solution containing no silane coupling agent in the above method were 70% and 85%, respectively.
【００１３】[0013]
【実施例４】実施例１で用いたパーフルオロ（−2,2-ジ
メチル−1,3-ジオキソール）系ポリマの溶液50ｇにHS(C
H2)3Si(OC2H5)3を0.01ｇ配合した溶液をポリメチルメタ
クリレート板、ポリカーボネート板、ポリスチレン板上
にコーティングし、乾燥後のフィルムの剥離率を測定し
たところ、それぞれ０％、10％、０％であった。また上
記方法においてシランカップリング剤を配合しないフッ
素樹脂溶液を用い、上記方法と同様にして各基材上に塗
布して形成した塗膜の剥離率はそれぞれ85％、100％、9
0％であった。Example 4 HS (C) was added to 50 g of a solution of the perfluoro (-2,2-dimethyl-1,3-dioxole) polymer used in Example 1.
H 2 ) 3 Si (OC 2 H 5 ) 3 was mixed with 0.01 g of a solution coated on a polymethylmethacrylate plate, a polycarbonate plate, and a polystyrene plate, and the peeling rate of the film after drying was measured to be 0%, respectively. It was 10% and 0%. Further, in the above method, using a fluororesin solution containing no silane coupling agent, the peeling rates of the coating films formed by coating on the respective substrates in the same manner as in the above methods are 85%, 100% and 9%, respectively.
It was 0%.
Claims (1)
ル−1,3-ジオキソール）であるフッ素樹脂に対し、メル
カプト基を有するシランカップリング剤を重量部にして
0.01wt％以上、１wt％以下なる割合で配合してなること
を特徴とするフッ素樹脂組成物。1. A silane coupling agent having a mercapto group is added to a fluororesin whose main monomer is perfluoro (-2,2-dimethyl-1,3-dioxole) in parts by weight.
A fluororesin composition characterized by being blended in a proportion of 0.01 wt% or more and 1 wt% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19454592A JPH0616725A (en) | 1992-06-30 | 1992-06-30 | Fluororesin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19454592A JPH0616725A (en) | 1992-06-30 | 1992-06-30 | Fluororesin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0616725A true JPH0616725A (en) | 1994-01-25 |
Family
ID=16326318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19454592A Pending JPH0616725A (en) | 1992-06-30 | 1992-06-30 | Fluororesin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0616725A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016104380A1 (en) * | 2014-12-25 | 2016-06-30 | 旭硝子株式会社 | Electrolyte material, liquid composition, and membrane-electrode assembly for solid polymer fuel cell |
-
1992
- 1992-06-30 JP JP19454592A patent/JPH0616725A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016104380A1 (en) * | 2014-12-25 | 2016-06-30 | 旭硝子株式会社 | Electrolyte material, liquid composition, and membrane-electrode assembly for solid polymer fuel cell |
| CN107108781A (en) * | 2014-12-25 | 2017-08-29 | 旭硝子株式会社 | Electrolyte, fluid composition and membrane-electrode assembly for polymer electrolyte fuel cell |
| JPWO2016104380A1 (en) * | 2014-12-25 | 2017-11-02 | 旭硝子株式会社 | Electrolyte material, liquid composition, and membrane electrode assembly for polymer electrolyte fuel cell |
| CN107108781B (en) * | 2014-12-25 | 2020-08-11 | Ａｇｃ株式会社 | Electrolyte material, liquid composition, and membrane electrode assembly for polymer electrolyte fuel cell |
| US10879551B2 (en) | 2014-12-25 | 2020-12-29 | AGC Inc. | Electrolyte material, liquid composition and membrane/electrode assembly for polymer electrolyte fuel cell |
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