JPS6141743B2 - - Google Patents
Info
- Publication number
- JPS6141743B2 JPS6141743B2 JP12853081A JP12853081A JPS6141743B2 JP S6141743 B2 JPS6141743 B2 JP S6141743B2 JP 12853081 A JP12853081 A JP 12853081A JP 12853081 A JP12853081 A JP 12853081A JP S6141743 B2 JPS6141743 B2 JP S6141743B2
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- base material
- adhesion
- thin film
- phosphorus
- 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.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- 239000010409 thin film Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 238000000576 coating method Methods 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 etc. Chemical compound 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910000680 Aluminized steel Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本発明は、燐を含有する基板上に弗素樹脂を被
覆形成した弗素樹脂薄膜複合体に関するものであ
る。
弗素樹脂は耐熱性，耐薬品性，耐摩耗性，非粘
着性，耐電気絶縁性などすぐれた特性を有してい
る。この特性を利用して、化学，電気，機械，食
品などの各種工業、およびフライパン，アイロン
などの家庭用品にまで広く使用されている。
ところが、この樹脂の非粘着性という特性は、
基材との接着性に乏しいことを意味し、種々の厳
しい使用条件に対して満足した特性が得られてい
ないのが現状であり、一般塗料に対して塗膜形成
上において特殊な方法を採用しなければならな
い。
すなわち、塗膜形成に先立つて、基材表面を物
理的，化学的に十分粗面化して表面積を増大し、
反応性に富む表面を形成して接着性を強め、樹脂
と基材の密着強度を得ようとするものであり、そ
の表面に弗素樹脂の接着性を向上させるための下
塗り（プライマー）塗装を行う。さらにその上に
弗素樹脂の被膜を形成して、希望の物品を得るの
が通常行う方法である。
従来、弗素樹脂と基材との密着性を向上させる
方法として、弗素樹脂デイスパージヨンの改
良、下塗り（プライマー）塗料の改良、基材
と下塗り塗料の間の接着力を改善するためにセラ
ミツクあるいは金属の多孔質層を形成する方法な
どの改善提案があらゆる角度から行われている。
例えば、弗素樹脂デイスパージヨンの改良として
は特公昭47−13194号公報、下塗り塗料の改良と
しては特開昭52−10332号、特公昭54−42366号公
報、基材と下塗り塗料間に多孔質層を形成する方
法としては特公昭40−9699号公報など種々の文献
に記載されている。
しかし、これらの方法はいずれも基材と弗素樹
脂を物理的に結合しようとするものであり、根本
的にはヒートサイクル等により剥離しやすい。
本発明は、弗素樹脂と基材間の結合手段とし
て、上記のような物理的結合に加え、化学的結合
を加味して強固な結合層を得ようとするものであ
る。
前述のように、従来は弗素樹脂，プライマー
層，多孔質層の研究は多方面にわたつて行われて
いるが、弗素樹脂と基材間の強固な結合層を得る
目的から基材そのものを研究した文献はまつたく
ない。
本発明者らは、以上に鑑み、基材と弗素樹脂と
の化学的結合をめざして基材そのものを種々検討
した結果、基材に燐を含有させることにより、上
記の目的を達成することに成功した。
以下に本発明を詳細に説明する。
基材表面に厚さ10μｍ内外の弗素樹脂薄膜層を
形成するには、弗素樹脂からなるエナメル材を塗
布し、乾燥後350〜430℃で５〜60分間の焼成が必
要である。この焼成期間中に、基材と弗素樹脂，
基材と炉内雰囲気で反応が生じ、基材が物理化学
的に変化するため、本発明の目的を完遂するには
まず、弗素樹脂の選択が重要である。
弗素樹脂デイスパージヨンは、弗素樹脂の微粉
末にコロイド安定剤，界面活性剤，溶着促進剤な
どの添加剤を加えて乳化重合した分散液を一定濃
度に濃縮して安定化したものである。一般に弗素
樹脂粒子の含有率は40〜70重量％で、平均粒径は
0.1〜0.8μｍであり、粘度は20〜30CP，PHは９〜
11，比重（25℃）1.3〜1.6の水性懸濁液である。
弗素樹脂は、一般的に非粘着性の物質である反
面、基材との密着性が非常に悪いという特性を有
する。
第１表は表面拡大処理を施していないアルミニ
ウム基材と弗素樹脂薄膜との密着性を示したもの
である。
The present invention relates to a fluororesin thin film composite formed by coating a fluororesin on a substrate containing phosphorus. Fluororesin has excellent properties such as heat resistance, chemical resistance, abrasion resistance, non-adhesiveness, and electrical insulation resistance. Taking advantage of this property, it is widely used in various industries such as chemical, electrical, mechanical, and food industries, and even in household items such as frying pans and irons. However, the non-adhesive property of this resin
This means that it has poor adhesion to the base material, and currently it is not possible to obtain properties that satisfy various harsh usage conditions, so a special method is used to form a film compared to general paints. Must. That is, prior to coating film formation, the surface of the base material is sufficiently roughened physically and chemically to increase the surface area.
The purpose is to form a highly reactive surface to strengthen adhesion and obtain adhesion strength between the resin and the base material, and the surface is coated with a primer to improve the adhesion of the fluororesin. . The usual method is to further form a fluororesin coating thereon to obtain the desired article. Conventionally, methods for improving the adhesion between fluororesin and base materials include improving fluororesin dispersions, improving primer paints, and using ceramics or Improvements have been proposed from all angles, including methods for forming porous metal layers.
For example, improvements in fluororesin dispersion are disclosed in Japanese Patent Publication No. 47-13194, improvements in undercoat paints are disclosed in Japanese Patent Publication No. 52-10332, and Japanese Patent Publication No. 54-42366. Methods for forming layers are described in various documents such as Japanese Patent Publication No. 40-9699. However, all of these methods attempt to physically bond the base material and the fluororesin, and fundamentally they tend to peel off due to heat cycles and the like. The present invention aims to obtain a strong bonding layer by adding chemical bonding in addition to the above-mentioned physical bonding as a bonding means between the fluororesin and the base material. As previously mentioned, research on fluororesins, primer layers, and porous layers has been conducted in a variety of fields, but research has focused on the base material itself in order to obtain a strong bonding layer between the fluororesin and the base material. I don't want to read the literature that has been published. In view of the above, the present inventors conducted various studies on the base material itself with the aim of creating a chemical bond between the base material and the fluororesin, and as a result, they determined that the above objective could be achieved by incorporating phosphorus into the base material. Successful. The present invention will be explained in detail below. In order to form a fluororesin thin film layer with a thickness of about 10 μm on the surface of a base material, it is necessary to apply an enamel material made of a fluororesin, dry it, and then bake it at 350 to 430° C. for 5 to 60 minutes. During this firing period, the base material and fluororesin,
Since a reaction occurs between the base material and the atmosphere in the furnace, and the base material changes physicochemically, the selection of the fluororesin is important in order to accomplish the purpose of the present invention. Fluororesin dispersion is made by adding additives such as colloidal stabilizers, surfactants, and adhesion promoters to fine fluororesin powder, emulsion polymerizing the resulting dispersion, and concentrating and stabilizing the dispersion to a certain concentration. Generally, the content of fluororesin particles is 40 to 70% by weight, and the average particle size is
0.1~0.8μm, viscosity 20~30CP, PH 9~
11. It is an aqueous suspension with a specific gravity (25℃) of 1.3 to 1.6. Although fluororesin is generally a non-adhesive substance, it has a characteristic that it has very poor adhesion to a base material. Table 1 shows the adhesion between the fluororesin thin film and the aluminum base material that has not been subjected to surface enlargement treatment.
【表】
上記表に示すアルミニウム基材Ａ〜Ｄは、約
380℃の弗素樹脂被覆層の焼成中に表面が著しい
酸化増量や酸化劣化することはないが、焼成後の
弗素樹脂はテープ剥離試験ですべて剥離し、密着
強度が得られないことが明らかになつた。
従来は、密着強度を得るためにアルミニウム基
材に表面拡大化処理を施し、物理的な接着効果に
より、密着強度を得ていた。たとえば第１図に示
すような製造法である。
基材表面は粉塵，油性物質，酸化防止剤が付着
しているので脱脂，洗浄が必要となる。その後、
乾燥し、次の工程として表面拡大化処理を施す。
この工程は弗素樹脂被覆の薄膜を均一に接着させ
て密着強度を得るためのものであり、基材の表面
はタリサーフ表面粗度計でRaが0.1〜1.8μｍ程度
が必要である。Raが0.1μｍ以下になると５〜10
μｍ内外の均一な弗素樹脂薄膜の密着強度が得ら
れない。一方Raが1.8μｍ以上になると５〜10μ
ｍ内外の均一な被膜厚の精度維持が困難となる。
このため中心線平均粗度Raは0.1〜1.8μｍの範囲
が最適である。
表面拡大化処理は通常、化学的エツチング法，
サンドブラスト法などの方法で行われるが、基材
と弗素樹脂の密着性を得るための方法としては、
上記のような表面凹凸形成法の他に、陽極酸化処
理，化成処理などが汎用されている。特にアルミ
ニウムの場合は化成処理が多用され、リン酸鉄
系，リン酸亜鉛系、リン酸マンガン系などを用い
るリン酸塩処理，クローメート処理，リン酸−ク
ロム酸処理などが適している。しかし、基材に表
面拡大化処理あるいは化学処理を施して形成した
弗素樹脂薄膜は、強固な密着性が得られる反面、
粗面化あるいは化成処理された基材表面に気泡が
残り、ピンホールのない薄膜を形成するのが非常
に困難である。また透明な弗素樹脂薄膜を形成し
た場合、灰黒色の酸化被膜（化成処理）あるいは
無光沢の表面相（サンドブラスト）を呈し、美し
い金属光沢面が得られず、装飾的な観点からまこ
とに不都合である。
本発明は、上記の点に鑑み、ピンホールがな
く、透明弗素樹脂薄膜を形成した時には金属光沢
面が得られるような弗素樹脂薄膜複合体を提供す
るものである。
第２図は本発明の一実施例である弗素樹脂薄膜
複合体の製造工程を示したものである。
本発明に用いられる基材は、銅，銅合金，アル
ミニウム，アルミニウム合金，鉄，鉄基合金，ア
ルミナイズド鋼板，亜鉛鉄板などの金属材料に燐
を添加した材料が適している。これらの材料に燐
を添加した場合の効果は後に詳述するが、基材に
燐を添加することにより、表面拡大化処理を施さ
なくても弗素樹脂と基材の強固な結合層が得ら
れ、透明薄膜を形成した場合でも美しい金属光沢
面を呈するとともに、製造工程を簡略化できる。
本発明で用いられる弗素樹脂としては、ポリ四
弗化エチレン，四弗化エチレン−六弗化プロピレ
ンの共重合体，ポリ三弗化エチレンなどの各樹脂
の単独またはこれらの樹脂の組み合わせが好まし
い。また、これらの樹脂の粒度はできるだけ細か
なものが本発明の目的に適うので、弗素樹脂の粒
度が平均粒径で0.8μｍ以下の乳化重合されたも
のが好ましい。
通常の基材の表面には酸化被膜，油分，水分、
および大気雰囲気下での種々の汚染物質が存在し
ている。このような汚染物質は、表面のぬれを減
少させ、基材と弗素樹脂薄膜との接着性を低下さ
せることが多い。特に酸化被膜は基材の耐食性に
は特徴的に寄与するが接着性に関しては好ましく
ない。
油分は加工防錆油などの素材金属の表面に必ず
関与する汚染物質の一つであり、表面に油性汚染
物質が存在すると弗素樹脂の被膜形成に際して、
密着不良を生じる原因となる。
したがつて、このような種々の汚染物質を除去
して清浄な接着性表面を得るために基材の脱脂，
洗浄工程が必要である。
次に洗浄工程で付着した水分を除去する乾燥工
程がある。この工程では物理吸着水を取り除く程
度であつて、数十〜数百分子層の結合水は取り除
くことはできない。乾燥温度は常温〜90℃の範囲
が好ましい。
次に乾燥工程を経て得られた清浄な表面に弗素
樹脂デイスパージヨンを塗布する。塗布方法はス
プレイ法，エアーナイフ法，ロール転写法などい
ずれの方法でも良いが、実施例では10μｍ内外の
薄膜を形成する観点からロール転写法を用いた。
ロール転写法によれば、10μｍ内外の均一な薄膜
を連続的に形成することができる。
弗素樹脂デイスパージヨンの塗布工程の後、乾
燥工程がある。乾燥が不十分であると焼成工程に
おいて弗素樹脂薄膜に亀裂が入る場合がある。ま
た乾燥が早すぎると塗布膜に亀裂，剥離，あるい
は気泡が発生し、良好な被膜を得ることができな
いので、弗素樹脂デイスパージヨンの性状に合わ
せて適正な乾燥条件を設定する必要がある。乾燥
温度は常温〜90℃の範囲で、乾燥時間は５分〜60
分が好ましい。
弗素樹脂塗膜を乾燥後、350℃〜430℃で焼成す
る。乾燥後の塗膜はやわらかく基材との密着は非
常に弱く、塗膜にさわると剥離する。したがつ
て、焼成工程において、融点以上に加熱し、粉末
同志を融着させるとともに基材と塗膜を結合させ
る。
弗素樹脂、特にポリ四弗化エチレン（PTFE）
はポリエチレンの水素原子を全部弗素原子で置換
した化学構造〔（−CF2−CF2−）ｎ〕で、炭素
原子鎖を骨格として、その周囲を弗素原子がとり
まき、きわめて強固なＣ−Ｆ結合および弗素原子
で強化されたＣ−Ｃ結合からなる線状高分子であ
り、対称構造を有しているため、耐熱性，耐薬品
性，絶縁性，誘電特性に優れている。その反面、
弗素樹脂はあらゆる液体に対してもつともぬれが
たい表面特性をもつている。ぬれの占度は、一般
に接触角θを用い、次式で表される。
Ａ＝γS−γSL＝γLcosθ
Ａ：ぬれの尺度（dyne／cm）
γS：固体の表面張力（dyne／cm）
γL：液体の表面張力（dyne／cm）
γLS：固体−液体間の界面張力（dyne／cm）
θ：接触角（度）
接触角θが大きい程、ぬれ性が悪い。弗素樹脂
の水に対する接触角（度）は114〜115であり、他
の物質より非常に大きい。このことは、弗素樹脂
がすぐれた離型性を有することを意味し、特異の
非粘着性があり、どんな粘着性の物質も粘着しな
いという特徴がある。しかし、非粘着性であると
いうことは基材と弗素樹脂被膜との接合が非常に
困難であることを意味し、事実、通常の塗料のよ
うに簡単には結合層は得られない。したがつて、
表面の非粘着性を維持しながら基材と被膜の結合
層を得るために、前述のようにプライマー層を設
けたり、基材を粗面化したり、弗素樹脂デイスパ
ージヨンを改良したり、多孔質層を設けるなどの
研究が行われてきた。
これらの方法は工程が複雑であつたり、物理的
結合のみである等の欠点を有する。また弗素樹脂
デイスパージヨンを改良して基材との接着性を良
くすると、表面の非粘着性が失われるなど従来の
方法には多くの欠点があつた。
本発明は基材に燐元素を添加することにより、
表面の非粘着性を維持しながら、基材と弗素樹脂
被膜との化学的結合層をこの焼成工程で形成する
ものである。
本発明で用いられる焼成炉の炉内雰囲気は、大
気雰囲気、不活性ガス気流中いずれでもよいが、
強固な化学的結合層を得ようとすれば、N2，
He，Ar等の不活性ガス、CO，CO2，H2などのガ
ス気流中で焼成した方が好ましい。特に高温の酸
化雰囲気中で焼成すると、基材の表面に酸化被膜
を生成して弗素樹脂被膜の密着力を低下させる場
合があるので、大気雰囲気中での焼成はさけた方
が良い。
冷却は水中で急冷した方が被膜の強じん性，透
明性，非粘着性を向上させる。
次に本発明の複合体の実施例についてのべる。
第２表は基材としての金属材料の化学成分を示
す。No.Ａ〜Ｆはアルミニウムおよびアルミニウム
合金、No.Ｇ〜Ｈはアルミニウムダイキヤスト、No.
Ｉ〜Ｐは銅および銅合金、No.Ｑ〜Ｔは鉄および鉄
基合金の実施例を示す。表には記載していない
が、No.Ｕとしてアルミナイズド鋼板のアルミニウ
ム被覆層に燐を0.3重量％添加したもの、No.Ｖと
して亜鉛鉄板の亜鉛被覆層に燐を0.3重量％添加
したものについても検討した。[Table] Aluminum base materials A to D shown in the above table are approximately
During firing of the fluororesin coating layer at 380°C, the surface does not undergo significant oxidation weight gain or oxidation deterioration, but after firing, the fluororesin completely peeled off in a tape peel test, and it became clear that no adhesion strength could be obtained. Ta. Conventionally, in order to obtain adhesion strength, an aluminum base material was subjected to surface enlarging treatment, and adhesion strength was obtained through a physical adhesion effect. For example, there is a manufacturing method as shown in FIG. The surface of the base material is covered with dust, oily substances, and antioxidants, so degreasing and cleaning are required. after that,
After drying, the next step is surface enlargement treatment.
This step is for uniformly adhering the fluororesin-coated thin film to obtain adhesion strength, and the surface of the base material needs to have an Ra of about 0.1 to 1.8 μm as measured by a Talysurf surface roughness meter. 5 to 10 when Ra is 0.1μm or less
Uniform adhesion strength of the fluororesin thin film within and outside μm cannot be obtained. On the other hand, when Ra is 1.8 μm or more, it is 5 to 10 μm.
It becomes difficult to maintain the accuracy of uniform coating thickness inside and outside m.
Therefore, the optimum centerline average roughness Ra is in the range of 0.1 to 1.8 μm. Surface enlarging treatment is usually carried out by chemical etching,
This is done using methods such as sandblasting, but the methods for achieving adhesion between the base material and fluororesin include:
In addition to the surface unevenness forming method described above, anodic oxidation treatment, chemical conversion treatment, etc. are commonly used. Particularly in the case of aluminum, chemical conversion treatments are often used, and phosphate treatment using iron phosphate, zinc phosphate, manganese phosphate, etc., chromate treatment, phosphoric acid-chromic acid treatment, etc. are suitable. However, while fluororesin thin films formed by subjecting the base material to surface enlargement treatment or chemical treatment can provide strong adhesion,
Bubbles remain on the surface of a substrate that has been roughened or chemically treated, making it extremely difficult to form a pinhole-free thin film. Furthermore, when a transparent fluororesin thin film is formed, it exhibits a gray-black oxide film (chemical conversion treatment) or a matte surface phase (sandblasting), making it impossible to obtain a beautiful metallic luster surface, which is truly inconvenient from a decorative point of view. . In view of the above points, the present invention provides a fluororesin thin film composite which is free from pinholes and provides a metallic luster surface when a transparent fluororesin thin film is formed. FIG. 2 shows the manufacturing process of a fluororesin thin film composite according to an embodiment of the present invention. Suitable substrates used in the present invention include materials in which phosphorus is added to metal materials such as copper, copper alloys, aluminum, aluminum alloys, iron, iron-based alloys, aluminized steel plates, and galvanized iron plates. The effects of adding phosphorus to these materials will be detailed later, but by adding phosphorus to the base material, a strong bonding layer between the fluororesin and the base material can be obtained without surface enlarging treatment. Even when a transparent thin film is formed, it exhibits a beautiful metallic luster surface, and the manufacturing process can be simplified. As the fluororesin used in the present invention, each resin such as polytetrafluoroethylene, a copolymer of tetrafluoroethylene-hexafluoropropylene, polytrifluoroethylene, or a combination of these resins is preferable. Furthermore, since the particle size of these resins should be as fine as possible for the purpose of the present invention, it is preferable that the fluororesin is emulsion polymerized and has an average particle size of 0.8 μm or less. The surface of ordinary base materials has an oxide film, oil, moisture, etc.
and the presence of various pollutants in the atmospheric environment. Such contaminants often reduce surface wetting and reduce adhesion between the substrate and the fluoropolymer film. In particular, the oxide film contributes characteristically to the corrosion resistance of the base material, but is unfavorable in terms of adhesion. Oil is one of the contaminants that are always involved in the surface of raw metals, such as processed rust preventive oil, and if oil-based contaminants are present on the surface, it will cause problems when forming a fluororesin film.
This may cause poor adhesion. Therefore, in order to remove these various contaminants and obtain a clean adhesive surface, it is necessary to degrease the substrate.
A cleaning step is required. Next, there is a drying process to remove moisture that has adhered during the cleaning process. This step only removes physically adsorbed water, but cannot remove bound water in tens to hundreds of molecular layers. The drying temperature is preferably in the range of room temperature to 90°C. Next, a fluororesin dispersion is applied to the clean surface obtained through the drying process. The coating method may be any method such as a spray method, an air knife method, or a roll transfer method, but in the examples, the roll transfer method was used from the viewpoint of forming a thin film of about 10 μm.
According to the roll transfer method, a uniform thin film of about 10 μm can be continuously formed. After the coating process of the fluororesin dispersion, there is a drying process. If drying is insufficient, cracks may occur in the fluororesin thin film during the firing process. Furthermore, if the coating is dried too quickly, cracks, peeling, or bubbles will occur in the coating, making it impossible to obtain a good coating, so it is necessary to set appropriate drying conditions according to the properties of the fluororesin dispersion. The drying temperature ranges from room temperature to 90℃, and the drying time ranges from 5 minutes to 60 minutes.
Minutes are preferred. After drying the fluororesin coating film, it is fired at 350°C to 430°C. After drying, the paint film is soft and has very weak adhesion to the substrate, and will peel off if you touch it. Therefore, in the firing step, the powder is heated above its melting point to fuse the powders together and bond the base material and the coating film. Fluororesins, especially polytetrafluoroethylene (PTFE)
has a chemical structure [(-CF 2 - CF 2 -) n] in which all hydrogen atoms in polyethylene are replaced with fluorine atoms, with a carbon atom chain as the backbone, surrounded by fluorine atoms, and an extremely strong C-F bond. It is a linear polymer consisting of C--C bonds reinforced with fluorine atoms, and has a symmetrical structure, so it has excellent heat resistance, chemical resistance, insulation, and dielectric properties. On the other hand,
Fluororesin has surface properties that make it difficult to wet with any liquid. The degree of wetting is generally expressed by the following equation using the contact angle θ. A = γ S − γ SL = γ L cosθ A: Measure of wetting (dyne/cm) γ S : Surface tension of solid (dyne/cm) γ L : Surface tension of liquid (dyne/cm) γ LS : Solid − Interfacial tension between liquids (dyne/cm) θ: Contact angle (degrees) The larger the contact angle θ, the worse the wettability. The contact angle (degrees) of fluororesin with water is 114-115, which is much larger than other substances. This means that the fluororesin has excellent mold release properties, and has a unique non-adhesive property, meaning that it does not stick to any sticky substance. However, non-adhesiveness means that it is very difficult to bond the substrate and the fluororesin coating, and in fact, a bonding layer cannot be obtained as easily as with ordinary paints. Therefore,
In order to obtain a bonding layer between the substrate and the coating while maintaining the non-adhesion of the surface, it is necessary to provide a primer layer as described above, roughen the surface of the substrate, improve the fluororesin dispersion, or create a porous layer. Research has been conducted on creating qualitative layers. These methods have drawbacks such as complicated steps and only physical bonding. Furthermore, when the fluororesin dispersion was improved to improve its adhesion to the substrate, the conventional methods had many drawbacks, such as the loss of non-stick properties on the surface. In the present invention, by adding phosphorus element to the base material,
This baking step forms a chemical bonding layer between the base material and the fluororesin coating while maintaining the non-adhesive surface. The atmosphere inside the firing furnace used in the present invention may be either air atmosphere or an inert gas stream.
To obtain a strong chemical bonding layer, N 2 ,
It is preferable to perform firing in an inert gas such as He or Ar, or in a gas stream such as CO, CO 2 or H 2 . In particular, firing in a high-temperature oxidizing atmosphere may generate an oxide film on the surface of the base material and reduce the adhesion of the fluororesin film, so it is better to avoid firing in the air. Rapid cooling in water improves the toughness, transparency, and non-adhesion of the film. Next, examples of the composite of the present invention will be described. Table 2 shows the chemical composition of the metal material as a base material. No.A to F are aluminum and aluminum alloy, No.G to H are aluminum die casting, and No.
I to P show examples of copper and copper alloys, and No.Q to T show examples of iron and iron-based alloys. Although not listed in the table, No.U contains 0.3% by weight of phosphorus in the aluminum coating layer of an aluminized steel sheet, and No.V contains 0.3% by weight of phosphorus in the zinc coating layer of a galvanized iron plate. Also considered.
【表】【table】
【表】
これらの基材に、上記の製造法に基づき、ポリ
四弗化エチレンのデイスパージヨンをロール転写
法で各種の膜厚に塗布し、乾燥後窒素雰囲気中に
おいて380℃または390℃で10分間焼成して弗素樹
脂薄膜を形成した。
こうして得た試料について、弗素樹脂膜をナイ
フにより基材から剥離させ、その剥離部分を基板
に密着している膜に対して直角の方向に引張つて
密着性を評価した。この場合、引張りにより基材
に密着している膜が一様に剥離したものを×印、
一部剥離するが、大部分は切れて剥離しないもの
を〇印、切れてしまい全く剥離しないものを◎印
で表わした。この結果を第３表に示す。[Table] Based on the above manufacturing method, polytetrafluoroethylene dispersion was applied to various film thicknesses by roll transfer method to these base materials, and after drying, it was heated at 380°C or 390°C in a nitrogen atmosphere. A fluororesin thin film was formed by baking for 10 minutes. For the sample thus obtained, the fluororesin film was peeled off from the substrate using a knife, and the peeled portion was pulled in a direction perpendicular to the film adhering to the substrate to evaluate adhesion. In this case, the film that adheres to the base material is uniformly peeled off due to tension is marked with an
Items that partially peeled off but most of them were cut and did not peel off were marked with ◎, and cases that broke and did not peel off at all were marked with ◎. The results are shown in Table 3.
【表】【table】
【表】
第３表から明らかなように、基材に燐を添加す
ると基材と弗素樹脂被覆層との密着力が大巾に向
上する。特に燐とZn，Al，Snとを共存させた場
合にその効果が顕著に表れている。
燐を添加した場合に密着力が向上する理由はま
だ明らかではないが、次のように考えられる。す
なわち、第１に、燐が接着促進材としての働きが
あつて、基材の表面と弗素樹脂被覆層との親和性
を増加し、得られる接着界面のエネルギーをより
低くすることによつて安定な接着を作りだす作
用、つまり基材表面の改質材としての働きがある
ものと推定できる。
第２の理由として、弗素樹脂塗膜に含まれる、
乳化重合された弗素樹脂，非イオン界面活性剤，
水と基材に含まれる燐，亜鉛，アルミニウム，ス
ズなどの金属元素との間、および380℃の不活性
ガス気流中を考慮すると、弗素樹脂被覆層と基材
の界面で化学反応が進行して、リン酸塩、〔一般
式MO・xP2O・yH2O（ｘ，ｙは実数）〕を形成し
ているものと思われる。たとえば、リン酸アルミ
ニウム，リン酸亜鉛，リン酸スズ等である。ま
た、弗素樹脂中の弗素と燐との反応も考えられ
る。
このように、基材に燐を添加することにより、
弗素樹脂被覆層と基材の間で化学的結合層を形成
し、強固な結合力を有する弗素樹脂薄膜複合体を
提供することができる。
次に基材に添加する燐の添加量は、基材の化学
組成にもよるが、最低0.01重量％は必要であり、
それ以下では接着力の向上はみられなかつた。ま
た、1.0重量％を越える量の燐を基材に添加する
と、基材本来の特性、たとえば、機械的性質，物
理的性質，化学的性質を大巾に変質させ好ましく
ない。したがつて、基材への燐の添加量は0.01〜
1.0重量％の範囲で調整すべきである。
以上のように、本発明によれば、基材に表面拡
大化処理を施すことなく、基材と弗素樹脂被膜と
の強固な密着力が得られ、透明被膜を形成した場
合でも美しい金属光沢面が得られる。また、本発
明の弗素樹脂複合体は、機能的には装飾用，耐
食，耐熱性を要求される物品，電気絶縁性を要求
される物品、誘電体としての利用など多方面に応
用することができる。[Table] As is clear from Table 3, adding phosphorus to the base material greatly improves the adhesion between the base material and the fluororesin coating layer. This effect is particularly noticeable when phosphorus coexists with Zn, Al, and Sn. The reason why adhesion is improved when phosphorus is added is not yet clear, but it is thought to be as follows. First, phosphorus acts as an adhesion promoter, increasing the affinity between the surface of the base material and the fluororesin coating layer, and lowering the energy of the resulting adhesive interface to stabilize it. It can be presumed that it has the effect of creating strong adhesion, that is, it acts as a modifier for the surface of the base material. The second reason is that the fluororesin coating contains
Emulsion polymerized fluororesin, nonionic surfactant,
Considering that water and metal elements such as phosphorus, zinc, aluminum, and tin contained in the base material and in an inert gas stream at 380°C, chemical reactions proceed at the interface between the fluororesin coating layer and the base material. Therefore, it is thought to form a phosphate, [general formula MO·xP 2 O·yH 2 O (x, y are real numbers)]. For example, aluminum phosphate, zinc phosphate, tin phosphate, etc. A reaction between fluorine and phosphorus in the fluororesin is also considered. In this way, by adding phosphorus to the base material,
A chemical bonding layer can be formed between the fluororesin coating layer and the base material, and a fluororesin thin film composite having strong bonding strength can be provided. Next, the amount of phosphorus added to the base material depends on the chemical composition of the base material, but a minimum of 0.01% by weight is required.
No improvement in adhesion was observed below this level. Furthermore, if phosphorus is added in an amount exceeding 1.0% by weight to the base material, the inherent properties of the base material, such as mechanical properties, physical properties, and chemical properties, will be drastically altered, which is not preferable. Therefore, the amount of phosphorus added to the base material is 0.01~
It should be adjusted within the range of 1.0% by weight. As described above, according to the present invention, strong adhesion between the base material and the fluororesin coating can be obtained without subjecting the base material to surface enlarging treatment, and even when a transparent coating is formed, a beautiful metallic luster surface can be obtained. is obtained. Furthermore, the fluororesin composite of the present invention can be functionally applied to a wide range of applications, such as decoration, articles requiring corrosion resistance and heat resistance, articles requiring electrical insulation, and use as a dielectric. can.
第１図は従来の弗素樹脂被覆層を形成する製造
工程を示す図、第２図は本発明の実施例による製
造工程を示す図である。
FIG. 1 is a diagram showing a conventional manufacturing process for forming a fluororesin coating layer, and FIG. 2 is a diagram showing a manufacturing process according to an embodiment of the present invention.
Claims (1)
金，鉄および鉄基合金よりなる群から選択された
基材で、かつ燐を含有する基材上に弗素樹脂を主
成分とする薄膜を形成した弗素樹脂薄膜複合体。 ２ 基材中の燐の含有量が0.01〜1.0重量％であ
る特許請求の範囲第１項記載の弗素樹脂薄膜複合
体。 ３ アルミニウム，アルミニウム合金，銅，銅合
金，鉄および鉄基合金よりなる群から選択された
基材で、かつ燐を含有する基材を脱脂，洗浄する
工程と、乾燥の後弗素樹脂を塗布する工程と、塗
布された前記弗素樹脂を乾燥，焼成する工程から
なる弗素樹脂薄膜複合体の製造法。[Scope of Claims] 1. A thin film containing fluororesin as a main component on a substrate selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, iron, and iron-based alloy, and containing phosphorus. A fluororesin thin film composite formed of. 2. The fluororesin thin film composite according to claim 1, wherein the phosphorus content in the base material is 0.01 to 1.0% by weight. 3 Degreasing and cleaning the base material selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, iron and iron-based alloy and containing phosphorus, and applying fluororesin after drying. 1. A method for producing a fluororesin thin film composite, which comprises a step of drying and baking the applied fluororesin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56128530A JPS5829660A (en) | 1981-08-17 | 1981-08-17 | Fluoroplastic thin-film composite body and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56128530A JPS5829660A (en) | 1981-08-17 | 1981-08-17 | Fluoroplastic thin-film composite body and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5829660A JPS5829660A (en) | 1983-02-21 |
| JPS6141743B2 true JPS6141743B2 (en) | 1986-09-17 |
Family
ID=14987024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56128530A Granted JPS5829660A (en) | 1981-08-17 | 1981-08-17 | Fluoroplastic thin-film composite body and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5829660A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5243099B2 (en) * | 2008-05-10 | 2013-07-24 | 古河スカイ株式会社 | Aluminum alloy coating |
-
1981
- 1981-08-17 JP JP56128530A patent/JPS5829660A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5829660A (en) | 1983-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0675928B1 (en) | Coating composition for non-stick substrates | |
| US4542048A (en) | Powder metal and/or refractory coated ferrous metals | |
| JP2004524957A (en) | Corrosion resistant coating for glazing effect | |
| US4628004A (en) | Powder metal and/or refractory coated ferrous metal | |
| EP0365602A1 (en) | Thermal spraying of stainless steel. | |
| BE1015838A5 (en) | Manufacturing method for enameled steel sheet, involves spraying slurry to form slurry layer on surface of substrate, and firing formed slurry layer | |
| US3511690A (en) | Production of polytetrafluoroethylene-containing coatings on metallic bases | |
| US4678717A (en) | Powder metal and/or refractory coated ferrous metals | |
| JPS5853960A (en) | Composition for covering fluorine-contained resin | |
| JPH0213898B2 (en) | ||
| JPS6141743B2 (en) | ||
| JP3014561B2 (en) | Lubricated steel sheet with excellent workability and corrosion resistance | |
| JPS6344968A (en) | Fluorocarbon resin coated aluminum material | |
| JP4132687B2 (en) | Heat-resistant pre-coated steel plate with excellent workability and spot weldability | |
| CN114058996A (en) | A kind of easily degreasing coated steel plate and preparation method thereof and painted steel plate | |
| JP2000026786A (en) | Paint composition and coated product obtained by applying the same | |
| JPS60201945A (en) | Precoated steel plate | |
| JPH06344505A (en) | Covering of surface of metal with fluoroplastic film | |
| JP2002212754A (en) | Surface-treated metal sheet excellent in press galling resistance and coil deformation resistance, and method for producing the same | |
| JPS62755B2 (en) | ||
| JPH03243755A (en) | Organic composite alloying hot dip galvanized steel sheet excellent in press formability | |
| KR940008460B1 (en) | Two layer si-zn coated steel sheet of removing of fingerprint with an excellant corrosion resistance and adhesion and method for making the same | |
| JPH0328380A (en) | Surface treated steel sheet having excellent lubricity and corrosion resistance | |
| KR980009499A (en) | Method of manufacturing zinc-iron alloy-plated steel sheet | |
| JPH05228434A (en) | Fluororesin coating and method for producing the same |