JPS62280236A - Fluorocarbon resin having fine cell and its production - Google Patents
Fluorocarbon resin having fine cell and its productionInfo
- Publication number
- JPS62280236A JPS62280236A JP12211286A JP12211286A JPS62280236A JP S62280236 A JPS62280236 A JP S62280236A JP 12211286 A JP12211286 A JP 12211286A JP 12211286 A JP12211286 A JP 12211286A JP S62280236 A JPS62280236 A JP S62280236A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- fluororesin
- cell diameter
- foaming
- thermoplastic fluororesin
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 title abstract description 28
- 239000011347 resin Substances 0.000 title abstract description 28
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title abstract description 7
- 239000006260 foam Substances 0.000 claims abstract description 55
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 26
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000005187 foaming Methods 0.000 claims description 22
- -1 fluoroalkyl fluorovinyl ether Chemical compound 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000004088 foaming agent Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000006835 compression Effects 0.000 abstract description 13
- 238000007906 compression Methods 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 210000004027 cell Anatomy 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000009413 insulation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 6
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 6
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 6
- 238000010292 electrical insulation Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 230000005865 ionizing radiation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920001973 fluoroelastomer Polymers 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 2
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 2
- 229940099364 dichlorofluoromethane Drugs 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WBCLZGYCULJPDT-UHFFFAOYSA-N 2-tert-butylperoxy-2,5-dimethylhexane Chemical compound CC(C)CCC(C)(C)OOC(C)(C)C WBCLZGYCULJPDT-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 229920006370 Kynar Polymers 0.000 description 1
- 239000004341 Octafluorocyclobutane Substances 0.000 description 1
- 102100033213 Teneurin-1 Human genes 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003855 cell nucleus Anatomy 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 108010063973 teneurin-1 Proteins 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- FPDZOFFZSWSOSL-UHFFFAOYSA-N trifluoromethoxyethene Chemical compound FC(F)(F)OC=C FPDZOFFZSWSOSL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
産業上の利用分野
本発明は微細気泡を有するフッ素樹脂発泡体及びその製
造方法に関するものである。さらに詳しくいえば、本発
明は、特に表面平滑性とクッション性が要求される印刷
版用クッション材、印刷機や複写機などの転写ロール材
、ガスシール材、あるいは高周波絶縁性が要求されるコ
ンピューターや通信回線などの高速通信用絶縁材、表面
平滑性と微小研磨粒の均一分散性が要求される精密研磨
用の研磨布、輻射エネルギーの遮断性が要求され”る屋
上断熱防水材や消防服用断熱材などに有用な微細気泡を
有するフッ素樹脂発泡体、及びその製造方法に関するも
のである。Detailed Description of the Invention 3. Detailed Description of the Invention Field of Industrial Application The present invention relates to a fluororesin foam having fine cells and a method for producing the same. More specifically, the present invention is particularly applicable to cushioning materials for printing plates that require surface smoothness and cushioning properties, transfer roll materials for printing machines and copying machines, gas sealing materials, and computers that require high frequency insulation properties. Insulating materials for high-speed communications such as those used in communication lines and communication lines, abrasive cloths for precision polishing that require surface smoothness and uniform dispersion of minute abrasive particles, rooftop insulation and waterproofing materials that require radiant energy blocking, and fire protection clothing. The present invention relates to a fluororesin foam having fine cells that is useful as a heat insulating material, and a method for producing the same.
従来の技術
従来、フッ素樹脂発泡体としては、例えばポリテトラフ
ルオロエチレンの微粒子を焼結して得られる空孔率６０
チ程度の多孔体（特公昭４２−４９７４ 号公報）、テ
トラフルオロエチレン−パーフルオロ−α−オレフィン
共重合体をフルオロメタンで発泡して得られた発泡体（
米国特許第３，０７２，５８３号明細書）が知られてい
る。しがしながら、前者の多孔体は、その製法上連続気
泡体となるため、電気絶縁性の一定したものが得られず
、品質上の問題を有しており、また後者の発泡体におい
ては、一般に気泡径が２００〜３００μｍと大きく、か
つ発泡倍率も１．７〜２．５倍の範囲であって、電気絶
縁性や断熱性に劣るという欠点がある。Conventional technology Conventionally, fluororesin foams have a porosity of 60 and are obtained by sintering fine particles of polytetrafluoroethylene, for example.
(Japanese Patent Publication No. 42-4974), a foam obtained by foaming a tetrafluoroethylene-perfluoro-α-olefin copolymer with fluoromethane
U.S. Pat. No. 3,072,583) is known. However, because the former porous material is made into an open-celled material due to its manufacturing method, it is not possible to obtain a uniform electrical insulation property, which poses a quality problem. Generally, the cell diameter is as large as 200 to 300 μm, and the expansion ratio is also in the range of 1.7 to 2.5 times, which has the drawback of poor electrical insulation and heat insulation properties.
一方、熱可塑性フッ素樹脂から成る空孔率５〜７０チ、
気泡径１００μｍ以下の発泡体（特開昭５７−１７７０
８１号公報）も開発されている。しかしながら、このも
のは、電気絶縁性及び断熱性が実用に耐えうるほど十分
であるとはいえない。On the other hand, a porosity of 5 to 70 cm made of thermoplastic fluororesin,
Foam with a cell diameter of 100 μm or less (Japanese Patent Application Laid-Open No. 57-1770
No. 81) has also been developed. However, it cannot be said that the electrical insulation and heat insulation properties of this material are sufficient for practical use.
また、これらの発泡体は熱可塑性のフッ素樹脂を用いて
いるために、いずれも弾力性、引張強度、引裂強度、圧
縮永久歪などに劣るという欠点を有している。Furthermore, since these foams use thermoplastic fluororesin, they all have the disadvantage of being inferior in elasticity, tensile strength, tear strength, compression set, etc.
さらに、低粘度のフッ素エラストマーに加硫剤と発泡剤
とを混合し、加圧下に加熱して得られた発泡体も知られ
て−いる（米国特許第３，８６８，３３７号明細書）。Furthermore, a foam obtained by mixing a vulcanizing agent and a blowing agent with a low-viscosity fluoroelastomer and heating the mixture under pressure is also known (US Pat. No. 3,868,337).
しかしながら、このものは気泡が大きく、かつエラスト
マーをペースとしているために、柔らかすぎて用途が限
定されるのを免れない。However, since this material has large bubbles and is made of elastomer, it is too soft and its uses are inevitably limited.
発明が解決しようとする問題点
本発明の目的は、このような従来のフッ素樹脂発泡体が
有する欠点を改良し、弾力性、引張強度、引裂強度、圧
縮永久歪などに優れる上に、良好な断熱性、電気絶縁性
、クッション性、表面平滑性を有するなど、優れた特徴
をもつフッ素樹脂発泡体を提供することにある。Problems to be Solved by the Invention The purpose of the present invention is to improve the drawbacks of conventional fluororesin foams, and to create a foam that has excellent elasticity, tensile strength, tear strength, compression set, etc. The object of the present invention is to provide a fluororesin foam having excellent characteristics such as heat insulation, electrical insulation, cushioning properties, and surface smoothness.
問題点を解決するための手段
本発明者らは前記の優れた特徴を有するフッ素樹脂発泡
体を開発するために鋭意研究を重ねた結果、基材のフッ
素樹脂として、熱可塑性フッ素樹脂の架橋化物を用い、
微細な気泡が形成されるように発泡させることにより、
その目的を達成しうろことを見出し、この知見に基づい
て本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted extensive research in order to develop a fluororesin foam having the above-mentioned excellent characteristics. As a result, we have developed a crosslinked thermoplastic fluororesin as the base fluororesin. using
By foaming to form fine bubbles,
We have found a way to achieve this objective, and based on this knowledge, we have completed the present invention.
すなわち、本発明は、熱可塑性フッ素樹脂の架橋化物を
発泡させて成る平均気泡径が９０μｍ以下の微細気泡を
有するフッ素樹脂発泡体を提供するものである。このフ
ッ素樹脂発泡体は、熱可塑性フッ素樹脂を架橋化処理し
たのち、これに発泡剤を配合するか、あるいは該フッ素
樹脂に発泡剤を配合したのち、これを架橋化処理するこ
とにより発泡性組成物を調製し、次いでこれを加熱して
発泡させることにより製造することができる。That is, the present invention provides a fluororesin foam having fine cells with an average cell diameter of 90 μm or less, which is obtained by foaming a crosslinked thermoplastic fluororesin. This fluororesin foam can be produced by crosslinking a thermoplastic fluororesin and then adding a blowing agent thereto, or by adding a blowing agent to the fluororesin and then subjecting it to a crosslinking treatment. It can be manufactured by preparing a product and then heating and foaming it.
本発明においては、基材樹脂として熱可塑性フッ素樹脂
を架橋処理したものが用いられる。In the present invention, a crosslinked thermoplastic fluororesin is used as the base resin.
この架橋処理されたフッ素樹脂を用いることにより、発
泡倍率が大きく、かつ気泡径が均一で、機械的強度や弾
力性に優れた発泡体が得られ、しかも広幅のシート状発
泡体を安定して製造することができる。By using this cross-linked fluororesin, it is possible to obtain a foam with a large expansion ratio, uniform cell diameter, and excellent mechanical strength and elasticity. can be manufactured.
この架橋処理は、該フッ素樹脂に、化学架橋剤、例えば
ジベンゾイルパーオキンドのようなジアンルバーオキシ
ド、ジクミルパーオキンド、ジーを一ブチルパーオキシ
ド、ｔ−ブチルパーオキシアセテート、七−ブテルバー
オキシイソグロビルカーボネ−）、ｔ−プチルパーオキ
ンペンゾエートのようなパーオキシエステル類などのモ
ノパーオキン化合物、２，５−ジメチル−２，５−ジー
（１−ブチルパーオキシ）−ヘキシン−３，２，５−ジ
メチル−２，５−（ｔ−ブチルパーオキシ）−ヘキサン
、α、α′−ビス−（ｔ−ブチルパーオキシ）−ｐ−ジ
イソプロピルベンゼン、２．５−ジメチル−２゜５−ジ
ー（ペンゾイルパーオキン）−ヘキサンなどのジパーオ
キン化合物などを添加し、加熱することにより、また、
該フッ素樹脂に、電離性放射線、例えばα線、β線、γ
線、中性子線、加速粒子線、Ｘ線、電子線などを空気中
、真空中、あるいはアルゴン、ヘリウム、窒素などの不
活性ガス中や水中において照射することにより、あるい
は架橋性官能基を有する共重合可能なモノマーを共重合
して成る架橋性フッ素樹脂に、該官能基を付加反応させ
る触媒を添加して加熱するか、あるいは該官能基と反応
する活性な低分子化合物を添加し、加熱することにより
行われる。This crosslinking treatment involves applying a chemical crosslinking agent to the fluororesin, such as dianruburoxide such as dibenzoyl peroquine, dicumyl peroquine, monobutyl peroxide, t-butyl peroxyacetate, and 7-butyl peroxide. monoperoquine compounds such as peroxy esters such as t-butylperoquine penzoate, 2,5-dimethyl-2,5-di(1-butylperoxy) -Hexyne-3,2,5-dimethyl-2,5-(t-butylperoxy)-hexane, α,α'-bis-(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl -2゜5-di(penzoylperoquine)-By adding a diperoquine compound such as hexane and heating,
The fluororesin is exposed to ionizing radiation, such as α rays, β rays, γ rays.
By irradiating radiation, neutron beam, accelerated particle beam, X-ray, electron beam, etc. in air, vacuum, inert gas such as argon, helium, nitrogen, etc., or in water, A catalyst for an addition reaction with the functional group is added to a crosslinkable fluororesin formed by copolymerizing a polymerizable monomer, or an active low-molecular compound that reacts with the functional group is added and heated. This is done by
また、必要に応じ、アリル化合物、硫黄、有機アミン類
、メタクリレート類、アクリレート類、ジビニル化合物
、オキシム化合物などの架橋助剤を添加して架橋するこ
とも可能である。Further, if necessary, crosslinking can be carried out by adding a crosslinking aid such as an allyl compound, sulfur, organic amines, methacrylates, acrylates, divinyl compound, or oxime compound.
このようにして、架橋化処理されたフッ素樹脂の架橋度
合は、得られる発泡体の所望性能、倍率、樹脂の種類な
どに応じ適宜選択され、その値は該樹脂の動的粘弾性の
測定によって求めることができる。一般的には、該樹脂
の融点より３０℃高い温度における動的ずり貯蔵弾性率
に対する動的ずり損失弾性率の比が０．６〜０．９の範
囲にあるように架橋されたものが用いられる。この弾性
率の比が０．９を超えるものは発泡体の気泡構造が不均
一となって大きな空洞が生じ、表面も凹凸となる上、気
泡膜にピンホールや破れなどが生じて好ましくない。ま
た、０．６未謂のものでは発泡倍率が小さくなり、得ら
れる発泡体は弾力性に劣る上に、気泡膜に破れ、ピンホ
ールなどが多くて機械的強度にも劣り好ましくない。In this way, the degree of crosslinking of the crosslinked fluororesin is appropriately selected depending on the desired performance of the obtained foam, the magnification, the type of resin, etc., and its value is determined by measuring the dynamic viscoelasticity of the resin. You can ask for it. Generally, a crosslinked resin is used such that the ratio of dynamic shear loss modulus to dynamic shear storage modulus at a temperature 30°C higher than the melting point of the resin is in the range of 0.6 to 0.9. It will be done. If the elastic modulus ratio exceeds 0.9, the cell structure of the foam becomes non-uniform, resulting in large cavities, the surface becomes uneven, and pinholes and tears occur in the cell membrane, which is undesirable. On the other hand, if it is less than 0.6, the foaming ratio will be small, and the obtained foam will not only have poor elasticity, but also have many tears and pinholes in the cell membrane, and will have poor mechanical strength, which is not preferable.
本発明において用いられる熱可塑性フッ素樹脂トシテハ
、例えばモノフルオロエチレン、ｉ、１−ジフルオロエ
チレン、１，１．２− ） ９フルオロエチレン、モノ
クロロトリフルオロエチレン、テトラフルオロエチレン
ナトのフルオロエチレン、ペンタフルオロプロピレン、
ヘキサフルオロプロピレン、パーフルオロペ／テン−１
などのフルオロ−α−オレフィン、トリフルオロメチル
パーフルオロビニルエーテル、パーフルオコエチルバー
フルオロビニルエーテル、パーフルオロプロピルパーフ
ルオロビニルエーテルなどのフルオロアルキルフルオロ
ビニルエーテル、トリフルオロメチルビニルエーテル、
パーフルオロエチルビニルエーテル、パーフルオロプロ
ピルビニルエーテルナト（７）フルオロアルキルビニル
エーテルなどの中から選ばれた少なくとも１種のモノマ
ーを主成分として得られた含フツ素重合体が挙げられる
。また、該熱可塑性フッ素樹脂には、所望に応じ、その
好ましい特性をあまりそこなわない範囲で、例えばエチ
レン、プロピレン、ブテンなどの万レフイン、アルキル
ビニルエーテル、アクリル酸エステル、メタクリル酸エ
ステルなどの共重合可能なモノマーの単位を含ませるこ
とができる。Thermoplastic fluororesins used in the present invention, such as monofluoroethylene, i,1-difluoroethylene, 1,1.2-)9 fluoroethylene, monochlorotrifluoroethylene, tetrafluoroethylene, fluoroethylene, pentafluoropropylene ,
Hexafluoropropylene, perfluorope/ten-1
Fluoro-α-olefins such as trifluoromethyl perfluorovinyl ether, perfluorocoethyl perfluorovinyl ether, fluoroalkyl fluorovinyl ethers such as perfluoropropyl perfluorovinyl ether, trifluoromethyl vinyl ether,
Examples include fluorine-containing polymers obtained using at least one monomer selected from perfluoroethyl vinyl ether, perfluoropropyl vinyl ether (7) fluoroalkyl vinyl ether, and the like as a main component. If desired, the thermoplastic fluororesin may be copolymerized with, for example, ethylene, propylene, butene, etc., alkyl vinyl ether, acrylic ester, methacrylic ester, etc., to the extent that its desirable properties are not significantly impaired. Possible monomer units can be included.
さらに、該熱可塑性フッ素樹脂として、所望に応じ、−
ＳＯ□Ｆ、 −〇〇Ｆ 、 −ＣＯＯＨ、−ＣＯＯＲ、
−ＣＮなどの官能基を有する共重合可能なモノマー１例
えば前記官能基を有するテトラフルオコエヂルーパーフ
ルオロアルキルパーフルオロビニルエーテル、パーフル
オロアルキルパーフルオロビニルエーテルなどを０．１
〜５５重量％、好ましくは１〜１０重ｆｆｉ％の範囲で
共重合させた樹脂も使用できる。Furthermore, as the thermoplastic fluororesin, -
SO□F, -〇〇F, -COOH, -COOR,
Copolymerizable monomer having a functional group such as -CN 1 For example, tetrafluorocoedyl perfluoroalkyl perfluorovinyl ether, perfluoroalkyl perfluorovinyl ether, etc. having the above-mentioned functional group at 0.1
Copolymerized resins can also be used in a range of 55% by weight, preferably 1 to 10% by weight.
本発明で使用される熱可塑性フッ素樹脂の例としては、
ポリビニルフルオリド、ポリビニリデンフルオリド、エ
チレン−テトラフルオロエチレン共重合体、プロピレン
−テトラフルオロエチレン共重合体、ビニリデンフルオ
リトーチトラフルオロエチレン共重合体、ビニリデンフ
ルオリドーベンタフルオロプロピレン共重合体、ビニリ
デンフルオリドーへキサフルオロプロピレン共重合体、
テトラフルオロエチレンービニリデンフルオリドーへキ
サフルオロプロピレン共重合体、ビニリチンフルオリド
ーパ−フルオロアルキルパーフルオロビニルエーテル共
重合体、テトラフルオロニチレンーバーフルオロアルキ
ルビニルエーテル共重合体、エチレン−クロロトリフル
オロエチレン共重合体、テトラフルオロエチレンーパー
フルオロアルキルビニルエーテルービニリデンフルオリ
ト共重合体などの分子鎖中に水素原子を含有するフッ素
樹脂、テトラフルオロエチレン−パー７／ｌｚオロアル
キルパーフルオロビニルエーテルー（２−ンアノテトラ
フルオロエチルオキシ）パーフルオロプロピルパーフル
オロビニルエーテル共重合体、テトラフルオロエチレン
−パーフルオロアルキルパーフルオロビニルエーテル−
２−ンアノパーフルオロエチルパーフルオロビニルエー
テル共重合体、テトラフルオロエチレン−パーフルオロ
アルキルパーフルオロビニルエーテル−６−クロロスル
ホニルパーフルオロプロピルパーフルオロビニルエーテ
ル共重合体など、あるいは付加反応や活性な低分子化合
物との反応により架橋する官能基をもつフッ素樹脂、さ
らにはアリル化合物、イオウ、有機アミン類、メタクリ
レート化合物、アクリレート化合物、ジビニル化合物、
オキンム化合物などの架橋助剤を添加したフッ素樹脂な
どが挙げられる。Examples of thermoplastic fluororesins used in the present invention include:
Polyvinyl fluoride, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, propylene-tetrafluoroethylene copolymer, vinylidene fluoride trifluoroethylene copolymer, vinylidene fluoride-bentafluoropropylene copolymer, vinylidene fluoride hexafluoropropylene copolymer,
Tetrafluoroethylene-vinylidene fluoride hexafluoropropylene copolymer, vinylitine fluoride perfluoroalkyl perfluorovinyl ether copolymer, tetrafluoronylene-verfluoroalkyl vinyl ether copolymer, ethylene-chlorotrifluoroethylene copolymer , fluororesins containing hydrogen atoms in the molecular chain such as tetrafluoroethylene-perfluoroalkyl vinyl ether-vinylidene fluorite copolymer, tetrafluoroethylene-per7/lz-oloalkyl perfluorovinyl ether (2-anotetra Fluoroethyloxy) perfluoropropyl perfluorovinyl ether copolymer, tetrafluoroethylene-perfluoroalkyl perfluorovinyl ether-
2-anoperfluoroethyl perfluorovinyl ether copolymer, tetrafluoroethylene-perfluoroalkyl perfluorovinyl ether-6-chlorosulfonyl perfluoropropyl perfluorovinyl ether copolymer, or addition reaction or active low molecular compound. Fluororesins with functional groups that crosslink by reaction, as well as allyl compounds, sulfur, organic amines, methacrylate compounds, acrylate compounds, divinyl compounds,
Examples include fluororesins to which crosslinking aids such as ocimu compounds are added.
これらのフッ素樹脂は、フッ素エラストマーとは異なり
、ＤＳＣ分析で吸熱ピークを有する樹脂である。また、
前記フッ素樹脂には、所望によりその物性をそこなわな
い範囲で、例えばフッ素エラストマーやフッ素系ワック
スなどを配合することもできる。この際、該配合量は通
常０．１〜５０重量％の範囲で選ばれる。These fluororesins are resins that have an endothermic peak in DSC analysis, unlike fluoroelastomers. Also,
If desired, the fluororesin may be blended with, for example, a fluoroelastomer or a fluorine wax within a range that does not impair its physical properties. At this time, the blending amount is usually selected within the range of 0.1 to 50% by weight.
このような熱可塑性フッ素樹脂の中で、分子鎖中に水素
原子を含有するフッ素樹脂は、電離性放射線の照射、あ
るいは化学架橋剤により容易に架橋化され、均一な架橋
構造を有するフッ素樹脂となり、機械的強度に優れ、か
つ弾力性に富ん絃高発泡の発泡体を形成しうるので特に
有利である。Among such thermoplastic fluororesins, fluororesins containing hydrogen atoms in their molecular chains are easily crosslinked by irradiation with ionizing radiation or chemical crosslinking agents, resulting in fluororesins with a uniform crosslinked structure. This is particularly advantageous because it can form a foam with excellent mechanical strength and high elasticity.
本発明のフッ素樹脂発泡体は、例えば化学発泡剤、物理
発泡剤、不活性ガスなどの発泡剤や、高融点有機化合物
、無機微粉末などの核剤を用い、従来公知の方法、例え
ば押出発泡法、フラッシュ発泡法、常圧発泡法、加圧・
型内発泡法などにより製造される。この際、化学発泡剤
を使用する場合には、微粉末を用いて樹脂中に均一に分
散する必要があり、また核剤を用いる場合も、所望の気
泡径に応じて造核能に優れた微細なものを適宜選択して
使用することが重要であるが、電気特性を劣化させず、
工業的に均質な発泡体が容易に得られる点から、核剤を
用いることなく、熱可塑性フッ素樹脂の融解開始温度よ
り１５℃低い温度から１５℃高い温度までの範囲の臨界
温度を有する揮発性物理発泡剤を使用することが好まし
い。The fluororesin foam of the present invention can be produced by a conventional method such as extrusion foaming using a blowing agent such as a chemical blowing agent, a physical blowing agent, or an inert gas, or a nucleating agent such as a high melting point organic compound or an inorganic fine powder. method, flash foaming method, normal pressure foaming method, pressurized
Manufactured by in-mold foaming method. At this time, when using a chemical foaming agent, it is necessary to use fine powder to uniformly disperse it in the resin, and when using a nucleating agent, it is necessary to use a fine powder with excellent nucleating ability depending on the desired bubble diameter. It is important to select and use the appropriate materials, but without deteriorating the electrical characteristics.
Since industrially homogeneous foams can be easily obtained without using a nucleating agent, a volatile material with a critical temperature ranging from 15°C lower to 15°C higher than the melting start temperature of the thermoplastic fluororesin is used. Preference is given to using physical blowing agents.
この揮発性物理発泡剤を使用することにより、本発明の
発泡体が容易に得られる理由については必ずしも明らか
ではないが、樹脂を加熱し、発泡させる過程で、樹脂自
体の結晶相からの造核作用と、それに伴う発泡剤の拡散
、ガス化、さらにこれと同時に起る樹脂の軟化、膨張が
バランスよく進行し、極めて多数の微小な気泡核が生成
して安定に膨張し、発泡体として安定化されるためと考
えられる。臨界温度が前記範囲外の物理発泡剤を使用す
ると、気泡径が９０μｍ より大きくなったり、大きな
空洞が生じるため好ましくない。The reason why the foam of the present invention can be easily obtained by using this volatile physical foaming agent is not necessarily clear, but in the process of heating and foaming the resin, nucleation occurs from the crystalline phase of the resin itself. The action, the accompanying diffusion and gasification of the blowing agent, and the softening and expansion of the resin that occur simultaneously proceed in a well-balanced manner, producing an extremely large number of microscopic cell nuclei that expand stably and become stable as a foam. This is thought to be due to the fact that it is If a physical blowing agent having a critical temperature outside the above range is used, the cell diameter may become larger than 90 μm or large cavities may be formed, which is not preferable.
このような揮発性物理発泡剤としては、使用するフッ素
樹脂の性質、特に融解開始温度に応じ、慣用されている
ものの中から適当に選択されるが、一般的にはプロパン
、ブタン、ペンタンなどの炭化水素、クロロホルム、塩
化メチノベ塩化メチレン、四塩化炭素などの塩化炭化水
素、ジクロロジフルオロメタン、ジクロロフルオロメタ
ン、トリクロロモノフルオロメタン、トリクロロトリフ
ルオロエタン、テトラクロロジフルオロエタン、クロロ
ジフルオロエタン、ジフルオロエタン、オクタフルオロ
シクロブタン、クロコベンタフルオロエタンなどのフッ
化塩化炭化水素などが用いられる。これらはそれぞれ単
独で用いてもよいし、２種以上組み合わせて用いてもよ
く、またこれらを少なくとも５０モル係含有する他の揮
発性有機化合物との混合物として用いてもよい。Such volatile physical blowing agents are appropriately selected from commonly used ones depending on the properties of the fluororesin used, especially the melting start temperature, but generally propane, butane, pentane, etc. Hydrocarbons, chloroform, chlorinated hydrocarbons such as methylene chloride, carbon tetrachloride, dichlorodifluoromethane, dichlorofluoromethane, trichloromonofluoromethane, trichlorotrifluoroethane, tetrachlorodifluoroethane, chlorodifluoroethane, difluoroethane, octafluorocyclobutane, Fluorochlorinated hydrocarbons such as crocobentafluoroethane are used. Each of these may be used alone or in combination of two or more, or may be used as a mixture with another volatile organic compound containing at least 50 moles.
物理発泡剤を含有させる方法としては、例えば耐圧容器
内に樹脂と発泡剤を入れて、密閉して加熱する方法、あ
るいは押出成形機の出口側に設けた注入装置により溶融
した樹脂に圧入して冷却しなから押出成形する方法など
が適宜用いられる。Methods for incorporating a physical foaming agent include, for example, placing the resin and foaming agent in a pressure-resistant container, sealing it, and heating it, or press-fitting it into the molten resin using an injection device installed on the exit side of an extrusion molding machine. A method such as extrusion molding after cooling may be used as appropriate.
本発明のフッ素樹脂発泡体は、熱可塑性フッ素樹脂を前
記のようにして架橋化処理したのち、これに発泡剤を配
合して発泡性組成物を調製し、次いでこれを加熱発泡さ
せるか、あるいは該フッ素樹脂に発泡剤を配合したのち
、これを架橋化処理して発泡性組成物を調製し、次いで
これを加熱発泡させて製造することができる。すなわち
、熱可塑性のフッ素樹脂をシート状に押出したもの、あ
るいは圧縮成形したものに電離性放射線を照射して架橋
シートとし、次いでこれをオートクレーブなどの耐圧容
器内に入れ、物理発泡剤を気体状又は液体状で注入して
加圧下、加熱して含浸し、冷却したのち取り出す方法、
架橋性の官能基を有する架橋性フッ素樹脂に架橋剤を均
一に混合し、押出し、射出又は圧縮成形によって架橋フ
ッ素樹脂成形品としたのち、耐圧容器内でこれに物理発
泡剤を含浸させろ方法、シート状、糸状、フィルム状な
どに成形されたフッ素樹脂に、耐圧容器内で物理発泡剤
を含浸させ、次いで電離性放射線を照射して架橋する方
法など、その目的に応じた方法を用いて発泡性組成物を
調製し、次いで加熱発泡させる。The fluororesin foam of the present invention can be obtained by crosslinking a thermoplastic fluororesin as described above, adding a foaming agent thereto to prepare a foamable composition, and then heating and foaming the composition. After blending a foaming agent into the fluororesin, this can be crosslinked to prepare a foamable composition, and then this can be produced by heating and foaming. That is, a thermoplastic fluororesin extruded or compression molded into a sheet is irradiated with ionizing radiation to form a crosslinked sheet, which is then placed in a pressure-resistant container such as an autoclave, and a physical blowing agent is added to the gaseous form. Or, a method in which it is injected in liquid form, impregnated by heating under pressure, and then taken out after cooling.
A method of uniformly mixing a crosslinking agent with a crosslinkable fluororesin having a crosslinkable functional group, forming a crosslinked fluororesin molded product by extrusion, injection or compression molding, and impregnating the product with a physical foaming agent in a pressure-resistant container; Foaming is performed using a method depending on the purpose, such as impregnating a fluororesin formed into a sheet, thread, or film with a physical foaming agent in a pressure-resistant container and then irradiating it with ionizing radiation to crosslink it. A synthetic composition is prepared and then heated and foamed.
この加熱発泡は、通常該樹脂の融点より３０℃低い温度
から３０℃高い温度までの範囲の温度に加熱することに
よって行われる。This thermal foaming is usually carried out by heating the resin to a temperature ranging from 30° C. lower to 30° C. higher than the melting point of the resin.
本発明のフッ素樹脂発泡体は、その平均気泡径が９０μ
ｍ以下であることが必要である。この平均気泡径が９０
μｍを超えると、例えば絶縁破壊強さが基材樹脂のそれ
よりも著しく小さくなるし、表面熱伝達抵抗が小さくな
って断熱性が劣化し、あるいは表面平滑性が劣化する。The fluororesin foam of the present invention has an average cell diameter of 90 μm.
It is necessary that it is less than m. This average bubble diameter is 90
If it exceeds .mu.m, for example, the dielectric breakdown strength will be significantly smaller than that of the base resin, the surface heat transfer resistance will decrease, the heat insulation properties will deteriorate, or the surface smoothness will deteriorate.
平均気泡径の好ましい範囲は１〜５０μｍであり、この
範囲の発泡体は、電気特性をはじめ、機械的強さ、表面
平滑性、熱伝達抵抗などの特性のバランスがとれていて
、実用上有用である。The preferred range of average cell diameter is 1 to 50 μm, and foams in this range have well-balanced properties such as electrical properties, mechanical strength, surface smoothness, and heat transfer resistance, and are useful in practice. It is.
本発明の発泡体は、その発泡倍率が１．５〜５０倍、特
に２．５〜３０倍の範囲にあるものが好適である。この
発泡倍率が１．５倍未満のものは、電気絶縁性や断熱性
能に劣る上に、圧縮回復率が低く、例えば繰り返し圧縮
変形を受ける印刷版用クッション材、転写ロール材、研
磨材などの用途には好ましくない。一方５０倍を超える
ものは、引張強度や引裂強度などの機械的強度が低く好
ましくない。特に発泡倍率が２．５〜３０倍の範囲のも
のは、電気特性、断熱性、圧縮回復率、繰り返し圧縮回
復率、引張強度、引裂強度、圧縮永久歪などのバランス
がとれていて好ましい。The foam of the present invention preferably has an expansion ratio of 1.5 to 50 times, particularly 2.5 to 30 times. Foaming with a foaming ratio of less than 1.5 times not only has poor electrical insulation and heat insulation performance, but also has a low compression recovery rate. Not suitable for use. On the other hand, if it exceeds 50 times, mechanical strength such as tensile strength and tear strength is low and is not preferred. In particular, those having an expansion ratio in the range of 2.5 to 30 times are preferable because they have a well-balanced electrical property, heat insulating property, compression recovery rate, repeated compression recovery rate, tensile strength, tear strength, compression set, etc.
本発明のフッ素樹脂発泡体は、その用途に応じて、シー
ト状、フィルム状、糸状、筒状、棒状などに成形され、
また、顔料、充てん剤、補強材などを含有させることも
可能である。The fluororesin foam of the present invention can be formed into a sheet, film, string, cylinder, rod, etc. depending on its use.
It is also possible to contain pigments, fillers, reinforcing materials, etc.
発明の効果
本発明のフッ素樹脂発泡体は、熱可塑性フッ素樹脂の架
橋化物を発泡させて成る平均気泡径９０μｍ以下の微細
気泡を有する発泡体であるため、引張強度、引裂強度、
圧縮永久歪などの機械的特性に優れ、かつ圧縮回復率が
良好で弾力性に富み、さらに気泡が微細で均一であって
、電気絶縁性、断熱性、表面平滑性などに優れている。Effects of the Invention The fluororesin foam of the present invention is a foam made by foaming a crosslinked thermoplastic fluororesin and has fine cells with an average cell diameter of 90 μm or less, so it has high tensile strength, tear strength,
It has excellent mechanical properties such as compression set, good compression recovery rate, and is rich in elasticity.Furthermore, the bubbles are fine and uniform, and it has excellent electrical insulation, heat insulation, and surface smoothness.
したがって、本発明のフッ素樹脂発泡体は、例えば印刷
用のロール、クッション材、高周波絶縁材、電線被覆材
、精密研磨用の研磨布、輻射エネールギー遮断材、ガス
ンール材などとして有用である。Therefore, the fluororesin foam of the present invention is useful as, for example, a printing roll, a cushioning material, a high-frequency insulating material, a wire covering material, an abrasive cloth for precision polishing, a radiant energy shielding material, a gas-n-wheel material, and the like.
実施例 次に実施例により本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
なお、各測定値は次のようにして求めた。In addition, each measurement value was calculated|required as follows.
（１）フッ素樹脂のメルトフローレートＡＳＴＭ Ｄ２
１１６−７５に記載されている装置を使用して、ＡＳＴ
Ｍ Ｄ１２３１１ｒに記載の条件（ポリビニリデンフル
オリド及び共重合体）又はＡＳＴＭ Ｄ３１５９記載の
条件（エチレン−テトラフルオロエチレン共重合体など
）で測定した。(1) Fluororesin melt flow rate ASTM D2
AST using the apparatus described in 116-75.
It was measured under the conditions described in MD12311r (polyvinylidene fluoride and copolymers) or the conditions described in ASTM D3159 (ethylene-tetrafluoroethylene copolymer, etc.).
（２）フッ素樹脂の融点及び融解開始温度融点はＡＳＴ
Ｍ Ｄ５１５９−７３に記載の方法で測定し、融解開始
温度は、ベースライン法で融解ピークの立上り開始点を
求め、その点の温度を開始温度とした。(2) Melting point and melting start temperature of fluororesin The melting point is AST
The melting start temperature was measured by the method described in MD5159-73, and the starting point of the melting peak was determined by the baseline method, and the temperature at that point was taken as the starting temperature.
（３）動的粘弾性特性
レオメトリックス社製ダイナミックスペクトロメーター
ＲＤＳ−７７００型を用い、窒素雰囲気下に樹脂の融点
より３０℃高い温度において、角周波数ｉ Ｑ ｒａｄ
ｉａｎ ／ Ｓｅｃ 、歪量５係の条件で動的ずり損失
弾性率（Ｇつと動的ずり貯蔵弾性率（Ｇ′）を測定し、
それらの比（Ｇ“フル′）を求めた。(3) Dynamic viscoelastic properties Using a dynamic spectrometer RDS-7700 manufactured by Rheometrics, the angular frequency i Q rad was measured in a nitrogen atmosphere at a temperature 30°C higher than the melting point of the resin.
ian/Sec, dynamic shear loss elastic modulus (G) and dynamic shear storage elastic modulus (G') were measured under the conditions of strain amount 5 factor,
Their ratio (G "full'") was determined.
なお、測定には、パラレルプレートモードラ使用し、サ
ンプルは厚み１．２ ＷＭで直径２５朋の円盤状のもの
を用いた。Note that a parallel plate model was used for the measurement, and the sample was a disk-shaped sample with a thickness of 1.2 WM and a diameter of 25 mm.
（４）発泡倍率
サンプルの重量と水浸法で求めた体積とから計算した発
泡体の密度と樹脂の密度から次式により計算した。(4) Expansion ratio The foam density was calculated from the weight of the sample and the volume determined by the water immersion method and the density of the resin using the following formula.
（５）平均気泡径
サンプルの厚み断面を電子顕微鏡で観察し、ランダムに
選んだ２０個以上の気泡の長径及び短径を測定し、これ
らの平均値で示した。(5) Average bubble diameter The thickness cross-section of the sample was observed with an electron microscope, and the long and short axes of 20 or more randomly selected bubbles were measured, and the average value was expressed.
（６）圧縮回復率
ＪＩＳＫ６３０１ に記載の圧縮試験法で５０％圧縮
歪を与え、荷重を除いた１０分後の厚さを測定し、次式
により求めた。(6) Compression recovery rate A 50% compressive strain was applied using the compression test method described in JIS K6301, and the thickness was measured 10 minutes after the load was removed, and was calculated using the following formula.
（７）表面平滑性
発泡体シートをレザーで切断し、切断面を５０倍に拡大
し、ランダムに選んだシート表面の断面を複察し、表面
に接する直線と、発泡体表面との最大距離とを測定し、
以下の基準で評価した。(7) Cut a foam sheet with a smooth surface using a razor, magnify the cut surface 50 times, carefully examine the cross section of the sheet surface selected at random, and calculate the maximum distance between the straight line touching the surface and the foam surface. measure,
Evaluation was made based on the following criteria.
０２１０８ｍ以下
△：１０μｍより太き（５０ｌｉｍ以下×：５０μｍよ
り大きい
（８）表面熱伝達抵抗
発泡体シートを２００ Ｘ ２０Ｑ ｓｍの大きさに切
断し、その裏面と表面に熱電対を貼り付け、ＡＳＴＭ
Ｃ２５６に準じた方法により、サンプルを通じて流れる
熱量Ｑａ（＆／ｈ）、高温側の空気温度（θＨ）及び高
温側のサンプル表面温度（θＨ８）を測定し、次式によ
り求めた。02108m or less △: Thicker than 10μm (50lim or less
The amount of heat Qa (&/h) flowing through the sample, the air temperature on the high temperature side (θH), and the sample surface temperature on the high temperature side (θH8) were measured by a method according to C256, and calculated using the following formula.
（９）絶縁破壊強度比
ＡＳＴＭ Ｄ１４９に記載の方法に準じ、ＩＫＶ／ｓｅ
ｃで昇圧して絶縁破壊強さを測定し、次式により基材樹
脂との比を求めた。(9) Dielectric breakdown strength ratio IKV/se according to the method described in ASTM D149
The dielectric breakdown strength was measured by increasing the pressure at c, and the ratio to the base resin was determined using the following formula.
絶縁破壊強度比（％）＝
実施例１，２
ビニリデンフルオリドーへキサフルオロプロピレン共重
合体（ペンウォルト社製、登録商標Ｋｙｎａｒ ：＃２
８００ ）を、加熱プレ、ｚ、 テ厚さ１．２罪のシー
トに成形し、電子線照射装置で架橋処理をした。架橋フ
ッ素樹脂の動的粘弾性を測定した結果、弾性率比（Ｇ’
７Ｇ’）は０．４であり、またＤＳＣによる融解開始温
度、及びピーク温度はそれぞれ１１２’（：；、１４６
℃であった。得られた架橋フッ素樹脂のシートを、密閉
容器に入れジクロロジフルオロメタンを圧入し、７５℃
で５ｏ時間含浸して、樹脂１１当り０．６５モルのジク
ロロジフルオロメタンを含有する発泡性シートを得た。Dielectric breakdown strength ratio (%) = Examples 1, 2 Vinylidene fluoride hexafluoropropylene copolymer (manufactured by Pennwalt, registered trademark Kynar: #2
800) was heated and formed into a sheet with a thickness of 1.2 mm, and crosslinked using an electron beam irradiation device. As a result of measuring the dynamic viscoelasticity of crosslinked fluororesin, the elastic modulus ratio (G'
7G') is 0.4, and the melting start temperature and peak temperature by DSC are respectively 112'(:;, 146
It was ℃. The obtained crosslinked fluororesin sheet was placed in a sealed container, dichlorodifluoromethane was press-fitted, and the temperature was increased to 75°C.
A foamable sheet containing 0.65 mol of dichlorodifluoromethane per 11 resin was obtained.
当該シートを空気中に放置して、ジクロロジフルオロメ
タン含浸量が口、５（モル／樹脂１１）となったものを
６．０ｋｇ／ｃｙｉ’ゲージ圧のスチームで３０秒間加
熱して発泡させた。得られた発泡体は、発泡倍率１６倍
で、平均気泡径２０μｍの均一な気泡を有するもので、
圧縮回復率は８７係、表面熱伝達抵抗０．１８ｙｒ＋”
ｈ・’Ｃ／１ａ１１絶縁破壊強さ２３ ＫＶ ／ｍｙテ
強度強度比ハロ００チれた特性を有するものであった。The sheet was left in the air and the amount of dichlorodifluoromethane impregnated was 5 (mole/11 resin) and heated with steam at 6.0 kg/cyi' gauge pressure for 30 seconds to foam. The obtained foam had a foaming ratio of 16 times and uniform cells with an average cell diameter of 20 μm.
Compression recovery rate: 87, surface heat transfer resistance: 0.18yr+”
h・'C/1a11 dielectric breakdown strength 23 KV/myte strength ratio halo00.
（実施例発泡処理の加熱条件を２．５ ｋｇ ／ ａｘ
２ゲージ圧スデスチーム０秒間加熱した以外は、上記と
同じ方法で発泡体を得た（実施例２）。(The heating conditions for the example foaming treatment were 2.5 kg/ax.
A foam was obtained in the same manner as above (Example 2) except that it was heated with 2 gauge pressure steam for 0 seconds.
得られた発泡体の特性を第１表に示す。The properties of the obtained foam are shown in Table 1.
実施例３〜９
実施例１において、フッ素樹脂及び発泡剤として第１表
に示すものを使用した以外は、実施例１と同様にして発
泡体を得た。得られた発泡体は第１表に示したとおり、
優れた性能を有するものであった。Examples 3 to 9 Foamed bodies were obtained in the same manner as in Example 1, except that the fluororesin and foaming agent shown in Table 1 were used. The obtained foam was as shown in Table 1.
It had excellent performance.
比較例１〜３
実施例１において、発泡剤を１，２−ジクロロテトラフ
ルオロエタン（比較例２）及びジクロロモノフルオロメ
タン（比較例３）に変えてそれぞれ発泡性シートを得た
。得られたノートを２．５に９／ｄゲージ圧のスチーム
で加熱して、発泡体を得た。Comparative Examples 1 to 3 In Example 1, foamable sheets were obtained by changing the blowing agent to 1,2-dichlorotetrafluoroethane (Comparative Example 2) and dichloromonofluoromethane (Comparative Example 3). The resulting notebook was heated with steam at 2.5 to 9/d gauge pressure to obtain a foam.
また架橋しないこと以外は、実施例１と同様にして発泡
体を得た（比較例１）。これらの結果を第２表に示す。Further, a foam was obtained in the same manner as in Example 1 except that it was not crosslinked (Comparative Example 1). These results are shown in Table 2.
比較例４，５
実施例７において、発泡剤をジクロロジフルオロメタン
に変えた以外は、実施例７と同様にして発泡体を得た（
比較例４）。また、発泡剤をジクロロジフルオロメタン
に変え、かつ架橋しないこと以外は、実施例７と同様に
して発泡体を得た（比較例５）。Comparative Examples 4 and 5 A foam was obtained in the same manner as in Example 7, except that the blowing agent was changed to dichlorodifluoromethane (
Comparative example 4). Further, a foam was obtained in the same manner as in Example 7 except that the blowing agent was changed to dichlorodifluoromethane and no crosslinking was performed (Comparative Example 5).
これらの結果を第２表に示す。These results are shown in Table 2.
第１表及び第２表から明らかなように、本発明の発泡体
は圧縮回復率、表面熱伝達抵抗及び絶縁破壊強さの各位
が大きく、かつ基材樹脂とほぼ同じ破壊性を示す上に、
表面平滑性にも優れている。As is clear from Tables 1 and 2, the foam of the present invention has a high compression recovery rate, a high surface heat transfer resistance, and a high dielectric breakdown strength, and also exhibits almost the same fracture properties as the base resin. ,
It also has excellent surface smoothness.
Claims (1)
均気泡径が９０μｍ以下の微細気泡を有するフッ素樹脂
発泡体。 ２ 熱可塑性フッ素樹脂がフルオロエチレン、フルオロ
−α−オレフィン、フルオロアルキルフルオロビニルエ
ーテル及びフルオロアルキルビニルエーテルの中から選
ばれた少なくとも１種のモノマーを主成分として得られ
たものである特許請求の範囲第１項記載の発泡体。 ３ 熱可塑性フッ素樹脂が分子鎖中に水素原子を含有す
るものである特許請求の範囲第１項又は第２項記載の発
泡体。 ４ 熱可塑性フッ素樹脂の架橋化物がその融点より３０
℃高い温度における動的ずり貯蔵弾性率に対する動的ず
り損失弾性率の比が０．３〜０．９の範囲のものである
特許請求の範囲第１項ないし第３項のいずれかに記載の
発泡体。 ５ 発泡倍率が２．５〜３０倍である特許請求の範囲第
１項ないし第４項のいずれかに記載の発泡体。 ６ 平均気泡径が１〜５０μｍである特許請求の範囲第
１項ないし第５項のいずれかに記載の発泡体。 ７ 熱可塑性フッ素樹脂を架橋化処理したのち、これに
発泡剤を配合するか、あるいは該フッ素樹脂に発泡剤を
配合したのち、これを架橋化処理することにより発泡性
組成物を調製し、次いでこれを加熱して発泡させること
を特徴とする、平均気泡径９０μｍ以下の微細気泡を有
するフッ素樹脂発泡体の製造方法。 ８ 発泡剤が熱可塑性フッ素樹脂の融解開始温度より１
５℃低い温度から１５℃高い温度までの範囲の臨界温度
を有する揮発性物理発泡剤である特許請求の範囲第７項
記載の製造方法。 ９ 熱可塑性フッ素樹脂がフルオロエチレン、フルオロ
−α−オレフィン、フルオロアルキルフルオロビニルエ
ーテル及びフルオロアルキルビニルエーテルの中から選
ばれた少なくとも１種のモノマーを主成分として得られ
たものである特許請求の範囲第７項又は第８項記載の製
造方法。 １０ 熱可塑性フッ素樹脂が分子鎖中に水素原子を含有
するものである特許請求の範囲第７項ないし第９項のい
ずれかに記載の製造方法。 １１ 架橋化処理された熱可塑性フッ素樹脂が、その融
点より３０℃高い温度における動的ずり貯蔵弾性率に対
する動的ずり損失弾性率の比が０．３〜０．９の範囲の
ものである特許請求の範囲第７項ないし第１０項のいず
れかに記載の製造方法。 １２ ２．５〜３０倍の発泡倍率に発泡させる特許請求
の範囲第７項ないし第１１項のいずれかに記載の製造方
法。 １３ 発泡体の平均気泡径が１〜５０μｍである特許請
求の範囲第７項ないし第１２項のいずれかに記載の製造
方法。[Scope of Claims] 1. A fluororesin foam having fine cells with an average cell diameter of 90 μm or less, which is obtained by foaming a crosslinked thermoplastic fluororesin. 2. Claim 1, in which the thermoplastic fluororesin is obtained mainly from at least one monomer selected from fluoroethylene, fluoro-α-olefin, fluoroalkyl fluorovinyl ether, and fluoroalkyl vinyl ether. Foam as described in Section. 3. The foam according to claim 1 or 2, wherein the thermoplastic fluororesin contains a hydrogen atom in its molecular chain. 4 The crosslinked product of thermoplastic fluororesin is 30% lower than its melting point.
Claims 1 to 3, wherein the ratio of dynamic shear loss modulus to dynamic shear storage modulus at a high temperature of 0.3 to 0.9 is in the range of 0.3 to 0.9. foam. 5. The foam according to any one of claims 1 to 4, which has an expansion ratio of 2.5 to 30 times. 6. The foam according to any one of claims 1 to 5, having an average cell diameter of 1 to 50 μm. 7. A foamable composition is prepared by crosslinking a thermoplastic fluororesin and then adding a foaming agent thereto, or by adding a foaming agent to the fluororesin and subjecting it to a crosslinking treatment, and then A method for producing a fluororesin foam having fine cells with an average cell diameter of 90 μm or less, the method comprising heating and foaming the foam. 8 The blowing agent is 1 higher than the melting start temperature of the thermoplastic fluororesin.
8. The method of claim 7, which is a volatile physical blowing agent having a critical temperature ranging from 5° C. lower to 15° C. higher. 9. Claim 7, wherein the thermoplastic fluororesin is obtained with at least one monomer selected from fluoroethylene, fluoro-α-olefin, fluoroalkyl fluorovinyl ether, and fluoroalkyl vinyl ether as a main component. The manufacturing method described in item 1 or item 8. 10. The manufacturing method according to any one of claims 7 to 9, wherein the thermoplastic fluororesin contains a hydrogen atom in its molecular chain. 11 A patent in which the crosslinked thermoplastic fluororesin has a ratio of dynamic shear loss modulus to dynamic shear storage modulus at a temperature 30°C higher than its melting point, in the range of 0.3 to 0.9. The manufacturing method according to any one of claims 7 to 10. 12. The manufacturing method according to any one of claims 7 to 11, wherein foaming is performed to an expansion ratio of 2.5 to 30 times. 13. The manufacturing method according to any one of claims 7 to 12, wherein the foam has an average cell diameter of 1 to 50 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12211286A JPS62280236A (en) | 1986-05-29 | 1986-05-29 | Fluorocarbon resin having fine cell and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12211286A JPS62280236A (en) | 1986-05-29 | 1986-05-29 | Fluorocarbon resin having fine cell and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62280236A true JPS62280236A (en) | 1987-12-05 |
| JPH0374696B2 JPH0374696B2 (en) | 1991-11-27 |
Family
ID=14827933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12211286A Granted JPS62280236A (en) | 1986-05-29 | 1986-05-29 | Fluorocarbon resin having fine cell and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62280236A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814409A (en) * | 1994-05-10 | 1998-09-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Expanded fluorine type resin products and a preparation process thereof |
| EP0893629A1 (en) * | 1997-07-22 | 1999-01-27 | Bamberger Kaliko GmbH | Yarn for sealing |
| JP2001088013A (en) * | 1999-09-21 | 2001-04-03 | Toyobo Co Ltd | Polishing pad |
| JP2001232554A (en) * | 2000-02-22 | 2001-08-28 | Toyobo Co Ltd | Polishing pad and method for manufacturing thereof |
| CN112592549A (en) * | 2020-11-23 | 2021-04-02 | 深圳市长园特发科技有限公司 | Radiation crosslinking polyvinylidene fluoride foam material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6193268A (en) * | 1984-08-14 | 1986-05-12 | ユナイテツド・テクノロジ−ズ・デイ−ゼル・システムズ・インコ−ポレイテツド | Constantly opened type valve |
-
1986
- 1986-05-29 JP JP12211286A patent/JPS62280236A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6193268A (en) * | 1984-08-14 | 1986-05-12 | ユナイテツド・テクノロジ−ズ・デイ−ゼル・システムズ・インコ−ポレイテツド | Constantly opened type valve |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814409A (en) * | 1994-05-10 | 1998-09-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Expanded fluorine type resin products and a preparation process thereof |
| EP0893629A1 (en) * | 1997-07-22 | 1999-01-27 | Bamberger Kaliko GmbH | Yarn for sealing |
| JP2001088013A (en) * | 1999-09-21 | 2001-04-03 | Toyobo Co Ltd | Polishing pad |
| JP4542647B2 (en) * | 1999-09-21 | 2010-09-15 | 東洋ゴム工業株式会社 | Polishing pad |
| JP2001232554A (en) * | 2000-02-22 | 2001-08-28 | Toyobo Co Ltd | Polishing pad and method for manufacturing thereof |
| JP4591980B2 (en) * | 2000-02-22 | 2010-12-01 | 東洋ゴム工業株式会社 | Polishing pad and manufacturing method thereof |
| CN112592549A (en) * | 2020-11-23 | 2021-04-02 | 深圳市长园特发科技有限公司 | Radiation crosslinking polyvinylidene fluoride foam material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0374696B2 (en) | 1991-11-27 |
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