JP2011074129A - Water and oil repellent composition - Google Patents
Water and oil repellent composition Download PDFInfo
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- JP2011074129A JP2011074129A JP2009224615A JP2009224615A JP2011074129A JP 2011074129 A JP2011074129 A JP 2011074129A JP 2009224615 A JP2009224615 A JP 2009224615A JP 2009224615 A JP2009224615 A JP 2009224615A JP 2011074129 A JP2011074129 A JP 2011074129A
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- 239000000203 mixture Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 13
- 230000002940 repellent Effects 0.000 title abstract description 3
- 239000005871 repellent Substances 0.000 title abstract description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 58
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 58
- 239000010419 fine particle Substances 0.000 claims abstract description 45
- 239000002270 dispersing agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 38
- 229910052731 fluorine Inorganic materials 0.000 claims description 38
- 239000011737 fluorine Substances 0.000 claims description 38
- 125000001931 aliphatic group Chemical group 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 10
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VJRSWIKVCUMTFK-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F VJRSWIKVCUMTFK-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- RKOOOVKGLHCLTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.OCC(O)CO RKOOOVKGLHCLTP-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
Description
本発明は、金属等の表面に撥水、撥油性能を付与させるのに有用な含フッ素オリゴマーを含む分散剤に関する。 The present invention relates to a dispersant containing a fluorine-containing oligomer useful for imparting water repellency and oil repellency to a surface of metal or the like.
ＰＴＦＥ（ポリテトラフルオロエチレン）微粒子は、表面エネルギーが低く、撥水性・撥油性および比重が大きいことから、一般的な有機溶媒中には分散しにくい。また、ＰＴＦＥ微粒子のみを金属表面にコーティングした場合、良好な撥水性を示すが、撥油性の点では十分ではない。このため、ＰＴＦＥ微粒子は、ＰＦＯＡ（パーフルオロオクタン酸）、ＰＦＯＳ（パーフルオロオクタンスルホン酸）、テロメリゼーション法で製造された含フッ素オリゴマー等を含む有機溶媒等に分散して、各種用途に使用されている。 PTFE (polytetrafluoroethylene) fine particles have low surface energy, high water repellency / oil repellency, and high specific gravity, and are therefore difficult to disperse in general organic solvents. Further, when only the PTFE fine particles are coated on the metal surface, good water repellency is exhibited, but the oil repellency is not sufficient. For this reason, PTFE fine particles are dispersed in organic solvents including PFOA (perfluorooctanoic acid), PFOS (perfluorooctanesulfonic acid), fluorine-containing oligomers produced by the telomerization method, and used for various applications. Has been.
しかしながら、近年、ＰＦＯＡ、ＰＦＯＳは、環境での残留性、生体での蓄積性、及び有毒性が懸念されており、各国で使用規制が設けられてきている。また、従来使用されてきた含フッ素オリゴマー分散剤は、熱等により分解し、ＰＦＯＡ（パーフルオロオクタン酸）、ＰＦＯＳ（パーフルオロオクタンスルホン酸）等のフッ素化合物を生成するので、このようなオリゴマーを使用することも好ましくない。このような背景のもと、ＰＦＯＡ、ＰＦＯＳ、分解してＰＦＯＡやＰＦＯＳといったフッ素化合物を生成する含フッ素オリゴマー分散剤に代わる分散剤の開発が望まれている。 However, in recent years, PFOA and PFOS are concerned about persistence in the environment, bioaccumulation, and toxicity, and use restrictions have been established in each country. In addition, conventionally used fluorine-containing oligomer dispersants are decomposed by heat or the like to generate fluorine compounds such as PFOA (perfluorooctanoic acid) and PFOS (perfluorooctanesulfonic acid). It is also not preferable to use it. Against this background, development of a dispersant that replaces PFOA, PFOS, and fluorine-containing oligomer dispersants that decompose to produce fluorine compounds such as PFOA and PFOS is desired.
本発明は、ＰＴＦＥ微粒子の分散性に優れ、かつ、ＰＴＦＥのコーティング膜とした時の撥水性及び撥油性の両方に優れる、ＰＴＦＥ微粒子の分散剤を提供することを主な課題とする。 The main object of the present invention is to provide a PTFE fine particle dispersant that is excellent in dispersibility of PTFE fine particles and that is excellent in both water repellency and oil repellency when used as a coating film of PTFE.
本発明者は、上記課題を解決するために鋭意検討を重ねた結果、高度に分岐したパーフルオロアルケニル基を主鎖にもつ含フッ素オリゴマーとＰＴＦＥ微粒子とを併用することにより、金属等の表面に優れた撥水撥油性能を付与することができることを見出した。本発明は、このような知見に基づき完成された発明である。すなわち、本発明は、下記項１〜６に記載の分散剤、該分散剤とＰＴＦＥ微粒子を含む組成物、及び該組成物を熱処理して得られるコーティング膜に関する。 As a result of intensive studies in order to solve the above problems, the present inventor has used a fluorine-containing oligomer having a highly branched perfluoroalkenyl group in the main chain and PTFE fine particles in combination on the surface of metal or the like. It has been found that excellent water and oil repellency can be imparted. The present invention has been completed based on such findings. That is, the present invention relates to the dispersant according to items 1 to 6, the composition containing the dispersant and PTFE fine particles, and a coating film obtained by heat-treating the composition.
項１． 下記一般式（１）で表される含フッ素オリゴマー及び有機溶剤を含むＰＴＦＥ微粒子の分散剤。
項３． 項１又は２に記載の分散剤及びＰＴＦＥ微粒子を含む組成物であって、該組成物中の含フッ素オリゴマーの含有量が０．１〜３０．０重量％、有機溶剤の含有量が５０．０〜９９．８重量％、ＰＴＦＥ微粒子の含有量が０．１〜４０．０重量％である組成物。
項４． 前記分散剤の配合割合が前記組成物中の０．１〜３０．０重量％である項３に記載の組成物。
項５． 前記一般式（１）で表される含フッ素オリゴマーとＰＴＦＥ微粒子の配合量の比率（重量）が、下式：
1≦[ＰＴＦＥ微粒子]／[一般式（1）で表される含フッ素オリゴマー]≦４０
の関係にある項３又は４に記載の組成物。
項６． 項３〜５のいずれかに記載の組成物を金属、セラミックス又は樹脂の表面に塗布し、熱処理して得られるコーティング膜。
Item 1. A PTFE fine particle dispersant containing a fluorine-containing oligomer represented by the following general formula (1) and an organic solvent.
Item 3. Item 3. A composition comprising the dispersant according to Item 1 or 2 and PTFE fine particles, wherein the fluorine-containing oligomer content in the composition is 0.1 to 30.0% by weight, and the organic solvent content is 50. A composition having a content of 0 to 99.8% by weight and a PTFE fine particle content of 0.1 to 40.0% by weight.
Item 4. Item 4. The composition according to Item 3, wherein a blending ratio of the dispersant is 0.1 to 30.0% by weight in the composition.
Item 5. The ratio (weight) of the blending amount of the fluorine-containing oligomer represented by the general formula (1) and the PTFE fine particles is represented by the following formula:
1 ≦ [PTFE fine particles] / [fluorinated oligomer represented by general formula (1)] ≦ 40
Item 5. The composition according to Item 3 or 4, wherein
Item 6. A coating film obtained by applying the composition according to any one of Items 3 to 5 to the surface of a metal, ceramics, or resin and heat-treating it.
本発明によれば、ＰＴＦＥ微粉末の分散性に優れ、かつ、ＰＴＦＥ微粉末との混合物とした時の撥水性と撥油性の両方に優れた分散剤を得ることができる。該分散剤を使用することにより、ＰＴＦＥ微粉末の焼付けを１５０〜２５０℃程度と比較的低温行うことができるため、金属、セラミックス等の高温に耐える材料表面だけでなく、樹脂等の高温に弱い材料表面に撥水撥油性を付与することもできる。さらに、本発明の分散剤は、分解してもＰＦＯＡ、ＰＦＯＳといった環境での残留性等が懸念されるフッ素化合物を生じないので、従来のＰＴＦＥ微粒子の分散剤として好適に使用できる。 According to the present invention, it is possible to obtain a dispersant that is excellent in dispersibility of PTFE fine powder and excellent in both water repellency and oil repellency when mixed with PTFE fine powder. By using this dispersant, PTFE fine powder can be baked at a relatively low temperature of about 150 to 250 ° C., so that it is not only resistant to high temperatures of materials such as metals and ceramics but also to high temperatures of resins and the like. Water and oil repellency can also be imparted to the material surface. Furthermore, since the dispersant of the present invention does not produce a fluorine compound that is feared of persistence in the environment such as PFOA and PFOS even when decomposed, it can be suitably used as a dispersant for conventional PTFE fine particles.
以下、本発明の分散剤、組成物及びコーティング膜について詳述する。 Hereinafter, the dispersant, composition and coating film of the present invention will be described in detail.
１．分散剤
本発明の分散剤は、以下の含フッ素オリゴマー、及び有機溶剤といった他の成分を含む。
1. Dispersant The dispersant of the present invention contains the following fluorine-containing oligomer and other components such as an organic solvent.
含フッ素オリゴマー
本発明の分散剤は、ＰＴＦＥ微粒子を分散させるための分散剤であり、下記一般式（１）：
Fluorine-containing oligomer The dispersant of the present invention is a dispersant for dispersing PTFE fine particles, and has the following general formula (1):
で表される含フッ素オリゴマーを含むことを特徴とする。 It is characterized by including the fluorine-containing oligomer represented by these.
一般式（１）において、Ｒ１は炭素原子数が１〜５０の二価の飽和脂肪族炭化水素基である。該飽和脂肪族炭化水素基は、所望によりハロゲン原子、エーテル結合、エステル結合、アミド結合又はアリール基を複数有していてもよい。Ｒ１は、好ましくは炭素原子数が１〜２０の二価の飽和脂肪族炭化水素基である。 In the general formula (1), R 1 is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms. The saturated aliphatic hydrocarbon group may have a plurality of halogen atoms, ether bonds, ester bonds, amide bonds or aryl groups as desired. R 1 is preferably a divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms.
特に好ましいＲ１としては、下記一般式で表される二価の飽和脂肪族炭化水素基が挙げられる。
−（ＣＨ２）ｎ１− （ｎ１＝２〜１０）
−（ＣＨ２）ｎ２ＯＣＯＣ６Ｈ４− （ｎ２＝２〜１０）
−（ＣＨ２）ｎ３Ｃ６Ｈ４− （ｎ３＝１〜１０）
−（ＣＨ２ＣＨ２Ｏ）ｎ４ＣＨ２ＣＨ２− （ｎ４＝１〜１０）
−（ＣＨ２ＣＨ２Ｏ）ｎ５ＣＯＣ６Ｈ４− （ｎ５＝１〜１０）。
Particularly preferred R 1 includes a divalent saturated aliphatic hydrocarbon group represented by the following general formula.
- (CH 2) n1 - ( n1 = 2~10)
- (CH 2) n2 OCOC 6 H 4 - (n2 = 2~10)
- (CH 2) n3 C 6 H 4 - (n3 = 1~10)
- (CH 2 CH 2 O) n4 CH 2 CH 2 - (n4 = 1~10)
- (CH 2 CH 2 O) n5 COC 6 H 4 - (n5 = 1~10).
一般式（１）において、Ｒ２は炭素原子数が１〜１００の二価の飽和脂肪族炭化水素基である。該飽和脂肪族炭化水素基は所望によりハロゲン原子、エーテル結合、エステル結合、アミド結合又はアリール基を複数有していてもよい。Ｒ２は好ましくは炭素原子数が２〜５０の二価の飽和脂肪族炭化水素基である。 In the general formula (1), R 2 is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms. The saturated aliphatic hydrocarbon group may optionally have a plurality of halogen atoms, ether bonds, ester bonds, amide bonds or aryl groups. R 2 is preferably a divalent saturated aliphatic hydrocarbon group having 2 to 50 carbon atoms.
特に好ましいＲ２としては、下記一般式で表される二価の飽和脂肪族炭化水素基が挙げられる。
−（ＣＨ２）ｎ６− （ｎ６＝２〜１０）
−（ＣＨ２ＣＨ２Ｏ）ｎ７ＣＨ２ＣＨ２− （ｎ７＝１〜２０）
−（ＣＨ２ＣＨ２ＣＨ２Ｏ）ｎ８ＣＨ２ＣＨ２ＣＨ２− （ｎ８＝１〜１０）。
Particularly preferred R 2 includes a divalent saturated aliphatic hydrocarbon group represented by the following general formula.
- (CH 2) n6 - ( n6 = 2~10)
- (CH 2 CH 2 O) n7 CH 2 CH 2 - (n7 = 1~20)
- (CH 2 CH 2 CH 2 O) n8 CH 2 CH 2 CH 2 - (n8 = 1~10).
一般式（１）において、Ｒ３及びＲ４は、相互に独立してＨ又はメチル基である。 In the general formula (1), R 3 and R 4 are each independently H or a methyl group.
また、ｍ及びｎは、相互に独立して、１〜３０の整数である。ｍ及びｎは、好ましくは相互に独立して、０．１≦m／ｎ≦１０、特に好ましくは０．３≦m／ｎ≦５である。
一般式（１）において、各繰り返し単位の順番は特定されず、ランダムでもブロックでもよい。
Moreover, m and n are the integers of 1-30 independently of each other. m and n are preferably independently of each other, 0.1 ≦ m / n ≦ 10, particularly preferably 0.3 ≦ m / n ≦ 5.
In the general formula (1), the order of each repeating unit is not specified and may be random or block.
一般式（１）で表される含フッ素オリゴマーの重量平均分子量は、通常３０００〜５００００程度、好ましくは４０００〜２５０００程度である。なお、重量平均分子量は、ゲル・パーミエイション・クロマトグラフィ（GPC）によって測定した値である。 The weight average molecular weight of the fluorine-containing oligomer represented by the general formula (1) is usually about 3000 to 50000, preferably about 4000 to 25000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC).
一般式（１）において、Ｒｆは下記式（２）又は（３）で示される基である。 In the general formula (1), Rf is a group represented by the following formula (2) or (3).
一般式（１）において、ｎ個のＲｆは、一般式（２）、（３）で表される基が混合していてもよく、どちらか一方のみでも良い。また、一般式（２）、（３）で表される基の比も特に限定されない。 In the general formula (1), the n Rf groups may be a mixture of the groups represented by the general formulas (2) and (3), or may be only one of them. Further, the ratio of the groups represented by the general formulas (2) and (3) is not particularly limited.
また、前記一般式（１）で示される含フッ素オリゴマーは、例えば、下記式（１Ａ）
ＣＨ２＝ＣＲ３−ＣＯＯ−Ｒ１−Ｏ−Ｒｆ （１Ａ）
（式中、Ｒ１、Ｒ３及びＲｆは、前記に定義される通りである）
で表される含フッ素モノマー、下記式（１Ｂ）
ＣＨ２＝ＣＲ４−ＣＯＯ−Ｒ２−ＯＨ （１Ｂ）
（式中、Ｒ２及びＲ４は、前記に定義される通りである）
で表されるエステル系モノマーを、前記ｎ：ｍの比率で混合し、重合開始剤（例えば、アゾビスイソブチロニトリル、過酸化ベンゾイル等）を適量加えて、溶媒の存在下に室温〜１００℃程度の温度で１〜２４時間程度反応させることにより得ることができる。この際、前記式（１Ａ）、（１Ｂ）の混合順序は特に限定されない。
The fluorine-containing oligomer represented by the general formula (1) is, for example, the following formula (1A)
CH 2 = CR 3 -COO-R 1 -O-Rf (1A)
(Wherein R 1 , R 3 and Rf are as defined above)
A fluorine-containing monomer represented by the following formula (1B)
CH 2 = CR 4 -COO-R 2 -OH (1B)
Wherein R 2 and R 4 are as defined above.
Is mixed at the ratio of n: m, a polymerization initiator (for example, azobisisobutyronitrile, benzoyl peroxide, etc.) is added in an appropriate amount, and room temperature to 100 in the presence of a solvent. It can be obtained by reacting at a temperature of about 0 C for about 1 to 24 hours. At this time, the mixing order of the formulas (1A) and (1B) is not particularly limited.
式（１Ａ）、（１Ｂ）で表されるモノマーは、公知の方法により得ることができ、市販品を使用することもできる。 The monomers represented by the formulas (1A) and (1B) can be obtained by known methods, and commercially available products can also be used.
例えば、式（１B）で表されるモノマーの具体例としては、グリセリンモノメタクリレート（日油製、商品名：ブレンマーＧＬＭ等）、２−ヒドロキシエチルメタクリレート（日油製 商品名：ブレンマーＥ等）、ポリエチレングリコールモノメタクリレート（日油製 商品名：ブレンマーＰＥ９０、ＰＥ２００、ＰＥ３５０等）、ポリエチレングリコールモノアクリレート（日油製 商品名：ブレンマーＡＥ９０、ＡＥ２００、ＡＥ４００等）、ヒドロキシプロピルメタクリレート（日油製 商品名：ブレンマーＰ等）、ポリプロピレングリコールモノメタクリレート（日油製 商品名：ブレンマーＰＰ１０００、ＰＰ５００、ＰＰ８００等）、ポリプロピレングリコールモノアクリレート（日油製 商品名：ブレンマーＡＰ１５０、ＡＰ４００、ＡＰ５５０等）、ポリ（エチレングリコール・プロピレングリコール）−モノメタクリレート（日油製 商品名：ブレンマー５０ＰＥＰ−３００等）、ポリエチレングリコール・ポリプロピレングリコール−モノメタクリレート（日油製 商品名：ブレンマー７０ＰＥＰ−３５０Ｂ等）、ポリ（エチレングリコール・テトラメチレングリコール）−モノメタクリレート（日油製 商品名：ブレンマー５５ＰＥＴ−８００等）、ポリ（プロピレングリコール・テトラメチレングリコール）−モノメタクリレート（日油製 商品名：ブレンマーＰＰＴ等）、プロピレングリコール・ポリブチレングリコール−モノメタクリレート（日油製 商品名：ブレンマー１０ＰＰＢ−５００Ｂ等）、２−ヒドロキシエチルアクリレート（大阪有機化学工業製 商品名：ＨＥＡ等）、２−ヒドロキシプロピルアクリレート（大阪有機化学工業製 商品名：ＨＰＡ等）、４−ヒドロキシブチルアクリレート（日本化成製 商品名：４ＨＢＡ、大阪有機化学工業製 商品名：４−ＨＢＡ等）、１、４−シクロヘキサンジメタノールモノアクリレート等が挙げられる。 For example, specific examples of the monomer represented by the formula (1B) include glycerin monomethacrylate (manufactured by NOF, trade name: Blemmer GLM, etc.), 2-hydroxyethyl methacrylate (trade name: manufactured by NOF, trade name: Blemmer E, etc.), Polyethylene glycol monomethacrylate (product name: Blenmer PE90, PE200, PE350, etc.), polyethylene glycol monoacrylate (product name: Blemmer AE90, AE200, AE400, etc.), hydroxypropyl methacrylate (product name: NOF product name) Blenmer P etc.), polypropylene glycol monomethacrylate (manufactured by NOF Corporation name: BREMMER PP1000, PP500, PP800 etc.), polypropylene glycol monoacrylate (manufactured by NOF Corporation name: Blemmer AP150, AP400) , AP550, etc.), poly (ethylene glycol / propylene glycol) -monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer 50PEP-300, etc.), polyethylene glycol / polypropylene glycol-monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer 70PEP-350B, etc.) ), Poly (ethylene glycol / tetramethylene glycol) -monomethacrylate (manufactured by NOF, trade name: BREMMER 55PET-800, etc.), poly (propylene glycol / tetramethylene glycol) -monomethacrylate (manufactured by NOF, trade name: BLEMMER PPT, etc.) ), Propylene glycol / polybutylene glycol-monomethacrylate (manufactured by NOF, trade name: BLEMMER 10PPB-500B, etc.), 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry) Product name: HEA, etc.), 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: HPA, etc.), 4-hydroxybutyl acrylate (trade name, manufactured by Nippon Kasei Chemical Co., Ltd., trade name: 4HBA, product made by Osaka Organic Chemical Industry, etc.): 4-HBA, etc. ), 1,4-cyclohexanedimethanol monoacrylate and the like.
式（１A）及び（１Ｂ）で表されるモノマーは、それぞれ１種単独で使用してもよいし、２種以上を混合して使用してもよい。 The monomers represented by the formulas (1A) and (1B) may be used alone or in combination of two or more.
前記一般式（１）で表される含フッ素オリゴマーを含む本発明の分散剤は、従来ＰＴＦＥ微粒子の分散剤として広く使用されてきた、ＰＦＯＡやＰＦＯＳと同等の分散性を有する。また、本発明の含フッ素オリゴマーは、上記一般式（２）及び（３）で示される分岐状パーフルオロカーボン鎖を分子内に有する。この分岐状パーフルオロカーボン鎖は、表面エネルギーの低下に極めて効果的である。したがって、後述の通り、前記一般式（１）で表される含フッ素オリゴマーを含む本発明の分散剤をＰＴＦＥ微粒子用の分散剤として使用することにより、高い表面改質効果を有するコーティング膜を得ることができる。また、該フッ素オリゴマーは、分解してもＰＦＯＡ又はＰＦＯＳを生成することはない。さらに、上記一般式（２）及び（３）で示される分岐状パーフルオロカーボン鎖の原料である含フッ素化合物（ヘキサフルオロプロペン３量体）は、比較的安価に製造できるため、コストの点でも優れた分散剤を製造することができる。 The dispersant of the present invention containing the fluorine-containing oligomer represented by the general formula (1) has a dispersibility equivalent to that of PFOA and PFOS, which has been widely used as a dispersant for conventional PTFE fine particles. The fluorine-containing oligomer of the present invention has a branched perfluorocarbon chain represented by the general formulas (2) and (3) in the molecule. This branched perfluorocarbon chain is extremely effective in reducing the surface energy. Therefore, as described later, a coating film having a high surface modification effect is obtained by using the dispersant of the present invention containing the fluorine-containing oligomer represented by the general formula (1) as a dispersant for PTFE fine particles. be able to. Further, the fluorine oligomer does not produce PFOA or PFOS even when decomposed. Furthermore, since the fluorine-containing compound (hexafluoropropene trimer) which is a raw material of the branched perfluorocarbon chain represented by the general formulas (2) and (3) can be produced at a relatively low cost, it is excellent in terms of cost. Dispersants can be produced.
他の成分
本発明の分散剤に含まれる他の成分としては、ＰＴＦＥ微粒子の分散剤に含まれる一般的な有機溶剤が挙げられる。このような分散剤としては、例えば、メチルエチルケトン、アセトン、アセトニトリル、ジメトキシエタン、１，３−ジメチル−２−イミダゾリジノン、メタノール、エタノール、イソプロピルアルコール、ジエチルエーテル、酢酸エチル、酢酸ブチル、N-メチル-2-ピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、ベンゼン、トルエン等が挙げられる。これらの有機溶剤は、一種単独で使用してもよいし、二種以上を混合して使用してもよい。
Other Components Other components contained in the dispersant of the present invention include general organic solvents contained in the PTFE fine particle dispersant. Examples of such a dispersant include methyl ethyl ketone, acetone, acetonitrile, dimethoxyethane, 1,3-dimethyl-2-imidazolidinone, methanol, ethanol, isopropyl alcohol, diethyl ether, ethyl acetate, butyl acetate, and N-methyl. -2-pyrrolidone, N, N-dimethylformamide, benzene, toluene and the like. These organic solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.
本発明の分散剤において、これら有機溶剤と前記一般式（１）で表される含フッ素オリゴマーの配合割合は、含フッ素オリゴマー１００重量部に対して、有機溶剤を通常１６６〜９９８０重量部程度とすればよい。 In the dispersant of the present invention, the blending ratio of these organic solvent and the fluorine-containing oligomer represented by the general formula (1) is usually about 166 to 9980 parts by weight of the organic solvent with respect to 100 parts by weight of the fluorine-containing oligomer. do it.
ＰＴＦＥ微粒子
本発明の分散剤は、ＰＴＦＥ微粒子の分散剤として使用される。ＰＴＦＥ微粒子は、表面改質を目的として使用されるものであれば、特に限定されず、公知の方法により製造することができ、市販品も容易に入手可能である。ＰＴＦＥ微粒子の市販品としては、例えば、株式会社広丘精機社製のＲＦ−４−６、ＲＦ−５−５、ダイキン工業株式会社製のルブロンＬ−２等が挙げられる。ＰＴＦＥ微粒子の数平均粒子径は、通常０．１〜１００．０μｍ程度、好ましくは０．５〜１０．０μｍ程度である。
PTFE fine particles The dispersant of the present invention is used as a dispersant for PTFE fine particles. The PTFE fine particles are not particularly limited as long as they are used for the purpose of surface modification, and can be produced by a known method, and commercially available products are also readily available. Examples of commercially available PTFE fine particles include RF-4-6 and RF-5-5 manufactured by Hirooka Seiki Co., Ltd., and Lubron L-2 manufactured by Daikin Industries, Ltd. The number average particle diameter of the PTFE fine particles is usually about 0.1 to 100.0 μm, preferably about 0.5 to 10.0 μm.
２．組成物
本発明の組成物は、前記ＰＴＦＥ微粒子、前記分散剤、及び必要に応じて配合される添加物との混合物である。
2. Composition The composition of the present invention is a mixture of the PTFE fine particles, the dispersant, and additives that are blended as necessary.
前記ＰＴＦＥ微粒子、前記分散剤、及び必要に応じて配合される添加物の混合方法は特に限定されず、これらの成分が均一に分散すればよい。また、混合の際の温度も特に限定されず、通常０〜１００℃程度で混合すればよい。 The mixing method of the PTFE fine particles, the dispersant, and additives to be blended as necessary is not particularly limited, and these components may be dispersed uniformly. Moreover, the temperature at the time of mixing is not specifically limited, Usually, what is necessary is just to mix at about 0-100 degreeC.
本発明の組成物において、ＰＴＦＥ微粒子の配合量は、通常０．１〜４０．０重量％程度、好ましくは１．０〜２０．０重量％程度である。また、含フッ素オリゴマーの配合量は、通常０．１〜３０．０重量％程度、好ましくは０．５〜５．０重量％程度である。さらに、前記有機溶剤の配合量は、通常５０．０〜９９．８重量％程度、好ましくは７５．０〜９８．５重量％程度である。 In the composition of the present invention, the blending amount of the PTFE fine particles is usually about 0.1 to 40.0% by weight, preferably about 1.0 to 20.0% by weight. Moreover, the compounding quantity of a fluorine-containing oligomer is about 0.1 to 30.0 weight% normally, Preferably it is about 0.5 to 5.0 weight%. Furthermore, the compounding amount of the organic solvent is usually about 50.0 to 99.8% by weight, preferably about 75.0 to 98.5% by weight.
本発明において、前記一般式（１）で表される含フッ素オリゴマーとＰＴＦＥ微粒子の配合量の比率（重量）は、下式：
０．１≦[ＰＴＦＥ微粒子]／[一般式（1）で表される含フッ素オリゴマー]≦４０
の関係にあることが好ましい。さらに、下式：
１≦[ＰＴＦＥ微粒子]／[一般式（1）で表される含フッ素オリゴマー]≦１５
の関係にあることがより好ましい。
In the present invention, the ratio (weight) of the blending amount of the fluorine-containing oligomer represented by the general formula (1) and the PTFE fine particles is expressed by the following formula:
0.1 ≦ [PTFE fine particles] / [fluorinated oligomer represented by the general formula (1)] ≦ 40
It is preferable that the relationship is In addition, the following formula:
1 ≦ [PTFE fine particles] / [fluorinated oligomer represented by general formula (1)] ≦ 15
It is more preferable that the relationship is
３．コーティング膜
本発明の組成物は、金属等の表面に塗布し、加熱処理を施すことにより、コーティング膜を形成する。該コーティング膜には、前記ＰＴＦＥ微粒子及び前記一般式（１）で表される含フッ素オリゴマーが含まれる。前記のとおり、ＰＴＦＥ微粒子のみを金属等の表面にコーティングした場合、良好な撥水性を示すものの、良好な撥油性を得ることができない。
3. Coating film The composition of the present invention is applied to the surface of a metal or the like and subjected to heat treatment to form a coating film. The coating film contains the PTFE fine particles and the fluorine-containing oligomer represented by the general formula (1). As described above, when only PTFE fine particles are coated on the surface of metal or the like, good water repellency is exhibited but good oil repellency cannot be obtained.
一方、本発明の組成物は、前記一般式（１）で表される含フッ素オリゴマーを分散剤に含むことにより、ＰＴＦＥ微粒子の分散性に優れているだけでなく、コーティング膜としたときの撥水性及び撥油性にも極めて優れている。 On the other hand, the composition of the present invention not only has excellent dispersibility of PTFE fine particles by containing the fluorine-containing oligomer represented by the general formula (1) in the dispersant, but also has a repellent property when used as a coating film. Excellent water and oil repellency.
また、通常、ＰＴＦＥ微粒子を含む組成物を加熱処理（ＰＴＦＥの焼付け）してコーティング膜を形成する際は、３５０〜４００℃程度という高温条件を必要とする。これに対して、本願発明の組成物は、１５０〜２５０℃程度と比較的低温で焼付けを行うことが可能である。このことから、本発明のコーティング膜は、金属、セラミックス等の高温条件に強い材料の表面だけでなく、比較的高温条件に弱い樹脂等の表面にも形成することができる。 In general, when a composition containing PTFE fine particles is subjected to a heat treatment (PTFE baking) to form a coating film, a high temperature condition of about 350 to 400 ° C. is required. On the other hand, the composition of the present invention can be baked at a relatively low temperature of about 150 to 250 ° C. Therefore, the coating film of the present invention can be formed not only on the surface of a material that is resistant to high temperature conditions such as metal and ceramics, but also on the surface of a resin that is relatively resistant to high temperature conditions.
コーティング膜を形成し得る材料の具体例としては、鉄・アルミニウム・ステンレス等の金属、ガラス・陶器、セメント等のセラミックス、ポリウレタン・プラスチック・ポリエステル等の樹脂が挙げられる。加熱処理時間は、通常１分間以上である。 Specific examples of the material that can form the coating film include metals such as iron, aluminum, and stainless steel, glass and ceramics, ceramics such as cement, and resins such as polyurethane, plastic, and polyester. The heat treatment time is usually 1 minute or longer.
本発明の組成物の塗布方法は、特に限定されないが、例えば、グラビア方式、バーコート方式、ワイヤーバー方式、スピンコート方式、ドクターブレード方式、ディップコート方式、スリットコート方式等が挙げられる。 The coating method of the composition of the present invention is not particularly limited, and examples thereof include a gravure method, a bar coating method, a wire bar method, a spin coating method, a doctor blade method, a dip coating method, and a slit coating method.
また、コーティング膜の厚みは、通常０．０１〜１００μm程度、好ましくは０．１〜１０μm程度である。 Moreover, the thickness of a coating film is about 0.01-100 micrometers normally, Preferably it is about 0.1-10 micrometers.
以下、本発明を実施例によって説明するが、本発明が実施例に限定されることは意図しない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, it is not intending that this invention is limited to an Example.
実施例１
サンプル管（５０ｍｌ）内に、下記表１に記載の含フッ素オリゴマー（Ｂ）０．５０ｇ、Ｎ−メチル−２−ピロリドン９．４０ｇ及び酢酸エチル０．５０ｇを入れた。得られた混合液に表２に記載のＰＴＦＥ微粒子（Ａ）０．５０ｇを徐々に加え、ＰＴＦＥ微粉末の分散液を１０．００ｇ得た。得られた分散液を金属表面（ＳＵＳ）に塗布し、２００℃で１時間加熱処理（焼付け）を行い、金属表面にＰＴＦＥの膜を形成した。得られたＰＴＦＥ膜について、水、及びヘキサデカンを用いて接触角を測定した。接触角の評価方法は表３、配合比率、焼付け条件、及び各試験結果は表４の通りである。なお、表４〜７中のＰＴＦＥ微粒子、フッ素オリゴマー、及び溶剤の数値は、重量比である。
Example 1
In a sample tube (50 ml), 0.50 g of the fluorine-containing oligomer (B) described in Table 1 below, 9.40 g of N-methyl-2-pyrrolidone and 0.50 g of ethyl acetate were placed. 0.50 g of PTFE fine particles (A) shown in Table 2 were gradually added to the obtained mixed liquid to obtain 10.00 g of a dispersion of fine PTFE powder. The obtained dispersion was applied to a metal surface (SUS) and subjected to heat treatment (baking) at 200 ° C. for 1 hour to form a PTFE film on the metal surface. About the obtained PTFE film | membrane, the contact angle was measured using water and hexadecane. Table 3 shows the contact angle evaluation method, and Table 4 shows the blending ratio, baking conditions, and test results. In addition, the numerical value of PTFE microparticles | fine-particles in Tables 4-7, a fluorine oligomer, and a solvent is a weight ratio.
実施例２〜４４
実施例１と同様にして、表１及び表２に記載の含フッ素オリゴマー及びＰＴＦＥ微粒子を用いてコーティング膜を形成した。得られたＰＴＦＥ膜について、実施例１と同様にして接触角を測定した。実施例２〜４４の各成分の配合比率、焼付け条件、及び各試験結果は表４〜７の通りである。
Examples 2-44
In the same manner as in Example 1, a coating film was formed using the fluorine-containing oligomers and PTFE fine particles listed in Tables 1 and 2. The contact angle of the obtained PTFE membrane was measured in the same manner as in Example 1. The blending ratio of each component of Examples 2-44, baking conditions, and each test result are as Tables 4-7.
比較例１
サンプル管（５０ｍｌ）内に、Ｎ−メチル−２−ピロリドン１０．００ｇを入れた。Ｎ−メチル−２−ピロリドンを金属表面（ＳＵＳ）に塗布し、２００℃で１時間焼付けを行った。得られた膜について、実施例１と同様にして接触角を測定した。各成分の配合比率、焼付け条件、及び各試験結果は表７の通りである。
Comparative Example 1
In a sample tube (50 ml), 10.00 g of N-methyl-2-pyrrolidone was placed. N-methyl-2-pyrrolidone was applied to the metal surface (SUS) and baked at 200 ° C. for 1 hour. About the obtained film | membrane, it carried out similarly to Example 1, and measured the contact angle. Table 7 shows the blending ratio of each component, the baking conditions, and the test results.
比較例２
サンプル管（５０ｍｌ）内に、Ｎ−メチル−２−ピロリドン９．５０ｇを入れた。ＰＴＦＥ微粒子（Ａ）０．５０ｇを徐々に加えたが、ＰＴＦＥ分散液を得ることができなかった。配合比率は表７の通りである。
Comparative Example 2
In a sample tube (50 ml), 9.50 g of N-methyl-2-pyrrolidone was placed. Although 0.50 g of PTFE fine particles (A) were gradually added, a PTFE dispersion could not be obtained. The blending ratio is as shown in Table 7.
比較例３
サンプル管（５０ｍｌ）内に、含フッ素オリゴマー（Ｂ）０．２０ｇ、Ｎ−メチル−２−ピロリドン９．６０ｇ及び酢酸エチル０．２０ｇを入れ、含フッ素オリゴマー溶液１０．００ｇを得た。得られた溶液を各種金属表面（ＳＵＳ、Ａｌ、ＳＰＣＣ）に塗布し、２００℃で１時間焼付けを行い、金属表面に含フッ素オリゴマーの膜を形成した。得られた膜について、実施例１と同様にして接触角を測定した。各成分の配合比率、焼付け条件、及び各試験結果は表７の通りである。
Comparative Example 3
In a sample tube (50 ml), 0.20 g of the fluorine-containing oligomer (B), 9.60 g of N-methyl-2-pyrrolidone and 0.20 g of ethyl acetate were added to obtain 10.00 g of a fluorine-containing oligomer solution. The obtained solution was applied to various metal surfaces (SUS, Al, SPCC) and baked at 200 ° C. for 1 hour to form a fluorine-containing oligomer film on the metal surface. About the obtained film | membrane, it carried out similarly to Example 1, and measured the contact angle. Table 7 shows the blending ratio of each component, the baking conditions, and the test results.
比較例４〜７
実施例２と同様にして、表１及び表２に記載の含フッ素オリゴマー、ＰＴＦＥ微粒子を用いてコーティング膜を形成した。配合比率、焼付け条件、及び各試験結果は表７の通りである。
Comparative Examples 4-7
In the same manner as in Example 2, a coating film was formed using the fluorine-containing oligomers and PTFE fine particles listed in Tables 1 and 2. Table 7 shows the blending ratio, baking conditions, and test results.
式中、ｎ及びｍは表１の通りである。また、式中、Ｒｆは、下記（２）と（３）とが混合している。なお、一般式（１’）において、（２）と（３）とのモル比は、０．３≦（２）／（３）≦５であった。 In the formula, n and m are as shown in Table 1. In the formula, Rf is a mixture of the following (2) and (3). In the general formula (1 ′), the molar ratio of (2) to (3) was 0.3 ≦ (2) / (3) ≦ 5.
Claims (6)
1≦[ＰＴＦＥ微粒子]／[一般式（1）で表される含フッ素オリゴマー]≦４０
の関係にある請求項３又は４に記載の組成物。 The ratio (weight) of the blending amount of the fluorine-containing oligomer represented by the general formula (1) and the PTFE fine particles is represented by the following formula:
1 ≦ [PTFE fine particles] / [fluorinated oligomer represented by general formula (1)] ≦ 40
The composition according to claim 3 or 4, which has the following relationship.
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| JP5719014B1 (en) * | 2013-12-06 | 2015-05-13 | 共栄社化学株式会社 | Dispersant for fluoropolymer |
| CN106669319A (en) * | 2015-11-09 | 2017-05-17 | 郭绍华 | Filter for air purification |
| US10495992B2 (en) | 2016-03-29 | 2019-12-03 | Mitsubishi Chemical Corporation | Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, image forming apparatus, and dispersant for fluororesin |
| JP2019218539A (en) * | 2018-06-15 | 2019-12-26 | 富士ゼロックス株式会社 | Dispersant-attached polytetrafluoroethylene particle, composition, laminar material, electrophotographic photoreceptor, process cartridge, and image formation device |
| WO2022019183A1 (en) * | 2020-07-20 | 2022-01-27 | 第一工業製薬株式会社 | Dispersant for fluororesins, composition, dispersion liquid, article and copolymer |
| JP7136994B1 (en) | 2021-12-27 | 2022-09-13 | 第一工業製薬株式会社 | Dispersants for fluororesins, compositions, dispersions, articles and copolymers |
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| JP7136994B1 (en) | 2021-12-27 | 2022-09-13 | 第一工業製薬株式会社 | Dispersants for fluororesins, compositions, dispersions, articles and copolymers |
| WO2023127617A1 (en) * | 2021-12-27 | 2023-07-06 | 第一工業製薬株式会社 | Dispersant for fluororesin, composition, dispersion liquid, article, and copolymer |
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