JP2017094661A - Synovial membrane, method for producing the same, and article having surface coated therewith - Google Patents
Synovial membrane, method for producing the same, and article having surface coated therewith Download PDFInfo
- Publication number
- JP2017094661A JP2017094661A JP2015231603A JP2015231603A JP2017094661A JP 2017094661 A JP2017094661 A JP 2017094661A JP 2015231603 A JP2015231603 A JP 2015231603A JP 2015231603 A JP2015231603 A JP 2015231603A JP 2017094661 A JP2017094661 A JP 2017094661A
- Authority
- JP
- Japan
- Prior art keywords
- synovial
- synovial fluid
- group
- base film
- film
- 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
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- 238000004519 manufacturing process Methods 0.000 title description 11
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- 125000000524 functional group Chemical group 0.000 claims abstract description 19
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- 238000000034 method Methods 0.000 claims description 20
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
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- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 239000008168 almond oil Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- GUUHFMWKWLOQMM-NTCAYCPXSA-N alpha-hexylcinnamaldehyde Chemical compound CCCCCC\C(C=O)=C/C1=CC=CC=C1 GUUHFMWKWLOQMM-NTCAYCPXSA-N 0.000 description 1
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- ZEFSGHVBJCEKAZ-UHFFFAOYSA-N bis(2,4-ditert-butyl-6-methylphenyl) ethyl phosphite Chemical compound CC=1C=C(C(C)(C)C)C=C(C(C)(C)C)C=1OP(OCC)OC1=C(C)C=C(C(C)(C)C)C=C1C(C)(C)C ZEFSGHVBJCEKAZ-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- GTPDFCLBTFKHNH-UHFFFAOYSA-N chloro(phenyl)silicon Chemical compound Cl[Si]C1=CC=CC=C1 GTPDFCLBTFKHNH-UHFFFAOYSA-N 0.000 description 1
- IPAIXTZQWAGRPZ-UHFFFAOYSA-N chloro-methyl-phenylsilicon Chemical compound C[Si](Cl)C1=CC=CC=C1 IPAIXTZQWAGRPZ-UHFFFAOYSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical class ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
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- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000708 deep reactive-ion etching Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- RGHWXPPXQQVOKA-UHFFFAOYSA-N phenanthrene-1-carbaldehyde Chemical compound C1=CC2=CC=CC=C2C2=C1C(C=O)=CC=C2 RGHWXPPXQQVOKA-UHFFFAOYSA-N 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- 238000002174 soft lithography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- XUHUMYVYHLHMCD-UHFFFAOYSA-N tris(2-cyclohexylphenyl) phosphite Chemical compound C1CCCCC1C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C1CCCCC1)OC1=CC=CC=C1C1CCCCC1 XUHUMYVYHLHMCD-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は滑液膜、特にπ電子相互作用により滑液剤を保持した滑液膜、その製造方法、及びそれにより被覆された表面を有する物品に関する。 The present invention relates to a synovial fluid film, in particular, a synovial fluid film retaining a synovial agent by π-electron interaction, a method for producing the same, and an article having a surface coated thereby.
太陽電池、自動車、医療機器、燃料輸送、建築、食品容器等、多くの分野において、防汚表面の開発が望まれている。例えば、ロータス−リーフ（ハスの葉）効果に基づいた非ぬれ性の表面が、数十年にわたって研究されているものの、低表面張力の液体や、落下衝撃、極高温あるいは極高圧に対して安定なものを得るのは非常に難しかった。近年、新しいタイプの防汚表面として、Slippery Liquid-Infused Porous Surfaces (SLIPS)が報告されており、これは液体潤滑剤を含浸させた低エネルギーの微細孔表面である（非特許文献１参照）。SLIPSは、ほとんどすべての流体に対して非ぬれ性を示し、潤滑剤が細孔内にあるため、高温・高圧に対して安定である。このため、SLIPSは非常に魅力的な材料であると言える。 In many fields, such as solar cells, automobiles, medical equipment, fuel transportation, construction, and food containers, development of antifouling surfaces is desired. For example, although non-wetting surfaces based on the Lotus-leaf effect have been studied for decades, they are stable against low surface tension liquids, drop impacts, extreme temperatures or pressures It was very difficult to get something. In recent years, slippery liquid-infused porous surfaces (SLIPS) have been reported as a new type of antifouling surface, which is a low-energy microporous surface impregnated with a liquid lubricant (see Non-Patent Document 1). SLIPS is non-wetting to almost all fluids and is stable to high temperatures and pressures because the lubricant is in the pores. For this reason, SLIPS is a very attractive material.
SLIPSの製造方法については多数報告されているものの、以下の点から、未だ十分に汎用性の高いものとは言えなかった。Wonらは、潤滑剤を適用するための粗表面として、ポリ（テトラフルオロエチレン）メッシュ（以下、PTFEメッシュ）とエポキシ樹脂アレイを用いている（非特許文献１参照）。PTFEメッシュは成形性が非常に悪いため、複雑な構造の表面に適用することができず、また、可視光領域で透明でない。また、エポキシ樹脂アレイ表面は複雑な構造とすることができるものの、二段階のソフト−リソグラフィー工程は長時間を要する。これらの製造工程は、大量生産に不向きであり、汎用性が無い。 Although many SLIPS manufacturing methods have been reported, it has not been sufficiently versatile due to the following points. Won et al. Use a poly (tetrafluoroethylene) mesh (hereinafter referred to as PTFE mesh) and an epoxy resin array as a rough surface for applying a lubricant (see Non-Patent Document 1). PTFE mesh has very poor moldability, so it cannot be applied to surfaces with complex structures and is not transparent in the visible light region. In addition, although the epoxy resin array surface can have a complicated structure, the two-stage soft-lithography process takes a long time. These manufacturing processes are not suitable for mass production and are not versatile.
これらの他にも、煩雑且つ長時間を要し、高コストのプロセスとして、フォトリソグラフィー法、深部反応性イオンエッチング法、化学蒸着法等が挙げられる。反対に、粗面を形成する上でよりコストが低く簡易な方法として、Maらにより、アルミナゾル−ゲルによるSLIPS製造プロセスが報告されている（非特許文献２参照）。これは簡易な湿式プロセスであり、可視光領域における光透過性の高い層が得られる。しかし、４００℃程度の高温でのアニーリング及び表面エネルギーの低下を行なう必要があり、基板の選択性が限られるとともに、追加のプロセス及び材料が必要なため、コストも増加してしまう。その他、アルミニウムのベーマイト処理、銅のアルカリエッチング、ポリピロールの電解重合等の製法においても、同様の問題がある。 In addition to these, complicated and time consuming and expensive processes include photolithography, deep reactive ion etching, chemical vapor deposition, and the like. On the other hand, a SLIPS manufacturing process using alumina sol-gel has been reported by Ma et al. As a simple method with a lower cost for forming a rough surface (see Non-Patent Document 2). This is a simple wet process, and a layer having high light transmittance in the visible light region can be obtained. However, it is necessary to perform annealing at a high temperature of about 400 ° C. and decrease the surface energy, which limits the selectivity of the substrate and requires additional processes and materials, which increases costs. In addition, there are similar problems in production methods such as boehmite treatment of aluminum, alkaline etching of copper, and electrolytic polymerization of polypyrrole.
また、従来のSLIPSにおいて多孔性粗表面として用いられる基板のうち、フォトリソグラフィー法によるエポキシ樹脂アレイやエッチングによるポーラスシリコン等は、表面上に針状の微細凹凸、あるいは不連続な微細貫通孔（蓮根型貫通孔）を形成したものである。ゾル−ゲル法により形成したアルミナ薄膜も、単に表面上に微細な凹凸を有しているに過ぎない。このため、SLIPSとして、これらの多孔性粗表面上に含浸された液体潤滑剤は、比較的容易に滲出あるいは漏出してしまい、実際に使用するには頻繁に液体潤滑剤を補給しなければならない。 Also, among the substrates used as porous rough surfaces in conventional SLIPS, epoxy resin arrays by photolithography and porous silicon by etching, etc., have needle-like fine irregularities or discontinuous fine through-holes (lotus root) on the surface. Mold through hole). The alumina thin film formed by the sol-gel method also has only fine irregularities on the surface. For this reason, liquid lubricants impregnated on these porous rough surfaces as SLIPS exude or leak relatively easily and must be replenished frequently for actual use. .
延伸法により形成された多孔性PTFEシートは、より複雑な細孔構造を有しているものの、シートが一軸方向に引き伸ばされたスダレ状、あるいは二軸方向に引き伸ばされた蜘蛛の巣状であり、長期間にわたって液体潤滑剤を細孔内に保持することはできず、特に振動や圧力に対する耐久性の点で十分なものとは言えない。 The porous PTFE sheet formed by the stretching method has a more complex pore structure, but it is in the form of a saddle that is stretched in a uniaxial direction or a spider web that is stretched in a biaxial direction. The liquid lubricant cannot be held in the pores for a long period of time, and it cannot be said that it is particularly satisfactory in terms of durability against vibration and pressure.
また、例えば、窓ガラスや自動車のフロントガラス等、透明性が要求される製品に貼付して防汚効果を付与することのできる透明フィルムの開発は非常に有用であると考えられる。しかし、フォトリソグラフィーやエッチング、ゾルゲル法等を用いたSLIPSは、物品の表面を直接処理するものであり、独立した膜を形成するものではない。他方、延伸法による多孔性PTFEシートは、独立したフィルムとすることも可能であるが、比較的膜厚が厚いため、透明性に劣る。このため、従来のSLIPSにおいて、高い透明性を有しつつ、十分な強度を有するものはなかった。 In addition, for example, it is considered to be very useful to develop a transparent film that can be applied to a product that requires transparency, such as a window glass or an automobile windshield, to impart an antifouling effect. However, SLIPS using photolithography, etching, sol-gel method or the like directly treats the surface of an article and does not form an independent film. On the other hand, the porous PTFE sheet obtained by the stretching method can be an independent film, but is inferior in transparency because it is relatively thick. For this reason, none of the conventional SLIPS has sufficient strength while having high transparency.
本発明は前記従来技術に鑑みなされたものであり、その解決すべき課題は平坦表面上に容易に形成でき、且つ維持、修復性の高い滑液膜を提供することにある。 The present invention has been made in view of the above-described prior art, and a problem to be solved is to provide a synovial membrane that can be easily formed on a flat surface and has high maintainability and repairability.
前記課題を解決するため、本発明者らが鋭意検討を行なった結果、高濃度のπ電子を有するフェニル基等の官能基を物品の平坦表面上に修飾し、滑液剤をπ相互作用により前記平坦表面上に保持させることにより、滑液性、修復性に優れた滑液膜を形成し得ることを見出し、本発明を完成するに至った。
すなわち、本発明にかかる滑液膜は、
ベース膜としてπ電子を有する官能基を有する層と、
滑液剤層として前記ベース膜のπ電子官能基とπ相互作用により結合するπ相互作用部及び滑液対象となる流体と親和性の低い滑液作用部を分子内に有した層、
を含むことを特徴とする。
本発明において、前記ベース膜は物品の平坦表面上に形成されることが好適である。
また、本発明において、ベース膜は、芳香族基及び／またはアルキン基から選択される高濃度π電子含有官能基を有することが好適である。
また、本発明において、滑液剤のπ相互作用部は、π電子と相互作用を示すエトキシ基、メトキシ基、フェニル基、ヒドロキシ基、カルボニル基、アルデヒド基、−ＸＨ基（Ｘは任意の原子）から選択されることが好適である。
また、本発明において、滑液対象となる流体が親水性媒体であり、滑液剤の滑液作用部は、アルキル基、アルキル変性シロキサン基、アルキルフェニル変性シロキサン基、或いはフッ化アルキル基であることが好適である。
また、本発明にかかるベース膜形成方法は、π電子含有官能基を有するベース膜構成物質を物品表面に結合もしくは分子間相互作用させてベース膜を形成し、
前記ベース膜のπ電子官能基とπ相互作用により結合するπ相互作用部と、滑液対象となる流体と親和性の低い滑液作用部を分子内に有した滑液剤を、前記ベース膜上に塗布することを特徴とする。
また、本発明にかかる物品は、前記滑液膜により被覆された表面を有することを特徴とするものである。
また、本発明にかかる医療器具は、前記滑液膜により被覆された表面を有することを特徴とするものである。
In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, functional groups such as phenyl groups having a high concentration of π-electrons are modified on the flat surface of the article, and the lubricant is formed by the π-interaction. The inventors have found that a synovial membrane excellent in synovial fluid properties and repairability can be formed by holding on a flat surface, and the present invention has been completed.
That is, the synovial membrane according to the present invention is
A layer having a functional group having π electrons as a base film;
As a synovial fluid layer, a layer having in the molecule a π interaction part that binds by π interaction with the π electron functional group of the base film and a synovial fluid action part having a low affinity with the fluid to be synovial fluid,
It is characterized by including.
In the present invention, the base film is preferably formed on a flat surface of an article.
In the present invention, the base film preferably has a high concentration π electron-containing functional group selected from an aromatic group and / or an alkyne group.
In the present invention, the π-interaction part of the lubricant is an ethoxy group, a methoxy group, a phenyl group, a hydroxy group, a carbonyl group, an aldehyde group, or an —XH group (X is an arbitrary atom) that interacts with π electrons. Is preferably selected from:
In the present invention, the fluid to be synovial fluid is a hydrophilic medium, and the synovial fluid action part of the synovial fluid is an alkyl group, an alkyl-modified siloxane group, an alkylphenyl-modified siloxane group, or a fluorinated alkyl group. Is preferred.
In the base film forming method according to the present invention, a base film constituent material having a π-electron-containing functional group is bonded to the surface of the article or intermolecularly interacted to form a base film.
On the base film, a synovial agent having a π interaction part bonded to the π electron functional group of the base film by π interaction and a synovial liquid action part having a low affinity with the fluid to be synovial fluid in the molecule is provided on the base film. It is characterized by being applied to.
The article according to the present invention is characterized by having a surface coated with the synovial fluid film.
Moreover, the medical device concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.
また、本発明にかかる容器は、前記滑液膜により被覆された表面を有することを特徴とするものである。
また、本発明にかかる光学機器は、前記滑液膜により被覆された表面を有することを特徴とするものである。
また、本発明にかかる防汚ガラスは、前記滑液膜により被覆された表面を有することを特徴とするものである。
また、本発明にかかる太陽電池は、前記滑液膜により被覆された表面を有することを特徴とするものである。
本発明にかかる滑液膜は、送電線、建材（屋根、窓、壁）、運搬機器（自動車、船舶、航空機）、管材（熱伝達凝縮器、吸熱、放熱機器）等にも適用可能である。
なお、本発明にかかる滑液膜（以下、SPLASHということがある）は、従来のSLIPSと比較し、以下の特徴を有する。
(1) SLIPSが潤滑液保持のためのナノーマイクロオーダーのスポンジ構造下地層が必要であるのに対して、SPLASHは完全にフラット（Rrms=0.237 nm）な下地層で潤滑液を保持できる。
(2) これにより、潤滑液が減少した場合にも、下地凹凸構造の露出を防ぎ、安定した性能を発揮できる。
(3) 下地層が平坦であるため、極端に低粘度の潤滑液も保持できる（スポンジ構造ではしみこんでしまい、液膜を形成できない）。
(4) 下地層に凹凸が存在しないので潤滑液の流動抵抗を損なわない。
(5) (3)(4)よりＳＬＩＰＳよりも円滑な滑液性を示し、（微小液体の転落ができなかったＳＬＩＰＳに対して）ミストなどの微小液体を転落できた。密度の低いアイスなども同様。これまでほとんど報告のない高温液体、ボイル試験に対する耐久性も同様である。
(6) 下地層がフラットであり構造の破壊が心配されない。それによる高い耐久性を持つ。
(7) 下地層がフラットであり、透過率の散乱損失が小さいので従来よりも高い透明性を有する。
(8) フレキシビリティを持つ。ＳＬＩＰＳの場合だと折り曲げなどにより潤滑液の変化により下地凹凸構造の露出し、滑液対象液体を転落できなくなってしまう。しかしＳＰＬＡＳＨは下地層がフラットであり、潤滑液の高さ変化による凹凸構造の露出が存在しないため安定である。
(9) 簡易的、オールウェットプロセス、幅広い潤滑液選択性（ＳＬＩＰＳはほとんどがフッ素系の潤滑油に限定。せいぜいシリコンオイルかフッ素系油）を示す。
(10) π電子により潤滑液を吸着しているため、コットンでこすっても油がなくならない。剪断応力をかけても油の膜厚が保たれる（500 nm 程度）。
Moreover, the container concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.
The optical device according to the present invention is characterized in that it has a surface coated with the synovial fluid film.
The antifouling glass according to the present invention has a surface covered with the synovial fluid film.
Moreover, the solar cell concerning this invention has the surface coat | covered with the said synovial fluid film, It is characterized by the above-mentioned.
The synovial fluid film according to the present invention is also applicable to power transmission lines, building materials (roofs, windows, walls), transportation equipment (automobiles, ships, aircraft), pipe materials (heat transfer condensers, heat absorption, heat dissipation equipment), and the like. .
In addition, the synovial fluid film (hereinafter sometimes referred to as SPLASH) according to the present invention has the following characteristics as compared with conventional SLIPS.
(1) Whereas SLIPS requires a nano-micro order sponge structure underlayer for retaining the lubricant, SPLASH can hold the lubricant in a completely flat (Rrms = 0.237 nm) underlayer.
(2) Thereby, even when the lubricating liquid is reduced, exposure of the base uneven structure can be prevented and stable performance can be exhibited.
(3) Since the undercoat layer is flat, it can retain an extremely low viscosity lubricating liquid (the sponge structure soaks in and cannot form a liquid film).
(4) Since there are no irregularities in the underlayer, the flow resistance of the lubricating liquid is not impaired.
(5) From (3) and (4), it showed smoother synovial properties than SLIPS, and it was able to tumbl down micro liquids such as mist (relative to SLIPS where micro liquids could not fall). The same is true for low-density ice. The same applies to the durability of high temperature liquids and boil tests, which have hardly been reported so far.
(6) The underlying layer is flat and there is no worry about the destruction of the structure. It has high durability.
(7) Since the underlayer is flat and the scattering loss of transmittance is small, it has higher transparency than before.
(8) Has flexibility. In the case of SLIPS, the underlying concavo-convex structure is exposed due to a change in the lubricating liquid due to bending or the like, and the synovial fluid target liquid cannot fall down. However, SPLASH is stable because the underlying layer is flat and there is no exposure of the concavo-convex structure due to the change in the height of the lubricating liquid.
(9) Simple, all-wet process, and a wide range of lubricant selection (SLIPS is mostly limited to fluorine-based lubricants, at most silicon oil or fluorine-based oil).
(10) Since the lubricating liquid is adsorbed by π electrons, oil does not disappear even when rubbed with cotton. Even when shear stress is applied, the oil film thickness is maintained (about 500 nm).
本発明によれば、物品表面にベース膜を形成し、該ベース膜がπ相互作用により滑液剤を保持するので、容易に製造することができ、優れた防汚効果を示す滑液膜が得られ、また、その耐久性も非常に優れている。さらに、本発明によって、高い透明性を有し、且つ十分な強度を有する滑液膜が得られる。 According to the present invention, a base film is formed on the surface of an article, and the base film retains the lubricant by π interaction. In addition, its durability is very good. Further, according to the present invention, a synovial fluid film having high transparency and sufficient strength can be obtained.
［滑液膜］
図１に、本発明の一実施形態にかかる滑液膜の模式図を示す。
同図において、本発明にかかる滑液膜１０は、物品１２表面上に修飾されたπ電子官能基（フェニル基）１４を有するベース膜１６と、該ベース膜１６のπ電子官能基１４とπ相互作用により結合するπ相互作用部（メトキシ基）１８及び疎水性を呈する滑液作用部（炭化水素基）２０を分子内に有した滑液剤（デシルトリメトキシシラン）２２と、からなる。
そして、ベース膜のπ電子官能基１４にπ相互作用により保持されたデシルトリメトキシシラン２２の疎水性、滑水性により、膜１０上の水滴２４は、物品表面１２をわずかに傾けることにより滑落する。
また、滑液層にシリコーンオイルKF５４を用いた場合、マヨネーズ、しょうゆ、カルボナーラソース、ケチャップ、コーヒー、蜂蜜、カレーソースのいずれも表面に残留することなく滑落することを確認した。さらに、熱水、塩水、氷、血液も同様に滑落させることができる。
[Synovial membrane]
FIG. 1 shows a schematic diagram of a synovial fluid film according to an embodiment of the present invention.
In the figure, the synovial fluid film 10 according to the present invention includes a base film 16 having a π-electron functional group (phenyl group) 14 modified on the surface of an article 12, and π-electron functional groups 14 and π of the base film 16. And a synovial fluid (decyltrimethoxysilane) 22 having in its molecule a π-interacting portion (methoxy group) 18 bonded by interaction and a synovial fluid acting portion (hydrocarbon group) 20 exhibiting hydrophobicity.
Then, due to the hydrophobicity and water slidability of the decyltrimethoxysilane 22 held by the π-electron functional group 14 of the base film due to the π interaction, the water droplet 24 on the film 10 slides down by slightly tilting the article surface 12. .
Moreover, when silicone oil KF54 was used for the synovial fluid layer, it was confirmed that any of mayonnaise, soy sauce, carbonara sauce, ketchup, coffee, honey, and curry sauce slipped without remaining on the surface. Furthermore, hot water, salt water, ice and blood can be slid down as well.
［ベース膜］
本発明において、ベース膜１６は、高濃度のπ電子を有するπ電子官能基とともに、物品表面への固定基（たとえばシラン基）を有することが好適であり、前記π電子官能基としては、フェニル基を代表とする芳香族やアルキンなどが好ましい。
ベース膜構成物質の具体例としては、フェニルトリエトキシシラン、フェニルトリメトキシシラン、フェニルクロロシラン、フェニルメチルクロロシランなどが特に好適に例示される。なお、フェニル基などのπ電子官能基のπ電子濃度を上げるため、例えばフェニル基−絶縁性部位（たとえばＰｈ−ＳｉＯ２等）のように、絶縁部位（ＳｉＯ２）がπ電子の動きをフェニル基内に収めることが、特に好ましいと考えられる。
さらにベース膜構成物質として用い得るものとしては、アセチレン、グラフェン、ポリフェニレン系物質、カーボンチューブなどの疎水性共役系高分子、ポリスチレン、フェネチルアルコール、フェノール、フェナントレノール、クレゾールテトラヒドロ-フェナントレノール、などの芳香族アルコール類、フェニルアセトアルデヒド、メトキシベンズアルデヒド、クミンアルデヒド、ヘキシルシンナムアルデヒドなどの芳香族アルデヒド類、フェナントレンカルボキシアルデヒド、フタル酸、安息香酸などの芳香族カルボン酸類、タケネートなどの芳香族イソシアネート類、チオフェノールなどの芳香族チオール類、他にグラフェン60、61、70 含有アルコール、グラフェン60、61、70 含有アルデヒド、グラフェン60、61、70 含有カルボン酸類、生体由来物質ではβカロテンの単分子膜やヘモグロビン、フェニルクロライド類、アニリン類などがあげられる。
なお、これらのベース膜構成物質を用いてベース膜を形成するには、キャスト法、スキージー法、ディップ法、スピンコーティング法などを用いることができる。ベース膜を形成する物品表面は、ベース膜構成物質に対し親溶媒性を持つことが好ましいが、貧溶媒性であってもアルカリ処理やＵＶ／Ｏ３処理などを併用することによって成膜が可能である。
また、ベース膜形成後に洗浄を行う場合には、有機溶媒を用いることが好適である。洗浄用有機溶媒としては、トルエン、ベンゼン、ペンタン、ヘキサン、ヘプタン、シクロヘキサン、塩化メチル、臭化メチル、酢酸エチル、ジエチルエーテル、テトラヒドロフラン、エチルセロソルブ、アセトン、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、t-ブタノール、クロロホルムなどがあげられる。
[Base film]
In the present invention, the base film 16 preferably has a fixing group (for example, a silane group) on the surface of the article together with a π-electron functional group having a high concentration of π-electrons. Aromatics such as groups and alkynes are preferred.
Specific examples of the base film constituent material include phenyltriethoxysilane, phenyltrimethoxysilane, phenylchlorosilane, and phenylmethylchlorosilane. In order to increase the π-electron concentration of a π-electron functional group such as a phenyl group, the insulating part (SiO 2 ) can move the movement of π electrons to a phenyl group, such as a phenyl group-insulating part (for example, Ph-SiO 2 ). It is considered that it is particularly preferable to fit within the group.
In addition, as the base film constituent materials, acetylene, graphene, polyphenylene materials, hydrophobic conjugated polymers such as carbon tubes, polystyrene, phenethyl alcohol, phenol, phenanthreneol, cresol tetrahydro-phenanthrenol, etc. Aromatic alcohols such as phenylacetaldehyde, methoxybenzaldehyde, cuminaldehyde, hexylcinnamaldehyde, aromatic aldehydes such as phenanthrenecarboxaldehyde, phthalic acid and benzoic acid, aromatic isocyanates such as takenate, thio Aromatic thiols such as phenol, alcohols containing graphene 60, 61, 70, aldehydes containing graphene 60, 61, 70, carboxylic acids containing graphene 60, 61, 70, raw Examples of body-derived substances include β-carotene monolayer, hemoglobin, phenyl chlorides, and anilines.
In order to form a base film using these base film constituent materials, a casting method, a squeegee method, a dip method, a spin coating method, or the like can be used. The article surface on which the base film is formed preferably has a solvophilic property with respect to the base film constituent material, but even if it is poorly solvent, it can be formed by using alkali treatment or UV / O 3 treatment in combination. It is.
In the case where cleaning is performed after the base film is formed, it is preferable to use an organic solvent. Organic solvents for washing include toluene, benzene, pentane, hexane, heptane, cyclohexane, methyl chloride, methyl bromide, ethyl acetate, diethyl ether, tetrahydrofuran, ethyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n -Propanol, isopropanol, n-butanol, isobutanol, t-butanol, chloroform and the like.
［滑液剤］
本発明において滑液剤には、常温でほとんど揮発せず、滑液対象となる液体に対し疎液性を示す滑液作用部を持ち、なおかつπ電子と相互作用を示すπ相互作用部を有する液体であることが好適である。
前記π相互作用部としては、エトキシ基、メトキシ基、フェニル基、ヒドロキシ基、カルボニル基、アルデヒド基、-XH基（Ｘは任意の原子）などが好適に例示される。
前記π相互作用部を有し、且つ潤滑性を有する滑液剤であれば、粘度や表面張力にほとんど依存することなく液膜を形成し、安定した透明性（可視光域で約９０％）、滑液性能を示すことができる。本発明に用いられる滑液剤として、滑液対象が水性液体の場合、シリコーンオイルや脂肪酸、高級アルコール、シランカップラー、そのほかに有機系の疎水性液体物質が挙げられる。より具体的には、シリコーンオイルとしてデカメチルシクロテトラシロキサン、オクタメチルシクロテトラシロキサン、ドデカメチルシクロヘキサシロキサン、メチルシリコーン、メチルフェニルシリコーン、メチルヒドロキシシリコーン、アミノ変性シリコーンオイル、エポキシ変性シリコーンオイル、カルボキシ変性シリコーンオイル、カルビノール変性シリコーンオイル、メタクリル変性シリコーンオイル、メルカプト変性シリコーンオイル、フェノール変性シリコーンオイル、ポリエーテル変性シリコーンオイル、メチルスチリル変性シリコーンオイル、アルキル変性シリコーンオイル、脂肪酸エステル変性シリコーンオイル、部分フッ素変性シリコーンオイルなどが例示され、更に低級飽和脂肪酸、高級飽和脂肪酸、低級不飽和脂肪酸、高級不飽和脂肪酸、高級アルコール、および脂肪酸化合物（ごま油、菜種油、アーモンドオイル、綿実油、サラダ油など）、フルオロアルキルエトキシシラン、フルオロアルキルメトキシシラン、アルキルエトキシシラン、アルキルメトキシシラン、ＤＢ２−ＥＯＳ、ＥＦ−ＤＢ２、Ｐ３−ＥＯＳ、また揮発性の小さい炭化水素（ＣｎＨｘ（n>４ 以上）のアルカン、アルケン、アルキン）も用い得る。
以下のフェニル基を含む化合物は、ベース膜、あるいは滑液剤のいずれにも用いることが可能である。
2−(4,6−ジフェニル1,3,5−トリアジン−2−イル)−5−[(ヘキシル)オキシ]−フェノール、
１−［2−｛3−（3，5−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ｝エチル］−4−｛3−（3，5−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ｝−2,2,6,6−テトラメチルピペリジン、
4，4'−ビス（α，α−ジメチル−ベンジル）ジフェニルアミン、
2,4−ジアミノ−フェニル−1,3,5−トリアジン、
トリス(ノニルフェニル)フォスファイト、
トリス(ミックスド,モノおよびジノニルフェニル)フォスファイト、
トリス(2,4−ジ−t−ブチルフェニル)フォスファイト、
4,4'−ブチリデン−ビス(3−メチル−6−t−ブチルフェニル−ジ−トリデシルフォスファイト)、
1,1,3−トリス(2−メチル−4−ジ−トリデシルフォスファイト−5−t−ブチル−フェニル)ブタンとジフェニルフォスファイトとの混合物、
4,4'ビフェニレンジホスフィン酸テトラキス(2,4一ジ-t−ブチルフェニル)、
サイクリックネオペンタンテトライルビス(2,4−ジ−t−ブチルフェニルフォスファイト)、
トリス(シクロヘキシルフェニル)フォスファイト、
2−t−ブチル−α−(3−t−ブチル−4−ヒドロキシフェニル)−P−クメニルビス(P−ノニルフェニル)フォスファイト、
ビス−[2−メチル−4,6−ビス−(1,1−ジメチルエチル)フェニル]エチルフォスファイト、
3,9−ビス｛2,4−ビス(1−メチル−1−フェニルエチル)フェノキシ｝−2,4,8,10−テトラオキサ−3,9−ジホスファスピロ[5,5]ウンデカン、
6−[3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロポキシ−2,4,8,10−テトラ−t−ブチルベンズ[d, f] [1,3,2]ジオキサホスフェピン、
n−オクタデシル−β−(4'−ヒドロキシ−3',5'−ジ−t−ブチルフェニル)プロピオネート、
4,4'−ブチリデンビス(6−t−ブチル−m−クレゾール)又は1,1−ビス(2'−メチル−4'−ヒドロキシ−5'−t−ブチル−フェニル)ブタン、
トリエチレングリコールビス−3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート、
2,2'−オキサミドビス〔エチル3− (3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオネート〕、
1,1,3−トリス(2−メチル−4−ヒドロキシ−5−t−ブチルフェニル)ブタン）、
２−ｔ−ブチル−６-（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、
テトラキス〔メチレン−3−(3',5)ジ−t−ブチル−4'−ヒドロキシフェニル〕プロピオネート〕メタン、
ビス 〔3,3 −ビス(4'−ヒドロキシ−3'−t−ブチルフェニル)ブタン酸〕グリコールエステル、
1,4−ベンゼンジカルボン酸ビス〔2−(1,1−ジメチルエチル)−6−〔〔3−(1,エジメチルエチル)−2−ヒドロキシ−5−メチルフェニル〕メチル〕−4−メチルフェニル〕エステル、
N,N,−ビス{3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニル}ヒドラジン、
3,9-ビス[2-{3-(3-t-ブチル-4-ヒドロキシ-5-メチル フェニル)プロピオニルオキシ}-1,1-ジメチルエチル]−2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、
２−［１−（２−ヒドロキシ−３，５−ジ−ｔ−ペンチルフェニル）エチル］−４，６−ジ−ｔ−ペンチルフェニルアクリレート、
p−t−ブチルフェニルサリシレート、
2,4−ジ−t−ブチルフェニルー3,5−ジ−t−ブチル−4−ヒドロキシベンゾエ一ト、
2−(2'−ヒドロキシ−5'−メチルフェニル)ベンゾトリアゾール、
2−(2'−ヒドロキシ−3'−t−ブチル−5'−メチルフェニル)−5−クロロベンゾトリアゾール、
サリチル酸フェニル又はフェニルサリシレート、
2−(2H−ベンゾトリアゾール−2−イル)−4,6−ビス(1−メチル−1−フェニルエチル)フェノール、
2−(2'ハイドロキシ−5'−メタクリルオキシエチルフェニル)−2H−べンゾトリアゾールとメチルメタクリレトの共重合物、
2-シアノ-3,3-ジフェニルアクリル酸-2-エチルヘキシル、
ポリ(オキシ-1,2-エタンジイル),α-[4-(3-ブトキシ-2-シアノ-3-オキソ−１−プロペン−１−イル）−２−メトキシフェニル]-ω-ヒドロキシ-2−(2'−ヒドロキシ−3'5'−ジ)−t−アミルフェニル)ベンゾトリアゾール、
ポリオキシエチレン(4〜50モル)アルキル(C7以上)フェニルエーテル、
ポリオキシエチレン(4〜50モル) アルキル(C7以上)フェニルエーテルサルフェート(Na,NH4)、
ポリオキシエチレン(5〜55モル) ノニルフェニルホスフェート、
α(p−ノニルフェニル)−ω−ヒドロキシポリ(オキシエチレン)燐酸二水素エステル,燐酸一水素エステルの混合物、
メチルフェニルポリシロキサン、
ポリオルガノ(C1〜C32のアルキル基および/またはフェニル基)シロキサンとポリアルキレン(C2〜C3)グリコールの縮合物、
ベンゼン−１、２−ジメチル−４、５−ビス（１−フェニルエチル） （２５〜４５％）、
ベンゼン−４−（１、３ジフェニルブチル）−１、２ジメチル （２０〜４０％）、
ベンゼン［１−（３、４−ジメチルフェニル）エチル］（１−フェニルエチル）（２５〜４５％）の混合物、
分岐ポリカーボネート： 分岐剤はトリス(パラヒドロキシフェニル)エタンに限る。
分岐剤の添加量2.0%以下、
リン酸ビス（４−ｔ−ブチルフェニル）ナトリウム、
リン酸２，２'−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウム
フェニルホスホン酸亜鉛(II) 、
7,8,9-トリデオキシ-3,5:4,6-O-ビス-(4-プロピルフェニル）メチレン=D-グリセロ-L-グロ-ノニトール。
次の表１に、特に滑水性の高い滑液剤とその特性を示す。
[Synovial fluid]
In the present invention, the synovial fluid is a liquid having a synovial fluid action part that exhibits little lyophobic properties with respect to the liquid to be synovial fluid, and has a π interaction part that interacts with π electrons. It is preferable that
Preferable examples of the π interaction part include an ethoxy group, a methoxy group, a phenyl group, a hydroxy group, a carbonyl group, an aldehyde group, and an —XH group (X is an arbitrary atom).
If it is a lubricant that has the π-interaction part and has lubricity, it forms a liquid film almost independent of viscosity and surface tension, stable transparency (about 90% in the visible light region), Synovial fluid performance can be shown. When the synovial fluid is an aqueous liquid, examples of the synovial agent used in the present invention include silicone oil, fatty acid, higher alcohol, silane coupler, and other organic hydrophobic liquid substances. More specifically, decamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methylsilicone, methylphenylsilicone, methylhydroxysilicone, amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified as silicone oil Silicone oil, carbinol modified silicone oil, methacrylic modified silicone oil, mercapto modified silicone oil, phenol modified silicone oil, polyether modified silicone oil, methylstyryl modified silicone oil, alkyl modified silicone oil, fatty acid ester modified silicone oil, partially fluorine modified Examples include silicone oils, and lower saturated fatty acids, higher saturated fatty acids, and lower unsaturated fats. Acids, higher unsaturated fatty acids, higher alcohols, and fatty acid compounds (sesame oil, rapeseed oil, almond oil, cottonseed oil, salad oil, etc.), fluoroalkylethoxysilane, fluoroalkylmethoxysilane, alkylethoxysilane, alkylmethoxysilane, DB2-EOS, EF -DB2, P3-EOS, and low volatility hydrocarbons (CnHx (n> 4 or more) alkane, alkene, alkyne) may also be used.
The following compounds containing a phenyl group can be used for either the base film or the lubricant.
2- (4,6-diphenyl 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol,
1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy} -2,2,6,6-tetramethylpiperidine,
4,4′-bis (α, α-dimethyl-benzyl) diphenylamine,
2,4-diamino-phenyl-1,3,5-triazine,
Tris (nonylphenyl) phosphite,
Tris (mixed, mono and dinonylphenyl) phosphite,
Tris (2,4-di-t-butylphenyl) phosphite,
4,4'-butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite),
A mixture of 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-t-butyl-phenyl) butane and diphenyl phosphite;
4,4′biphenylenediphosphinic acid tetrakis (2,4 di-t-butylphenyl),
Cyclic neopentanetetraylbis (2,4-di-t-butylphenylphosphite),
Tris (cyclohexylphenyl) phosphite,
2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -P-cumenylbis (P-nonylphenyl) phosphite,
Bis- [2-methyl-4,6-bis- (1,1-dimethylethyl) phenyl] ethyl phosphite,
3,9-bis {2,4-bis (1-methyl-1-phenylethyl) phenoxy} -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane,
6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy-2,4,8,10-tetra-tert-butylbenz [d, f] [1,3,2] dioxa Phosfepin,
n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate,
4,4′-butylidenebis (6-t-butyl-m-cresol) or 1,1-bis (2′-methyl-4′-hydroxy-5′-t-butyl-phenyl) butane,
Triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate,
2,2′-oxamidobis (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate),
1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane),
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate,
Tetrakis [methylene-3- (3 ′, 5) di-tert-butyl-4′-hydroxyphenyl] propionate] methane,
Bis [3,3-bis (4′-hydroxy-3′-t-butylphenyl) butanoic acid] glycol ester,
1,4-Benzenedicarboxylic acid bis [2- (1,1-dimethylethyl) -6-[[3- (1, edimethylethyl) -2-hydroxy-5-methylphenyl] methyl] -4-methylphenyl 〕ester,
N, N, -bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine,
3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane,
2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate,
p-t-butylphenyl salicylate,
2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate,
2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole,
Phenyl salicylate or phenyl salicylate,
2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol,
2- (2′hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole and methyl methacrylate copolymer,
2-ethylhexyl 2-cyano-3,3-diphenylacrylate,
Poly (oxy-1,2-ethanediyl), α- [4- (3-butoxy-2-cyano-3-oxo-1-propen-1-yl) -2-methoxyphenyl] -ω-hydroxy-2- (2′-hydroxy-3′5′-di) -t-amylphenyl) benzotriazole,
Polyoxyethylene (4-50 mol) alkyl (C7 or higher) phenyl ether,
Polyoxyethylene (4 to 50 mol) alkyl (C7 or higher) phenyl ether sulfate (Na, NH4),
Polyoxyethylene (5-55 mol) nonylphenyl phosphate,
a mixture of α (p-nonylphenyl) -ω-hydroxypoly (oxyethylene) dihydrogen phosphate, monohydrogen phosphate,
Methylphenyl polysiloxane,
Polyorgano (C1-C32 alkyl group and / or phenyl group) siloxane and polyalkylene (C2-C3) glycol condensate,
Benzene-1,2-dimethyl-4,5-bis (1-phenylethyl) (25-45%),
Benzene-4- (1,3 diphenylbutyl) -1,2 dimethyl (20-40%),
A mixture of benzene [1- (3,4-dimethylphenyl) ethyl] (1-phenylethyl) (25-45%),
Branched polycarbonate: The branching agent is limited to tris (parahydroxyphenyl) ethane.
Addition amount of branching agent is 2.0% or less,
Bis (4-tert-butylphenyl) sodium phosphate,
2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate zinc zinc phosphate (II),
7,8,9-trideoxy-3,5: 4,6-O-bis- (4-propylphenyl) methylene = D-glycero-L-glo-nonitol.
Table 1 below shows a synovial fluid having particularly high water slidability and its characteristics.
［表１］
[Table 1]
図２に、本発明にかかる滑液膜の製造工程が示されている。
同図に示すように、物品（本実施形態においてはガラス）表面上にＵＶ／Ｏ３処理もしくは強アルカリ液により物品表面へ官能基（ＯＨ基）を形成し、その上にベース膜構成物質（本実施形態においては、フェニルトリエトキシシラン、以下ＰＴＥＳ）をスピンコーティングもしくはディップ法、スキージ法、キャスト法などにより塗布し、シラン反応を生じさせ、物品表面にベース膜を固定する。この際、フェニル基はシラン反応に関与しないため、ベース膜上にフェニル残基がペンダント状に修飾された状態となる。ＰＴＥＳによる表面の化学的な結合状態は図３に模式的に示すように推定される。
FIG. 2 shows the production process of the synovial fluid film according to the present invention.
As shown in the figure, a functional group (OH group) is formed on the surface of the article (in this embodiment, glass) by UV / O 3 treatment or strong alkaline solution, and a base film constituent material ( In this embodiment, phenyltriethoxysilane (hereinafter referred to as PTES) is applied by spin coating or dipping, squeegee, casting, or the like to cause a silane reaction and fix the base film on the article surface. At this time, since the phenyl group does not participate in the silane reaction, the phenyl residue is modified in a pendant form on the base film. The chemical bonding state of the surface by PTES is estimated as schematically shown in FIG.
次に、ベース膜をエタノール洗浄し、未反応ＰＴＥＳ等、物品表面に固定されなかった残存物を除去し、滑液剤（本実施形態においてはデシルトリメトキシシラン、以下ＤＴＭＳ：２５℃における粘度約０．００３Pa.s、表面張力２７ｍNm−１）を塗布する。そして、余剰ＤＴＭＳを除去し、物品表面上に滑液膜が形成される。
なお、製造工程の詳細は以下の通りである。
(a)ＰＴＥＳ：１．８mmol、ＴＭＯＳ：９．０６mmol、ＥｔＯＨ：１０．０mLを混合し１０分間撹拌する。
(b)Ｈ２Ｏ：０．０４２mol、ＨＣｌａｑ：２μＬを添加し、２４時間撹拌する。
(c)ガラス基板をＵＶ／Ｏ３処理する。
(d)前記ＰＴＥＳ溶液をスピンコーティング（１０００rpm，５sec→２０００rpm，１０sec）する。
(e)２４時間乾燥させる。
Next, the base membrane is washed with ethanol to remove unreacted PTES and other residues that are not fixed to the surface of the article, and a lubricant (in this embodiment, decyltrimethoxysilane, hereinafter DTMS: viscosity of about 0 at 25 ° C.) .003 Pa.s, surface tension 27 mNm −1 ) is applied. Then, excess DTMS is removed, and a synovial fluid film is formed on the surface of the article.
The details of the manufacturing process are as follows.
(a) PTES: 1.8 mmol, TMOS: 9.06 mmol, EtOH: 10.0 mL are mixed and stirred for 10 minutes.
(b) Add H 2 O: 0.042 mol, HClaq: 2 μL, and stir for 24 hours.
(c) The glass substrate is treated with UV / O 3 .
(d) The PTES solution is spin-coated (1000 rpm, 5 sec → 2000 rpm, 10 sec).
(e) Dry for 24 hours.
図４に本発明にかかる滑液膜の概念図が示されており、同図に示すようにガラス表面上にはベース膜が約１４４nmで形成され、その上にＣＨ−π相互作用により保持されたＤＴＭＳ層が５００〜８００nmの厚さで形成される。ＤＴＭＳ塗布時には余剰ＤＴＭＳ層が２〜３μｍ形成されたが、これは除去される。
ＤＴＭＳは液状であり、通常の物品表面上からは簡易なふき取りでほとんどが除去可能であるが、本実施形態においてはＤＴＭＳのメトキシ基がベース膜上のフェニル基とＣＨ−π相互作用により結合するため、ＤＴＭＳは流動性を保ちつつ、しっかりと滑液膜に保持されることとなる。
このＤＴＭＳの流動性は滑液膜の滑液性のみならず、修復性にも大きな影響を与え、ベース膜が破壊されない限り、仮に特定部位のＤＴＭＳが除去されても他の部位から流入したＤＴＭＳが再度ＣＨ−π相互作用により結合され、滑液性が修復する。
FIG. 4 shows a conceptual diagram of the synovial fluid film according to the present invention. As shown in the figure, a base film is formed on the glass surface at about 144 nm, and is retained on the surface by CH-π interaction. The DTMS layer is formed to a thickness of 500 to 800 nm. At the time of DTMS application, an excess DTMS layer of 2 to 3 μm was formed, but this is removed.
Although DTMS is in a liquid state and can be almost removed from the surface of a normal article by simple wiping, in this embodiment, the methoxy group of DTMS is bonded to the phenyl group on the base film by CH-π interaction. Therefore, DTMS is firmly held by the synovial membrane while maintaining fluidity.
The fluidity of this DTMS has a great influence not only on the synovial fluid of the synovial membrane but also on the restorability. Unless the base membrane is destroyed, even if the DTMS at a specific site is removed, DTMS that has flowed in from other sites Are re-coupled by the CH-π interaction and the synovial properties are restored.
なお、図５に示すように、物品表面上にＤＴＭＳを直接シラン反応により修飾した場合には、ＣＨ−π相互作用により他のＤＴＭＳを結合する能力はないため、ＤＴＭＳを余剰に塗布した場合にも本発明のような滑液剤層はほとんど形成されなかった。
ＤＴＭＳ直接結合膜の製造方法を、以下に具体的に示す。
(a)ＤＴＭＳ：１．８mmol、ＴＥＯＳ：９．０６mmol、ＥｔＯＨ：１０．０mLを混合し１０分間撹拌する。
(b)Ｈ２Ｏ：０．０４２mol、ＨＣｌａｑ：２μＬを添加し、２４時間撹拌する。
(c)ガラス基板をＵＶ／Ｏ３処理する。
(d)前記ＤＴＭＳ溶液をスピンコーティング（１０００rpm，５sec→２０００rpm，１０sec）する。
(e)２４時間乾燥させる。
As shown in FIG. 5, when DTMS is directly modified on the surface of the article by silane reaction, there is no ability to bind other DTMS by CH-π interaction, so when DTMS is applied excessively. However, the lubricant layer as in the present invention was hardly formed.
The manufacturing method of the DTMS direct bonding film is specifically shown below.
(a) DTMS: 1.8 mmol, TEOS: 9.06 mmol, EtOH: 10.0 mL are mixed and stirred for 10 minutes.
(b) Add H 2 O: 0.042 mol, HClaq: 2 μL, and stir for 24 hours.
(c) The glass substrate is treated with UV / O 3 .
(d) Spin coating (1000 rpm, 5 sec → 2000 rpm, 10 sec) with the DTMS solution.
(e) Dry for 24 hours.
図６に、物品表面に直接結合されたＤＴＭＳ結合膜（同図（ａ））と、ＰＴＥＳベース膜（同図（ｂ））の、Ｘ線光電子分光による評価結果を示す。同図（ｂ）より明らかなように、ＰＴＥＳ結合体にはπ電子に由来するピークが観察された。
以上のことから、本実施形態にかかるベース膜はπ電子を高濃度に持つフェニル基が有効に存在していることが確認された。
FIG. 6 shows the evaluation results by X-ray photoelectron spectroscopy of the DTMS coupling film (FIG. 6A) directly bonded to the article surface and the PTES base film (FIG. 6B). As is clear from FIG. 5B, a peak derived from π electrons was observed in the PTES conjugate.
From the above, it was confirmed that the base film according to the present embodiment effectively has phenyl groups having a high concentration of π electrons.
次に本発明者らは、本発明にかかる滑液膜の滑液性について評価を行った。
すなわち、図７に示すように、被検液を、滑液膜を形成したガラス板上に滴下し、該ガラス坂を傾斜させ、その滑落を生じる角度について検討を行った。なお、同図（ｂ）に示すように、被検液が濡れてしまう場合、該被検液は滑液剤としての特性を持つ可能性がある。
まず、本発明者らはガラス坂に対し直接ＤＴＭＳをシラン結合させたＤＴＭＳ結合膜の場合と、ガラス坂に対しＰＴＥＳをシラン結合させたＰＴＥＳベース膜の場合（ＤＴＭＳを塗布せず）について、各種被検液の滑落性について検討を行った。結果を図８に示す。
同図より明らかなように、水は、ＤＴＭＳ結合膜とＰＴＥＳベース膜の両者に対し、ともに２０度程度で滑落を生じ、大きな差は認められなかった。しかしながら、オレイン酸、トルエン、アセトン、メタノール、エタノールなどの極性有機溶剤は、ＤＴＭＳ結合膜に対してはいずれも１０度以下で滑落を生じるのに対し、ＰＴＥＳベース膜に対してはいずれも濡れを生じ滑落を生じなかった。 以上の点から、ＰＴＥＳベース膜は水および炭化水素に対してはある程度の滑液性があるが、極性溶媒に対してπ相互作用に基づく結合性が存在するものと考えられる。また、ＤＴＭＳ結合膜は液状滑液剤の保持能は有しないことが理解される。
Next, the present inventors evaluated the synovial fluid of the synovial membrane according to the present invention.
That is, as shown in FIG. 7, the test liquid was dropped on a glass plate on which a synovial fluid film was formed, the glass slope was inclined, and the angle at which the sliding occurred was examined. In addition, as shown to the same figure (b), when a test liquid will get wet, this test liquid may have the characteristic as a synovial fluid.
First, the present inventors have various cases in the case of a DTMS-bonded film in which DTMS is directly silane-bonded to a glass slope, and in the case of a PTES base film in which PTES is silane-bonded to a glass slope (without applying DTMS). The sliding property of the test solution was examined. The results are shown in FIG.
As is clear from the figure, the water slipped at about 20 degrees with respect to both the DTMS binding film and the PTES base film, and a large difference was not recognized. However, polar organic solvents such as oleic acid, toluene, acetone, methanol, and ethanol all cause slipping at 10 degrees or less for DTMS-bonded membranes, but all wet for PTES-based membranes. It did not slide down. From the above points, it is considered that the PTES base membrane has a certain synovial property with respect to water and hydrocarbons, but has a binding property based on π interaction with a polar solvent. It is also understood that the DTMS binding membrane does not have a liquid lubricant retention capability.
次に本発明者らはガラス、ＰＴＥＳベース膜、ＰＴＥＳベース膜＋ＤＴＭＳ（滑液剤）について、接触角及び滑落角度を検証した。結果を図９に示す。
まず接触角については、ガラスは濡れ性が高く２０度弱である。これに対し、ＰＴＥＳベース膜とＰＴＥＳベース膜＋ＤＴＭＳは、いずれも７０度近くであり、ほぼ同等に濡れ性が低い。
一方、滑落角度については、ガラスは濡れを生じるが、ＰＴＥＳベース膜は前記の通り２０度程度、ＰＴＥＳベース膜＋ＤＴＭＳは０．５度と、単に接触角が大きくなる（接触面積が小さくなる）ことによる転がり性ないしすべり性の向上とは異なる挙動が観察された。これには、ベース膜上のＤＴＭＳの流動性も大きく影響しているものと考えられる。
Next, the present inventors verified the contact angle and sliding-down angle for glass, PTES base film, PTES base film + DTMS (synovial fluid). The results are shown in FIG.
First, regarding the contact angle, glass has high wettability and is less than 20 degrees. On the other hand, the PTES base film and the PTES base film + DTMS are both close to 70 degrees, and have substantially the same low wettability.
On the other hand, as for the sliding angle, the glass causes wetting, but the PTES base film is about 20 degrees as described above, and the PTES base film + DTMS is 0.5 degrees, and the contact angle simply increases (the contact area decreases). A behavior different from the improvement of rolling property or sliding property due to was observed. It is considered that this has a great influence on the fluidity of DTMS on the base film.
さらに本発明者らは、滑液膜の光学的特性について評価を行った。すなわち、いわゆるＳＬＩＰＳは物品表面に多孔質状態を形成する必要があるため、透明性等の光学的特性が劣る傾向にある。これに対し、本実施形態にかかる滑液膜は物品表面に凹凸を形成する必要がなく、むしろベース膜形成および滑液剤層の形成により平坦化が進み、また、下地がフラットなので純滑液面が減っても下地による散乱損失が生じず、安定した透過性を得られることで光学的特性の向上が期待される。評価結果を図１０に示す。
同図より、基板（ガラス）に対してＤＴＭＳを直接シラン結合させた場合には、総透過率（Ｔ．Ｔ）及び直進透過率（Ｐ．Ｔ．）はほぼ同じであるが、ヘーズ値および拡散透過率（ＤＴＦ）は低下する傾向にある。
Furthermore, the present inventors evaluated the optical characteristics of the synovial fluid film. That is, since so-called SLIPS needs to form a porous state on the surface of an article, optical properties such as transparency tend to be inferior. On the other hand, the synovial fluid film according to the present embodiment does not need to form irregularities on the surface of the article. Rather, since the base film is flattened by forming the base film and the synovial agent layer, and the base is flat, the pure synovial surface Even if the thickness is reduced, scattering loss due to the base does not occur, and stable optical transparency can be obtained, so that an improvement in optical characteristics is expected. The evaluation results are shown in FIG.
From the figure, when DTMS is directly silane-bonded to the substrate (glass), the total transmittance (T. T) and the straight transmittance (P. T.) are almost the same, but the haze value and Diffusion transmittance (DTF) tends to decrease.
一方、ガラス基板に対しＰＴＥＳベース膜を形成した場合には、基板単独と比較し総透過率および直進透過率は大きな変化がないが、ヘーズ値および拡散透過率は大きく低下する。さらに、ガラス基板に対しＰＴＥＳベース膜を形成するとともにＤＴＭＳを滑液剤層として形成した場合は、ＰＴＥＳベース膜のみの場合と比較しヘーズ値および拡散透過率が上昇する傾向にあるが、ガラス基板およびＤＴＭＳを直接シラン結合させた場合と比較すると低く抑えることができる。 On the other hand, when the PTES base film is formed on the glass substrate, the total transmittance and the straight transmittance are not significantly changed as compared with the substrate alone, but the haze value and the diffuse transmittance are greatly reduced. Further, when the PTES base film is formed on the glass substrate and DTMS is formed as the lubricant layer, the haze value and the diffuse transmittance tend to increase as compared with the case of only the PTES base film. Compared with the case where DTMS is directly silane-bonded, it can be kept low.
これらのことから、本発明にかかる滑液膜は透明性が高く、光学的特性に優れることが理解され、特にＰＴＥＳベース膜ないしＤＴＭＳ層の形成で基板以上に平坦性が確保され、光学的特性が向上することが理解される。
また、図１１には本発明を缶内面に適用した場合についての検討結果が示されている。
すなわち、ＰＥＴ樹脂塗装されたスチール缶内面に、ＰＴＥＳベース膜およびオレイン酸（滑液剤）層を形成した場合について、ボイル試験及びレトルト試験を行った。結果を図１１に示す。
同図より明らかなように、滑液剤層にオレイン酸を用いた場合、蓋の開いた缶および密閉した缶内において９０℃の熱湯に３０分間浸漬した後でも、水滴に対して試験前と変わることなく、５度以下の転落角を示し、優れた滑液性能を保持した。
また、滑液剤層にＤＴＭＳを用いた場合には、ボイル試験に対しては優れた耐久性を示したが、レトルト試験については滑落角が増大（悪化）した。しかし、レトルト試験品についても、再度ＤＴＭＳの滴下、塗布を行うことにより、滑落角の低下が認められ、ベース膜は維持されていることが示唆された。
From these facts, it is understood that the synovial fluid film according to the present invention has high transparency and excellent optical characteristics, and in particular, the formation of a PTES base film or a DTMS layer ensures flatness more than the substrate, and the optical characteristics. Is understood to improve.
Further, FIG. 11 shows the result of study on the case where the present invention is applied to the inner surface of the can.
That is, a boil test and a retort test were performed on the case where a PTES base film and an oleic acid (lubricant) layer were formed on the inner surface of a steel can coated with PET resin. The results are shown in FIG.
As is clear from the figure, when oleic acid is used for the lubricant layer, even after being immersed in hot water at 90 ° C. for 30 minutes in a can with an open lid and a sealed can, it changes from before the test with respect to water droplets. Without falling, it showed a sliding angle of 5 degrees or less, and maintained excellent synovial fluid performance.
In addition, when DTMS was used for the lubricant layer, it showed excellent durability for the boil test, but the sliding angle increased (deteriorated) for the retort test. However, with respect to the retort test product as well, when the DTMS was dropped and applied again, the sliding angle was reduced, suggesting that the base film was maintained.
さらに本発明者らは、図１２に示すような滑液膜の折り曲げ耐性試験を行った。
すなわち、ＳＬＩＰＳの場合、表面の引き伸ばしにより滑液剤を保持する多孔質部分の凸部が露出し、該凸部によるピン止め効果で滑液効果が著しく低下することがある。
しかしながら、本実施形態にかかる滑液膜によれば、物品表面およびベース膜、滑液剤層のいずれもが平坦化されており、物品表面の折り曲げ等により滑液性が低下することはない。
また、本発明者らは図１３に示すように、鋭利な刃物により滑液膜を傷つけた場合のスクラッチ耐性試験を行ったが、滑液剤層はベース膜に対する親和性の高さにより修復が行われる。
Furthermore, the present inventors conducted a bending resistance test of the synovial fluid film as shown in FIG.
That is, in the case of SLIPS, the convex portion of the porous portion holding the lubricant is exposed by stretching the surface, and the synovial fluid effect may be significantly reduced due to the pinning effect by the convex portion.
However, according to the synovial fluid film according to the present embodiment, the article surface, the base film, and the synovial agent layer are all flattened, and the synovial properties are not lowered by bending or the like of the article surface.
Further, as shown in FIG. 13, the present inventors conducted a scratch resistance test when the synovial fluid film was damaged by a sharp blade, but the synovial agent layer was repaired due to its high affinity for the base membrane. Is called.
さらに図１４は滑液膜を摩擦した場合であり、この場合にも前記滑液膜を傷つけた場合と同様、滑液剤層の修復が行われる。
以上のように、本実施形態にかかる滑液膜は、修復性も極めて高く、優れた滑液膜であることが理解される。
なお、ガラス表面では水滴（１０μL）は滑落しないが、ＤＴＭＳによる滑液剤層を形成することにより滑落角度は０．５度で滑落した。また、一般的に超低粘度液体は下地がフラットでないと液膜を形成しないが、本実施形態ではフラットなガラス表面に超低粘度のDTMS を適用している。このように、本発明にかかる滑液膜によれば、滑液剤（純滑液）の選択性は非常に幅広く、従来のように使用可能な滑液剤が限定されるという問題を解決したといえる。
また、本実施形態ではガラスへの滑液膜形成を行ったが、本実施形態において用いられているシラン結合によるベース膜形成は、親水処理を行った表面であれば適用可能である。例えばPET フィルムにベース膜形成を行った場合にも優れた性能を示した。
また、本実施形態の滑液膜は、水、温水（90℃）、食塩水（５wt％）、氷塊、血液に対しても優れた滑落性を示した。熱水は水よりも表面張力が低く、なおかつ蒸気による微小液体の付着を伴うため、熱水の滑落に関する報告例はほとんど存在しないが、本件の膜は滑落できた。これは微小液体を滑らせることができ、液体粒の合一が進むためと考えられる。また、本実施形態にかかる滑液膜は、血液の滑落性を示した。また、血液へのディッピングテストや内視鏡レンズを通した出力画像に対しても血液の完全な非付着性能を示した。
これまで液体非付着表面のアプローチとしてはSLIPS、超撥水表面（SHS）が報告されている。SLIPS は非混和性潤滑油によって液体を滑落させる（条件によっては表面を転がる）が、一方で超撥水表面は液体と物品表面の界面に空気層を作製し、接触面積を減少させることで液体を転がすことができる。Zuankai Wang ら、Tak-sin wong らによると、液体滑落速度は滑液剤層の粘度におおよそ反比例する。また、KK Varanasi らにより、物品表面の凹凸が小さいほど液体滑落速度が速まることが報告されている。本発明者らも物品表面の凹凸が液体滑落性を著しく低下させることを確認している。そして、本実施形態によれば、従来の滑液剤よりも著しく低い粘度であるDTMS（μ＝0.003 Pa・sec）を保持することができ、また物品表面の凹凸はRMS＜１nm 以下であるため、滑落速度を非常に高めたといえる。
物品表面の凹凸構造を針状構造にして超撥水性SLIPS を形成した例もあるが、やはり超撥水SLIPS も滑油剤粘度依存をする。その結果本発明にかかる滑液膜 の水滑落速度は、SLIPS に比べて飛躍的に向上した。
また、SHS 表面においては微小液体が凹凸構造に挟まってしまうため、ピン止め効果が起き、滑落しない（＜５μL の時）。また、SLIPS に関しては、ある程度大きな液径にならない限りは、液体はかなりゆっくり滑る（ほとんど動いていない）。このため、液体の物品表面からの除去が難しい。微小液体をある程度の速度で滑らせることは非常に重要であり、例えば血液や氷核のように時間経過とともに凝固や成長を起こして除去が困難になってしまう液体を除去するのに重要である。特にSLIPS の場合は、滑液剤内に噴霧圧力などなんらかの外力の原因で液体が入り込んでしまった場合、該侵入液体が除去できないことがある。本実施形態にかかる滑液膜によれば、滑落速度は滴下液量の増加に伴い大きく上昇した。SLIPS、SHS、未処理表面は、度重なるミスト噴霧に対して濡れ状態に転移したのに対して、本実施形態にかかる滑液膜は、噴霧に対して抵抗性を示した。本実施形態にかかる滑液膜上で、微小液体はCoalescence プロセスとSweep プロセスの連続によって効率的に除去されていることが確認された。Coalescence プロセスは微小液体の集合現象である。本滑液膜 表面では微小液体も一定の滑落速度を持つ。微小液体はそれぞれの親和力も含めて集まっていき、次第に成長を行っていく。続いてSweep プロセスは、Coalescence プロセスによって成長した液体が微小液体を吸収しながらどんどん速度を増して滑っていく現象を生じる。微小液体の吸収力は、本滑液膜表面上にとどまろうとする力よりもはるかに小さいため、成長液体が掃除機のように微小液体を吸い込みながら滑落していき、表面の微小水滴をきれいにふき取る。この２つのプロセスの連続によって本滑落膜表面では微小液体の滑落を促進することができた。
本滑落膜は、氷のブロックの優れた滑落性を示したが、質量をｍ、ρを密度、Vを体積としたとき、ｍ＝ρV よりV が小さいものを滑落させられるということは、ρが小さい氷のような物体も滑落できると考えられる。
Further, FIG. 14 shows a case where the synovial fluid film is rubbed, and in this case as well, as in the case where the synovial fluid film is damaged, the synovial fluid layer is repaired.
As described above, it is understood that the synovial membrane according to the present embodiment has an extremely high repairability and is an excellent synovial membrane.
Water droplets (10 μL) did not slide down on the glass surface, but slipped down at a sliding angle of 0.5 ° by forming a lubricant layer with DTMS. In general, an ultra-low viscosity liquid does not form a liquid film unless the substrate is flat, but in this embodiment, ultra-low viscosity DTMS is applied to a flat glass surface. Thus, according to the synovial membrane according to the present invention, the selectivity of the synovial fluid (pure synovial fluid) is very wide, and it can be said that the problem that the synovial fluid that can be used as in the past is limited is solved. .
In this embodiment, the synovial fluid film is formed on the glass. However, the base film formation by the silane bond used in this embodiment can be applied to any surface subjected to hydrophilic treatment. For example, when a base film was formed on a PET film, excellent performance was exhibited.
In addition, the synovial membrane of this embodiment showed excellent sliding properties against water, warm water (90 ° C.), saline (5 wt%), ice blocks, and blood. Although hot water has a lower surface tension than water and is accompanied by the deposition of a micro liquid by vapor, there are few reports of hot water sliding down, but the membrane of this case was able to slide down. This is considered to be because the fine liquid can be slid and the coalescence of the liquid particles proceeds. Further, the synovial fluid film according to the present embodiment showed blood slidability. In addition, blood showed complete non-adhesion performance for the dipping test on blood and the output image through the endoscope lens.
So far, SLIPS and super water-repellent surface (SHS) have been reported as approaches for non-adherent liquid surfaces. SLIPS slides liquids with immiscible lubricants (rolls the surface depending on conditions), while super water-repellent surfaces create an air layer at the interface between the liquid and the surface of the article, reducing the contact area. Can be rolled. According to Zuankai Wang et al. And Tak-sin wong et al., The liquid sliding speed is roughly inversely proportional to the viscosity of the lubricant layer. In addition, KK Varanasi et al. Report that the liquid sliding speed increases as the unevenness of the article surface decreases. The present inventors have also confirmed that unevenness on the surface of the article significantly reduces the liquid sliding property. And according to the present embodiment, DTMS (μ = 0.003 Pa · sec) which is significantly lower than the viscosity of the conventional lubricant can be maintained, and the unevenness of the article surface is RMS <1 nm or less. It can be said that the sliding speed was greatly increased.
There is also an example of forming the super-water-repellent SLIPS by making the uneven structure on the surface of the article into a needle-like structure, but the super-water-repellent SLIPS also depends on the lubricant viscosity. As a result, the water sliding speed of the synovial fluid film according to the present invention was dramatically improved as compared to SLIPS.
On the SHS surface, micro liquid is trapped in the concavo-convex structure, so that the pinning effect occurs and does not slide down (when <5 μL). As for SLIPS, the liquid slides very slowly (almost does not move) unless the liquid diameter becomes large to some extent. For this reason, it is difficult to remove the liquid from the surface of the article. It is very important to slide a micro liquid at a certain speed, for example, it is important to remove liquid that becomes difficult to remove due to coagulation and growth over time, such as blood and ice nuclei. . In particular, in the case of SLIPS, if the liquid enters the lubricant due to some external force such as spray pressure, the intruding liquid may not be removed. According to the synovial fluid film according to the present embodiment, the sliding speed greatly increased as the amount of the dropped liquid increased. The SLIPS, SHS, and untreated surfaces were transferred to a wet state with respect to repeated mist spraying, whereas the synovial fluid film according to this embodiment exhibited resistance to spraying. On the synovial membrane according to the present embodiment, it was confirmed that the micro liquid was efficiently removed by continuous Coalescence process and Sweep process. The Coalescence process is an aggregation phenomenon of micro liquids. On the surface of this synovial membrane, micro liquid also has a constant sliding speed. The micro liquids will gather together, including their affinity, and will gradually grow. Subsequently, the Sweep process causes a phenomenon in which the liquid grown by the Coalescence process slips at a higher speed while absorbing a minute liquid. Since the absorption capacity of the micro liquid is much smaller than the force that tries to stay on the surface of the synovial membrane, the growing liquid slides down while sucking in the micro liquid like a vacuum cleaner, and cleans the micro water droplets on the surface. . The continuation of these two processes promoted the sliding of the micro liquid on the surface of the sliding film.
This sliding membrane showed excellent sliding properties of ice blocks, but when mass is m, ρ is density, and V is volume, it is possible to slide a material having V smaller than m = ρV. It is thought that even ice-like objects can slide down.
Claims (11)
滑液剤層として前記ベース膜のπ電子官能基とπ相互作用により結合するπ相互作用部及び滑液対象となる流体と親和性の低い滑液作用部を分子内に有した層、
を含むことを特徴とする滑液膜。 A layer having a functional group having π electrons as a base film;
As a synovial fluid layer, a layer having in the molecule a π interaction part that binds by π interaction with the π electron functional group of the base film and a synovial fluid action part having a low affinity with the fluid to be synovial fluid,
A synovial membrane characterized by containing.
前記ベース膜のπ電子官能基とπ相互作用により結合するπ相互作用部と、滑液対象となる流体と親和性の低い滑液作用部を分子内に有した滑液剤を、前記ベース膜上に塗布することを特徴とするベース膜形成方法。 A base film constituent material having a π-electron-containing functional group is bonded to the surface of the article or interacted between molecules to form a base film
On the base film, a synovial agent having a π interaction part bonded to the π electron functional group of the base film by π interaction and a synovial liquid action part having a low affinity with the fluid to be synovial fluid in the molecule is provided on the base film. A base film forming method comprising applying to a base material.
A solar cell, a power transmission line, a building material (roof, window, wall), a transporting device (automobile, ship, aircraft) characterized by having a surface covered with the synovial fluid film according to any one of claims 1 to 5. , Tube material (heat transfer condenser, heat absorption, heat dissipation equipment).
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| WO2019142805A1 (en) | 2018-01-16 | 2019-07-25 | 東洋製罐グループホールディングス株式会社 | Packaging material for surfactant-containing product |
| KR20200102475A (en) | 2018-01-16 | 2020-08-31 | 도요세이칸 그룹 홀딩스 가부시키가이샤 | Packaging material for products containing surfactants |
| US11370207B2 (en) | 2018-01-16 | 2022-06-28 | Toyo Seikan Group Holdings, Ltd. | Packing material for surfactant-containing products |
| WO2023008241A1 (en) * | 2021-07-27 | 2023-02-02 | 株式会社村上開明堂 | Water-slip membrane and article having water-slip membrane on surface |
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