JP7613288B2 - Fluoropolyether-modified amidosilane compound, surface treatment composition and article, and method for synthesizing fluoropolyether-modified amidosilane compound - Google Patents
Fluoropolyether-modified amidosilane compound, surface treatment composition and article, and method for synthesizing fluoropolyether-modified amidosilane compound Download PDFInfo
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- JP7613288B2 JP7613288B2 JP2021103332A JP2021103332A JP7613288B2 JP 7613288 B2 JP7613288 B2 JP 7613288B2 JP 2021103332 A JP2021103332 A JP 2021103332A JP 2021103332 A JP2021103332 A JP 2021103332A JP 7613288 B2 JP7613288 B2 JP 7613288B2
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- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- YDUIRQHSXOFAIE-UHFFFAOYSA-N n-but-3-enylbut-3-en-1-amine Chemical compound C=CCCNCCC=C YDUIRQHSXOFAIE-UHFFFAOYSA-N 0.000 description 1
- RFDSGAGBPXOEEY-UHFFFAOYSA-N n-hex-5-enylhex-5-en-1-amine Chemical compound C=CCCCCNCCCCC=C RFDSGAGBPXOEEY-UHFFFAOYSA-N 0.000 description 1
- GOUUPCCFOSXURY-UHFFFAOYSA-N n-pent-4-enylpent-4-en-1-amine Chemical compound C=CCCCNCCCC=C GOUUPCCFOSXURY-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- AQZYBQIAUSKCCS-UHFFFAOYSA-N perfluorotripentylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AQZYBQIAUSKCCS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000004243 sweat Anatomy 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Polyethers (AREA)
- Paints Or Removers (AREA)
Description
本発明は、撥水撥油性、離型性、防汚性等に優れた硬化被膜を与える新規なフルオロポリエーテル変性アミドシラン化合物、このアミドシラン化合物及び／又はその部分加水分解縮合物を主成分とする表面処理剤組成物、及びこの表面処理剤組成物の硬化被膜を有する物品、並びにフルオロポリエーテル変性アミドシラン化合物の合成方法に関する。
The present invention relates to a novel fluoropolyether-modified amidosilane compound that provides a cured coating film that is excellent in water and oil repellency, releasability, stain resistance, etc., a surface treatment agent composition containing this amidosilane compound and/or a partial hydrolysis condensate thereof as a main component, an article having a cured coating film of this surface treatment agent composition , and a method for synthesizing the fluoropolyether-modified amidosilane compound .
一般にフルオロポリエーテル基含有化合物は、その表面エネルギーが非常に小さいために、撥水撥油性、耐薬品性、潤滑性、離型性、防汚性などの性状を有する。その性質を利用して、工業的にはガラス、金属、樹脂、紙、繊維などの幅広い物質表面の撥水撥油防汚剤、磁気記録媒体の滑剤、精密機器の防油剤、離型剤、化粧料、保護膜など幅広く利用されている。 In general, fluoropolyether group-containing compounds have very low surface energy and therefore have properties such as water and oil repellency, chemical resistance, lubricity, release properties, and stain resistance. Taking advantage of these properties, they are widely used industrially as water and oil repellent and stain resistant agents for the surfaces of a wide range of materials such as glass, metal, resin, paper, and fiber, as lubricants for magnetic recording media, oil repellents for precision instruments, release agents, cosmetics, and protective films.
しかし、その性質は、同時に他の基材に対する非粘着性、非密着性があることを示しており、基材表面に塗布することはできても、被膜を形成し、密着させることはできなかった。 However, its properties also indicate that it is non-adhesive and non-adherent to other substrates, and although it can be applied to the surface of a substrate, it is not possible to form a coating and make it adhere to the substrate.
一方、ガラスや布などの基材表面と有機化合物とを結合させるものとしては、シランカップリング剤がよく知られている。シランカップリング剤は、１分子中に有機官能基と反応性シリル基（一般にはアルコキシシリル基）を有する。アルコキシシリル基は、空気中の水分などによって自己加水分解縮合反応を起こしてシロキサンとなり、被膜を形成する。それと同時に、ガラスや金属などの表面と化学的・物理的に結合することによって、耐久性を有する強固な被膜となる。シランカップリング剤はこの性質を利用して各種基材表面のコーティング剤として幅広く利用されている。 On the other hand, silane coupling agents are well known as agents that bond organic compounds to the surfaces of substrates such as glass and cloth. Silane coupling agents have an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group undergoes an autohydrolysis condensation reaction with moisture in the air to become siloxane, forming a coating. At the same time, it chemically and physically bonds with the surface of glass, metal, etc., forming a durable, strong coating. Taking advantage of this property, silane coupling agents are widely used as coating agents for the surfaces of various substrates.
これらの特徴を生かしたものとして、特開２０００－３２７７７２号公報（特許文献１）には、下記式で示されるようなフルオロアミドシラン化合物が示され、パーフルオロヘキサンに溶解した塗工液を塗布、硬化することで、ガラス表面にパーフルオロポリエーテル（ＰＦＰＥ）の特性を付与している。
また、特開２００２－１２１２７７号公報（特許文献２）では、より耐久性、潤滑性が優れる化合物として、以下の基を有する化合物が示され、パーフルオロ（２－ブチルテトラヒドロフラン）に溶解させた塗工液を塗布、硬化することで、ガラス表面にパーフルオロポリエーテルの特性を付与している。
これらのような化合物を使ってパーフルオロポリエーテルの特性を物質表面に付与するには、できるだけフッ素含有率が高い構造、つまり長鎖フルオロポリエーテル構造を有するほうがよい。その一方でフッ素含有率の高い化合物は、非フッ素系化合物（非フッ素系溶剤）への溶解性が極めて悪く、物質表面に均一に塗工するにはフッ素を含有する低分子の揮発性成分、すなわちフッ素系溶剤を配合する必要がある。 To use such compounds to impart the properties of perfluoropolyether to the surface of a material, it is better to have a structure with as high a fluorine content as possible, i.e., a long-chain fluoropolyether structure. On the other hand, compounds with a high fluorine content have extremely poor solubility in non-fluorinated compounds (non-fluorinated solvents), and in order to apply them uniformly to the surface of a material, it is necessary to mix in a low-molecular-weight volatile component that contains fluorine, i.e., a fluorinated solvent.
一方、近年、環境面や生物に対する蓄積性、毒性などの懸念からＰＦＯＳ（ペルフルオロオクタンスルホン酸）、ＰＦＯＡ（ペルフルオロオクタン酸）などに代表される低分子フッ素化合物の規制が強化されてきており、フッ素系溶剤を使用するには一般有機溶剤とは異なる専用の除外設備、作業者への安全対策の強化などが必要になってきている。また一般的な非フッ素系溶剤と比較してフッ素系溶剤の価格は高価であり、コスト面からもフッ素系溶剤の使用量は低減を求められている。 On the other hand, in recent years, regulations on low molecular weight fluorine compounds such as PFOS (perfluorooctane sulfonic acid) and PFOA (perfluorooctanoic acid) have been strengthened due to concerns about the environment, bioaccumulation, and toxicity, and the use of fluorine-based solvents has required specialized exclusion equipment different from that for general organic solvents, as well as strengthened safety measures for workers. Furthermore, fluorine-based solvents are more expensive than general non-fluorine-based solvents, and there is a demand to reduce the amount of fluorine-based solvents used from a cost perspective as well.
このような社会的な背景から、近年フッ素系溶剤は使用できる量や作業環境が大きく制限される傾向にあり、フッ素系溶剤を使用せずに硬化物表面に優れたフッ素ポリマー（フルオロポリエーテル基含有化合物）の特性を付与できる化合物が求められている。 Due to this social background, in recent years, there has been a trend toward significant restrictions on the amount of fluorine-based solvents that can be used and the working environment, and there is a demand for compounds that can impart the excellent properties of fluoropolymers (fluoropolyether group-containing compounds) to the surface of cured products without using fluorine-based solvents.
本発明は、上記事情に鑑みなされたもので、フッ素系溶剤を実質的に使用せずに物品表面に塗工でき、硬化物表面に優れた表面特性を付与することができる表面処理剤として使用できるフルオロポリエーテル変性アミドシラン化合物、及び該フルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を主成分とする塗工用組成物（表面処理剤組成物）、並びにフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物によって形成される硬化被膜を有する物品、並びにフルオロポリエーテル変性アミドシラン化合物の合成方法を提供することを目的とする。
The present invention has been made in view of the above circumstances, and has an object to provide a fluoropolyether-modified amidosilane compound that can be applied to the surface of an article substantially without using a fluorine-based solvent and can be used as a surface treatment agent capable of imparting excellent surface properties to the surface of a cured product; a coating composition (surface treatment agent composition) containing the fluoropolyether-modified amidosilane compound and/or a partial hydrolyzed condensate thereof as a main component; an article having a cured coating formed from the fluoropolyether-modified amidosilane compound and/or a partial hydrolyzed condensate thereof; and a method for synthesizing the fluoropolyether-modified amidosilane compound .
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、下記一般式（１）で示される新規なフルオロポリエーテル変性アミドシラン化合物が、フッ素原子を含まない有機溶剤で希釈、塗工することが可能であり、得られた塗膜を乾燥硬化させることで、物質表面に撥水撥油性、防汚性等、優れたパーフルオロポリエーテルの特性を付与することができることを見出し、本発明をなすに至った。
従って、本発明は、下記のフルオロポリエーテル変性アミドシラン化合物及び表面処理剤組成物並びに物品を提供する。
［１］
下記一般式（１）
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物。
［２］
上記一般式（１）において、Ｒｆが下記一般式（２）で示されるものである［１］に記載のフルオロポリエーテル変性アミドシラン化合物。
－ＣＦ（Ｙ）－Ｏ－Ｒｆ1－ＣＦ（Ｙ）－ （２）
（式中、ＹはＦ又はＣＦ3であり、Ｒｆ1は以下のパーフルオロオキシアルキレン単位の１種又は２種以上から選ばれる繰り返し単位からなる。）
－ＣＦ2Ｏ－
－ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ（ＣＦ3）ＣＦ2Ｏ－
－ＣＦ2ＣＦ（ＣＦ3）Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＯＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
［３］
上記一般式（１）において、Ｒｆが、以下のいずれかで示されるものである［１］又は［２］に記載のフルオロポリエーテル変性アミドシラン化合物。
－ＣＦ2Ｏ（ＣＦ2Ｏ）p（ＣＦ2ＣＦ2Ｏ）qＣＦ2－
（式中、ｐは１０～３００の整数、ｑは５～１７０の整数であり、かつｐ＋ｑは１５～４７０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数であり、各繰り返し単位の配列はランダムである。）
－ＣＦ2ＣＦ2Ｏ［ＣＦ2ＣＦ2ＣＦ2Ｏ］wＣＦ2ＣＦ2－
（式中、ｗは８～１１９の整数である。）
－ＣzＦ2zＯ（ＣＦ2ＣＦ2Ｏ）x（ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ）yＣzＦ2z－
（式中、ｘは２～３００の整数、ｙは２～８０の整数であり、かつｘ＋ｙは４～３８０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数である。ｚは単位毎に独立に１又は２である。各繰り返し単位の配列はランダムである。）
［４］
上記一般式（１）において、Ｚが下記式で示され、ａが３である［１］～［３］のいずれかに記載のフルオロポリエーテル変性アミドシラン化合物。
上記一般式（１）において、Ｍが炭素数１～１０のアルコキシ基である［１］～［４］のいずれかに記載のフルオロポリエーテル変性アミドシラン化合物。
［６］
不揮発性フッ素含有有機化合物を含有する表面処理剤組成物であって、該不揮発性フッ素含有有機化合物が、［１］～［５］のいずれかに記載のフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を８０質量％以上含むものである表面処理剤組成物。
［７］
不揮発性フッ素含有有機化合物の平均フッ素含有率が４０～６５質量％である［６］に記載の表面処理剤組成物。
［８］
更に、沸点が２５～２６０℃の有機溶剤を含有する表面処理剤組成物であって、該表面処理剤組成物中における上記フルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の含有率が０．０１～９５質量％である［６］又は［７］に記載の表面処理剤組成物。
［９］
有機溶剤がフッ素原子を含まないものである［８］に記載の表面処理剤組成物。
［１０］
［６］～［９］のいずれかに記載の表面処理剤組成物の硬化被膜を有する物品。
［１１］
下記一般式（４）
で示されるフルオロポリエーテルアミド化合物の４個のアルケニル基に、それぞれ下記一般式（５）
で示されるオルガノシロキサン化合物のＳｉＨ基をヒドロシリル化付加反応により付加して、下記一般式
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物を得るものであるフルオロポリエーテル変性アミドシラン化合物の合成方法。
［１２］
下記一般式（４）
で示されるフルオロポリエーテルアミド化合物の４個のアルケニル基に、モル当量として過剰量の下記一般式（６）
で示されるオルガノシロキサン化合物の片方のＳｉＨ基をヒドロシリル化付加反応によって付加させたのちに、残存する上記一般式（６）で示される化合物を取り除き、得られた下記一般式（７）
で示される化合物の分子鎖両末端のＳｉＨ基に、下記一般式（８）
で示されるアルケニル基含有加水分解性シラン化合物のアルケニル基をヒドロシリル化付加反応によって付加して、下記一般式
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物を得るものであるフルオロポリエーテル変性アミドシラン化合物の合成方法。
Accordingly, the present invention provides the following fluoropolyether-modified amidosilane compound, surface treatment agent composition, and article.
[1]
The following general formula (1)
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The fluoropolyether-modified amidosilane compound is represented by the formula:
[2]
The fluoropolyether-modified amidosilane compound according to [1], wherein Rf in the above general formula (1) is represented by the following general formula (2):
-CF(Y)-O-Rf 1 -CF(Y)- (2)
(In the formula, Y is F or CF3 , and Rf1 is a repeating unit selected from one or more of the following perfluorooxyalkylene units.)
-CF2O-
-CF2CF2O-
-CF 2 CF 2 CF 2 O-
-CF( CF3 ) CF2O-
-CF 2 CF(CF 3 )O-
-CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O-
[3]
The fluoropolyether-modified amidosilane compound according to [1] or [2], wherein in the general formula (1), Rf is any one of the following:
-CF 2 O (CF 2 O) p (CF 2 CF 2 O) q CF 2 -
(In the formula, p is an integer of 10 to 300, q is an integer of 5 to 170, and p+q is an integer of 15 to 470 such that the number average molecular weight of Rf is 1,500 to 20,000, and the arrangement of each repeating unit is random.)
-CF 2 CF 2 O [CF 2 CF 2 CF 2 O] w CF 2 CF 2 -
(In the formula, w is an integer from 8 to 119.)
-C z F 2z O (CF 2 CF 2 O) x (CF 2 CF 2 CF 2 CF 2 O) y C z F 2z -
(In the formula, x is an integer of 2 to 300, y is an integer of 2 to 80, and x+y is an integer of 4 to 380 such that the number average molecular weight of Rf is 1,500 to 20,000. z is independently 1 or 2 for each unit. The arrangement of each repeating unit is random.)
［ 4 ］
The fluoropolyether-modified amidosilane compound according to any one of [1] to [ 3 ], wherein, in the above general formula (1), Z is represented by the following formula, and a is 3:
The fluoropolyether-modified amidosilane compound according to any one of [1] to [ 4 ], wherein in the general formula (1), M is an alkoxy group having 1 to 10 carbon atoms.
［ ６ ］
A surface treatment agent composition containing a non-volatile fluorine-containing organic compound, the non-volatile fluorine-containing organic compound containing 80 mass% or more of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate according to any one of [1] to [ 5 ].
［ ７ ］
The surface treatment agent composition according to [ 7 ], wherein the non-volatile fluorine-containing organic compound has an average fluorine content of 40 to 65 mass%.
［ 8 ］
The surface treatment agent composition according to [6] or [7] further contains an organic solvent having a boiling point of 25 to 260°C, and the content of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate in the surface treatment agent composition is 0.01 to 95 mass%.
［ ９ ］
The surface treatment composition according to [ 8 ], wherein the organic solvent does not contain a fluorine atom.
[ 10 ]
An article having a cured coating of the surface treatment composition according to any one of [ 6 ] to [ 9 ].
［ １１ ］
The following general formula (4)
The four alkenyl groups of the fluoropolyether amide compound represented by the following general formula (5) are
The SiH group of the organosiloxane compound represented by the following general formula is added by hydrosilylation addition reaction to obtain a compound represented by the following general formula:
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The present invention relates to a method for synthesizing a fluoropolyether-modified amidosilane compound, the method comprising the steps of:
［ １２ ］
The following general formula (4)
and an excess amount of a compound represented by the following general formula (6) in terms of molar equivalent to four alkenyl groups of a fluoropolyetheramide compound represented by the following general formula (6):
The remaining compound represented by the above general formula (6) is removed to obtain an organosiloxane compound represented by the following general formula (7):
to the SiH groups at both ends of the molecular chain of a compound represented by the following general formula (8):
The alkenyl group of the alkenyl-containing hydrolyzable silane compound represented by the following general formula is added by hydrosilylation addition reaction to obtain a compound represented by the following general formula:
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The present invention relates to a method for synthesizing a fluoropolyether-modified amidosilane compound, the method comprising the steps of:
本発明の新規なフルオロポリエーテル変性アミドシラン化合物は、フッ素原子を含まない有機溶剤で希釈、塗工することが可能であり、該アミドシラン化合物及び／又はその部分加水分解縮合物を主成分とする表面処理剤組成物を物品の表面に塗工し、塗膜を乾燥硬化させて硬化被膜を得ることで、物質表面に撥水撥油性、防汚性等、優れたパーフルオロポリエーテルの特性を付与することができる。 The novel fluoropolyether-modified amidosilane compound of the present invention can be diluted and coated with an organic solvent that does not contain fluorine atoms. By coating the surface of an article with a surface treatment composition that contains the amidosilane compound and/or its partial hydrolysis condensate as the main component, and drying and curing the coating to obtain a cured coating, the excellent properties of perfluoropolyether, such as water and oil repellency and stain resistance, can be imparted to the surface of the material.
以下、本発明を詳細に説明する。
本発明のフルオロポリエーテル変性アミドシラン化合物は、下記一般式（１）で示されるものである。
The fluoropolyether-modified amidosilane compound of the present invention is represented by the following general formula (1).
上記一般式（１）において、Ｒｆは数平均分子量１，５００～２０，０００、好ましくは１，５００～１０，０００の２価パーフルオロポリエーテル基である。Ｒｆの数平均分子量が１，５００未満であると化合物中のフッ素含有率が低すぎるため付与できるパーフルオロポリエーテルの特性が不十分となり、２０，０００を超えるとフッ素含有基（パーフルオロポリエーテル基）の構造が長くなりすぎるため非フッ素系溶剤に対する溶解が困難になる。 In the above general formula (1), Rf is a divalent perfluoropolyether group having a number average molecular weight of 1,500 to 20,000, preferably 1,500 to 10,000. If the number average molecular weight of Rf is less than 1,500, the fluorine content in the compound is too low, making it difficult to impart perfluoropolyether properties, and if it exceeds 20,000, the structure of the fluorine-containing group (perfluoropolyether group) becomes too long, making it difficult to dissolve in a non-fluorine-based solvent.
なお、本発明において、分子量（又は重合度もしくは繰り返し単位の数）は、フッ素系溶剤を展開溶媒としたゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析によるポリスチレン換算あるいはポリメタクリル酸メチル換算の数平均分子量（又は数平均重合度）として求めることができるが、好適には、1Ｈ－ＮＭＲ分析及び19Ｆ－ＮＭＲ分析に基づくフルオロポリエーテル変性アミドシラン化合物の末端構造と主鎖構造との特性ピーク強度比率から算出される数平均分子量（又は数平均重合度）である（以下、同じ）。 In the present invention, the molecular weight (or degree of polymerization or number of repeating units) can be determined as a number average molecular weight (or number average degree of polymerization) in terms of polystyrene or polymethyl methacrylate by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the developing solvent, but is preferably a number average molecular weight (or number average degree of polymerization) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoropolyether-modified amidosilane compound based on 1H -NMR analysis and 19F-NMR analysis (the same applies below).
Ｒｆとして、特には、下記一般式（２）で示される２価パーフルオロポリエーテル基であることが好ましい。
－ＣＦ（Ｙ）－Ｏ－Ｒｆ1－ＣＦ（Ｙ）－ （２）
Rf is particularly preferably a divalent perfluoropolyether group represented by the following general formula (2).
-CF(Y)-O-Rf 1 -CF(Y)- (2)
ここで、一般式（２）中、ＹはＦ又はＣＦ3であり、Ｒｆ1は以下のパーフルオロオキシアルキレン単位の１種又は２種以上から選ばれる繰り返し単位からなる。なお、繰り返し単位数は、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数である。
－ＣＦ2Ｏ－
－ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ（ＣＦ3）ＣＦ2Ｏ－
－ＣＦ2ＣＦ（ＣＦ3）Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＯＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
In the general formula (2), Y is F or CF3 , and Rf1 is a repeating unit selected from one or more of the following perfluorooxyalkylene units. The number of repeating units is such that the number average molecular weight of Rf is 1,500 to 20,000.
-CF2O-
-CF2CF2O-
-CF 2 CF 2 CF 2 O-
-CF( CF3 ) CF2O-
-CF 2 CF(CF 3 )O-
-CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O-
特に、上記一般式（１）におけるＲｆ（又は上記一般式（２）；－ＣＦ（Ｙ）－Ｏ－Ｒｆ1－ＣＦ（Ｙ）－）で示される２価パーフルオロポリエーテル基としては、以下の例示式で示されるものが好ましい。
－ＣＦ2Ｏ（ＣＦ2Ｏ）p（ＣＦ2ＣＦ2Ｏ）qＣＦ2－、
－ＣzＦ2zＯ（ＣＦ2ＣＦ2Ｏ）x（ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ）yＣzＦ2z－
In particular, as the divalent perfluoropolyether group represented by Rf in the above general formula (1) (or the above general formula (2); --CF(Y)--O-- Rf.sub.1 --CF(Y)--), those represented by the following exemplary formulas are preferred.
-CF 2 O (CF 2 O) p (CF 2 CF 2 O) q CF 2 -,
-C z F 2z O (CF 2 CF 2 O) x (CF 2 CF 2 CF 2 CF 2 O) y C z F 2z -
上記式中、ｐは１０～３００の整数であり、好ましくは１０～１００の整数である。ｑは５～１７０の整数であり、好ましくは１０～１００の整数である。ｐ＋ｑは１５～４７０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数であり、好ましくは１７～３００の整数であって、Ｒｆの数平均分子量が１，５００～２０，０００を満たす場合であり、より好ましくは２０～２００の整数である。ｐ、ｑがこれらの範囲より小さいと、十分にパーフルオロポリエーテルの特性を与えることが難しくなり、これらの範囲より大きくなると沸点が２５～２６０℃の有機溶剤（特にフッ素原子を含まない有機溶剤）への溶解性（以下、溶解性に関して同じ）が低下する。更にｑ／ｐの値が０．７以上１．５以下であることが好ましく、０．８以上１．２以下であることがより好ましい。０．７より小さくなるとフルオロポリエーテル構造の耐久性が低下し、１．５より大きくなるとポリマーの柔軟性が失われ、溶解性が低下する。なお、ｐ、ｑが付された括弧内に示される各繰り返し単位の配列はランダムである。 In the above formula, p is an integer of 10 to 300, preferably an integer of 10 to 100. q is an integer of 5 to 170, preferably an integer of 10 to 100. p+q is an integer of 15 to 470, where the number average molecular weight of Rf is 1,500 to 20,000, preferably an integer of 17 to 300, where the number average molecular weight of Rf is 1,500 to 20,000, more preferably an integer of 20 to 200. If p and q are smaller than these ranges, it becomes difficult to give sufficient perfluoropolyether properties, and if they are larger than these ranges, the solubility in organic solvents (particularly organic solvents that do not contain fluorine atoms) with a boiling point of 25 to 260 ° C (hereinafter the same applies to solubility) decreases. Furthermore, the value of q/p is preferably 0.7 to 1.5, more preferably 0.8 to 1.2. If it is less than 0.7, the durability of the fluoropolyether structure decreases, and if it is more than 1.5, the polymer loses flexibility and its solubility decreases. Note that the arrangement of each repeating unit shown in parentheses with p and q is random.
上記式中、ｓ、ｔは独立に１～１２０の整数であり、好ましくは５～６０の整数であり、かつｓ＋ｔは２～２４０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数であり、好ましくは４～１１９の整数であって、Ｒｆの数平均分子量が１，５００～２０，０００を満たす場合であり、より好ましくは１０～１００の整数であり、更に好ましくは１５～１００の整数である。ｓ＋ｔがこれより小さいと十分にパーフルオロポリエーテルの特性を与えることが難しくなり、これより大きくなると溶解性が大きく低下する、ｕは１～６の整数であり、好ましくは２～４の整数であり、ｖは０～１０の整数であり、好ましくは１～４の整数である。 In the above formula, s and t are independently integers from 1 to 120, preferably from 5 to 60, and s+t is an integer from 2 to 240 such that the number average molecular weight of Rf is 1,500 to 20,000, preferably an integer from 4 to 119, in which case the number average molecular weight of Rf is 1,500 to 20,000, more preferably an integer from 10 to 100, and even more preferably an integer from 15 to 100. If s+t is smaller than this, it becomes difficult to impart sufficient perfluoropolyether properties, and if it is larger than this, the solubility is greatly reduced, u is an integer from 1 to 6, preferably an integer from 2 to 4, and v is an integer from 0 to 10, preferably an integer from 1 to 4.
上記式中、ｗは８～１１９の整数であり、好ましくは１０～１００の整数である。この範囲より小さいと、十分にパーフルオロポリエーテルの特性を与えることが難しくなり、これより大きくなると溶解性が低下する。 In the above formula, w is an integer between 8 and 119, and preferably between 10 and 100. If it is smaller than this range, it becomes difficult to impart sufficient perfluoropolyether properties, and if it is larger than this range, solubility decreases.
上記式中、ｘは２～３００の整数であり、好ましくは２～１００の整数であり、ｙは２～８０の整数であり、好ましくは２～６０の整数であり、ｘ＋ｙは４～３８０の整数
のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数であり、好ましくは５～１６３の整数であって、Ｒｆの数平均分子量が１，５００～２０，０００を満たす場合であり、より好ましくは６～１４０の整数であって、Ｒｆの数平均分子量が１，５００～２０，０００を満たす場合である。ｘ、ｙがこれらの範囲より小さいと、十分にパーフルオロポリエーテルの特性を与えることが難しくなり、これらの範囲より大きくなると溶解性が低下する。ｚは単位毎に独立に１又は２である。また、ｘ、ｙが付された括弧内に示される各繰り返し単位の並びはランダムであるが、－ＣＦ2ＣＦ2ＯＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－の配列を繰り返し構造としていてもよい。
In the above formula, x is an integer of 2 to 300, preferably an integer of 2 to 100, y is an integer of 2 to 80, preferably an integer of 2 to 60, and x+y is an integer of 4 to 380, where the number average molecular weight of Rf is 1,500 to 20,000, preferably an integer of 5 to 163, where the number average molecular weight of Rf is 1,500 to 20,000, and more preferably an integer of 6 to 140, where the number average molecular weight of Rf is 1,500 to 20,000. If x and y are smaller than these ranges, it becomes difficult to give sufficient perfluoropolyether properties, and if they are larger than these ranges, the solubility decreases. z is independently 1 or 2 for each unit. The repeating units shown in the parentheses to which x and y are added are arranged randomly, but may have a repeating structure of --CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O--.
これらの上記した群の繰り返し単位には、製法、精製法などの理由により、例示される繰り返し単位以外に炭素数が１～６のフルオロアルキルエーテル構造が溶解性や表面処理剤組成物として与える特性に影響の無い範囲、具体的には０～３モル％の範囲で混入していてもよい。 The repeating units in the above groups may contain, in addition to the repeating units exemplified, a fluoroalkyl ether structure having 1 to 6 carbon atoms within a range that does not affect the solubility or properties imparted to the surface treatment composition, specifically within a range of 0 to 3 mol %, due to reasons such as the manufacturing method and purification method.
上記一般式（１）において、Ｚはそれぞれ独立に少なくとも１つのＳｉ－Ｏ－Ｓｉの結合を含む２価の連結基、特には直鎖状のジオルガノポリシロキサン構造を含有する連結基であり、特に下記式（３）で示されるものが好ましい。なお、下記の構造において、左側の結合手はＮと、右側の結合手はＳｉと結合することが好ましい。
式（３）で示される構造としては、下記に示すものが例示できる。なお、下記の構造において、左側の結合手はＮと、右側の結合手はＳｉと結合する。
上記一般式（１）において、Ｍはそれぞれ独立に、炭素数１～１０、好ましくは炭素数１～６のアルコキシ基、炭素数２～１０、好ましくは炭素数２～４のアルコキシアルコキシ基、炭素数２～１０、好ましくは炭素数２～７のアシロキシ基、炭素数２～１０、好ましくは炭素数２～６のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基である。具体的には、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基、エトキシメトキシ基、エトキシエトキシ基等のアルコキシアルコキシ基、アセトキシ基等のアシロキシ基、イソプロペノキシ基等のアルケニルオキシ基、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子などが挙げられ、これらの中でも、特にメトキシ基、エトキシ基、メトキシメトキシ基、アセトキシ基が好適である。 In the above general formula (1), each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, preferably 2 to 7 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, and a halogen atom. Specific examples include alkoxy groups such as methoxy, ethoxy, propoxy, and isopropoxy groups, alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups, acyloxy groups such as acetoxy groups, alkenyloxy groups such as isopropenoxy groups, and halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Among these, methoxy, ethoxy, methoxymethoxy, and acetoxy groups are particularly preferred.
上記一般式（１）において、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基などが挙げられ、特にメチル基が好ましい。 In the above general formula (1), each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, and hexyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, and phenyl groups, with methyl being particularly preferred.
上記一般式（１）において、ａは２又は３であるが、特に３が好ましい。 In the above general formula (1), a is 2 or 3, with 3 being particularly preferred.
このようなフルオロポリエーテル変性アミドシラン化合物の具体的な合成方法としては、例えば、以下の方法を示すことができる。 Specific examples of methods for synthesizing such fluoropolyether-modified amidosilane compounds include the following:
第１の方法として、下記一般式（４）
で示される分子鎖両末端にそれぞれ２個ずつ（分子中に４個の）アルケニル基を有するフルオロポリエーテルアミド化合物の４個のアルケニル基に、それぞれ下記一般式（５）
で示される分子鎖片末端にＳｉＨ基（ケイ素原子に結合した水素原子）を有し、他方の末端に加水分解性シリル基を有するオルガノシロキサン化合物のＳｉＨ基をヒドロシリル化付加反応により付加する方法が挙げられる。
As a first method, a compound represented by the following general formula (4)
The four alkenyl groups of a fluoropolyetheramide compound having two alkenyl groups at each of both ends of the molecular chain (four alkenyl groups in the molecule), each of which is represented by the following general formula (5):
An example of such a method is to add, by hydrosilylation addition reaction, the SiH group of an organosiloxane compound having a SiH group (a hydrogen atom bonded to a silicon atom) at one end of the molecular chain and a hydrolyzable silyl group at the other end.
また第２の方法として、上記一般式（４）で示される分子鎖両末端にそれぞれ２個ずつ（分子中に４個の）アルケニル基を有するフルオロポリエーテルアミド化合物の４個のアルケニル基に、モル当量として過剰量の下記一般式（６）
で示される分子鎖両末端にＳｉＨ基（ケイ素原子に結合した水素原子）を有するオルガノシロキサン化合物の片方のＳｉＨ基をヒドロシリル化付加反応によって付加させたのちに、残存する上記一般式（６）で示される化合物を取り除き、得られた下記一般式（７）
で示される化合物の分子鎖両末端のＳｉＨ基に、下記一般式（８）
で示されるアルケニル基含有加水分解性シラン化合物のアルケニル基をヒドロシリル化付加反応によって付加することで合成できる。
As a second method, a fluoropolyetheramide compound having two alkenyl groups at each of both ends of the molecular chain (four alkenyl groups in the molecule) represented by the above general formula (4) is mixed with an excess amount of a compound represented by the following general formula (6) in terms of molar equivalent to the four alkenyl groups:
The organosiloxane compound having SiH groups (hydrogen atoms bonded to silicon atoms) at both ends of the molecular chain, represented by the following general formula (7), is then added with one of the SiH groups by hydrosilylation addition reaction, and the remaining compound represented by the above general formula (6) is removed to obtain
to the SiH groups at both ends of the molecular chain of a compound represented by the following general formula (8):
The compound can be synthesized by adding an alkenyl group to an alkenyl-containing hydrolyzable silane compound represented by the following formula (I):
ここで、上記一般式（４）で示される分子鎖両末端にそれぞれ２個ずつ（分子中に４個の）アルケニル基を有するフルオロポリエーテルアミド化合物は、例えば下記一般式（９）で示されるフルオロポリエーテルカルボン酸誘導体に、下記一般式（１０）で示される末端アルケニル基含有１価炭化水素基を２個有するアミン化合物を公知のアミド化の手法により反応させることで合成可能である。
［ＣＨ2＝ＣＲ1ＣdＨ2d］2－ＮＨ （１０）
（式中、Ｒ1、ｄは上記と同じであり、但し、連結するＣＨ2＝ＣＲ1ＣdＨ2dの炭素数の合計はそれぞれ２～１０である。）
Here, the fluoropolyether amide compound having two alkenyl groups at each of both molecular chain terminals (four alkenyl groups in the molecule) represented by the above general formula (4) can be synthesized, for example, by reacting a fluoropolyether carboxylic acid derivative represented by the following general formula (9) with an amine compound having two terminal alkenyl-containing monovalent hydrocarbon groups represented by the following general formula (10) by a known amidation method.
[CH 2 =CR 1 C d H 2d ] 2 -NH (10)
(In the formula, R 1 and d are the same as above, with the proviso that the total number of carbon atoms in each of the linked CH 2 ═CR 1 C d H 2d is 2 to 10.)
一般式（９）で示されるフルオロポリエーテルカルボン酸誘導体の具体的な例としては、下記に示すものを挙げることができる。
一般式（１０）で示される末端アルケニル基含有１価炭化水素基を２個有するアミン化合物の具体的な例としては、ジアリルアミン、ジ（３－ブテニル）アミン、ジ（４－ペンテニル）アミン、ジ（５－ヘキセニル）アミン等を示すことができる。 Specific examples of amine compounds having two terminal alkenyl-containing monovalent hydrocarbon groups as shown in general formula (10) include diallylamine, di(3-butenyl)amine, di(4-pentenyl)amine, and di(5-hexenyl)amine.
一般式（９）で示される化合物と一般式（１０）で示される化合物の反応では、特に一般式（９）で示される化合物がカルボン酸ハロゲン化物であるものに、必要に応じて、溶剤、反応触媒等を加えて攪拌、あるいは加熱攪拌する方法が簡便である。ここで、加熱する場合の条件としては、０～１５０℃、特に２０～１００℃にて５分～２００時間、特に３０分～２４時間とすることが好ましい。 In the reaction of a compound represented by general formula (9) with a compound represented by general formula (10), it is particularly convenient to add a solvent, a reaction catalyst, etc., as necessary, to the compound represented by general formula (9) which is an carboxylic acid halide, and then stir or heat and stir. Here, the heating conditions are preferably 0 to 150°C, particularly 20 to 100°C, for 5 minutes to 200 hours, particularly 30 minutes to 24 hours.
上記の反応に使用する一般式（１０）で示される化合物の量は、一般式（９）で示される化合物中に含まれるＣＯＸ基のモル数を１としたときに、１～５モル、好ましくは１～１．５倍モルであることが望ましい。１モルより小さいと、未反応の末端基が残存し、５モルより大きいと未反応の一般式（１０）で示される化合物を除去する際の負担が大きくなる。 The amount of the compound represented by general formula (10) used in the above reaction is desirably 1 to 5 moles, preferably 1 to 1.5 moles, when the number of moles of the COX group contained in the compound represented by general formula (9) is taken as 1. If it is less than 1 mole, unreacted terminal groups will remain, and if it is more than 5 moles, the burden of removing the unreacted compound represented by general formula (10) will be large.
また上記の反応は、溶剤が存在しなくても、反応系内を十分攪拌することで実施可能であるが、必要に応じて溶剤で希釈してもよい。このとき希釈溶剤は一般式（９）で示される化合物と一般式（１０）で示される化合物の両方を溶解する溶剤を利用することができるが、溶剤としては、沸点が目的とする反応温度以上でかつ反応を阻害せず、反応に使用する一般式（９）で示される化合物、一般式（１０）で示される化合物及び生成する一般式（４）で示される化合物が、上記反応温度において可溶であるものが好ましい。このような溶剤としては、例えば、ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等のフッ素変性芳香族炭化水素系溶剤、メチルパーフルオロブチルエーテル等のフッ素変性エーテル系溶剤などの部分フッ素変性された溶剤が望ましく、特にｍ－キシレンヘキサフロライドが好ましい。 The above reaction can be carried out without the presence of a solvent by thoroughly stirring the reaction system, but it may be diluted with a solvent if necessary. In this case, a solvent that dissolves both the compound represented by general formula (9) and the compound represented by general formula (10) can be used as the dilution solvent. However, the solvent is preferably one that has a boiling point equal to or higher than the target reaction temperature, does not inhibit the reaction, and is soluble in the compound represented by general formula (9) used in the reaction, the compound represented by general formula (10), and the compound represented by general formula (4) produced at the reaction temperature. As such a solvent, for example, a partially fluorinated solvent such as a fluorinated aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride, or a fluorinated ether solvent such as methyl perfluorobutyl ether is preferable, and m-xylene hexafluoride is particularly preferable.
溶剤を使用する場合、その使用量は、式（９）で示される化合物１００質量部に対して、好ましくは５～２，０００質量部であり、より好ましくは５０～５００質量部である。これより少なければ溶剤による希釈の効果が薄くなり、多ければ希釈度が高くなりすぎて反応速度の低下を招く場合がある。 When a solvent is used, the amount used is preferably 5 to 2,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of the compound represented by formula (9). If the amount is less than this, the effect of dilution by the solvent will be weak, and if the amount is more, the degree of dilution will be too high, which may lead to a decrease in the reaction rate.
反応触媒を用いる場合、公知のいかなるものを用いてもよいが、脱離するＨＸ（Ｘは上記と同じ）と塩を形成するトリエチルアミン等のトリアルキルアミンなどの３級アミン類や、ジアザビシクロウンデセン、ジアザビシクロノネン等及びこれらの混合物が望ましい。
反応触媒を用いる場合、その使用量は、脱離するＨＸ量に対して、好ましくは１～５倍モル、より好ましくは１～２倍モルである。反応触媒が１倍モルより少ないと塩を形成しないＨＸが残存するため除去しにくくなる場合があり、５倍モルより多いと余剰の触媒の除去がしにくくなる場合がある。
When a reaction catalyst is used, any known one may be used, but tertiary amines such as trialkylamines such as triethylamine which form salts with the HX (X is the same as above) to be eliminated, diazabicycloundecene, diazabicyclononene, etc., and mixtures thereof are preferable.
When a reaction catalyst is used, the amount used is preferably 1 to 5 times, more preferably 1 to 2 times, the molar amount of HX to be eliminated. If the reaction catalyst is used in an amount less than 1 time, HX that does not form a salt remains and may be difficult to remove, whereas if the amount is more than 5 times, the excess catalyst may be difficult to remove.
反応終了後、未反応の式（１０）で示される化合物、反応触媒、及び溶剤等を減圧留去、抽出、吸着等の公知の方法で除去することが好ましい。 After the reaction is completed, it is preferable to remove the unreacted compound represented by formula (10), the reaction catalyst, the solvent, and the like by a known method such as vacuum distillation, extraction, or adsorption.
上記一般式（４）で示される分子鎖両末端にそれぞれ２個ずつ（分子中に４個の）アルケニル基を有するフルオロポリエーテルアミド化合物としては、例えば、下記に示すものが例示できる。
上記一般式（５）で示される分子鎖片末端にＳｉＨ基（ケイ素原子に結合した水素原子）を有し、他方の末端に加水分解性シリル基を有するオルガノシロキサン化合物としては、例えば、下記に示すものが例示できる。
また、上記一般式（６）で示される分子鎖両末端にＳｉＨ基（ケイ素原子に結合した水素原子）を有するオルガノシロキサン化合物としては、例えば、下記に示すものが例示できる。
上記式（４）で示される化合物と上記式（５）又は式（６）で示される化合物との反応は、公知のヒドロシリル化反応によってなされる。このヒドロシリル化（付加）反応は、式（４）で示される化合物と、式（５）又は式（６）で示される化合物とを混合し、白金族金属系の付加反応触媒存在下、反応温度５０～１５０℃、好ましくは６０～１２０℃で、１分～４８時間、特に１０分～１２時間反応を行うことが望ましい。反応温度が低すぎると反応が十分に進行しないまま停止してしまう場合があり、高すぎるとヒドロシリル化の反応熱による温度上昇で反応が制御できなくなり、突沸や原料の分解などが起こる場合がある。 The reaction between the compound represented by formula (4) and the compound represented by formula (5) or (6) is carried out by a known hydrosilylation reaction. This hydrosilylation (addition) reaction is carried out by mixing the compound represented by formula (4) and the compound represented by formula (5) or (6) in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 48 hours, and particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the hydrosilylation reaction heat, and bumping or decomposition of the raw materials may occur.
上記式（４）で示される化合物と、上記式（５）で示される化合物の反応割合は、式（４）で示される化合物のアルケニル基の総モル数に対して、式（５）で示される化合物を１～２倍モル、特に１～１．５倍モル使用して反応させることが望ましい。式（５）で示される化合物がこれより少なすぎると式（４）で示される化合物の片末端にアルケニル基が残存した化合物が副生成物として発生する。式（５）で示される化合物がこれより多すぎると反応溶液の均一性が低下して反応速度が不安定となる。また反応後に未反応の式（５）で示される化合物の除去を行う場合に、加熱、減圧、抽出等の条件を未反応分が増える分だけ厳しくする必要が出てくる。 The reaction ratio of the compound represented by formula (4) and the compound represented by formula (5) is preferably 1 to 2 times, and particularly 1 to 1.5 times, the molar amount of the compound represented by formula (5) relative to the total number of moles of the alkenyl groups in the compound represented by formula (4). If the amount of the compound represented by formula (5) is less than this amount, a compound with an alkenyl group remaining at one end of the compound represented by formula (4) is generated as a by-product. If the amount of the compound represented by formula (5) is more than this amount, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when removing the unreacted compound represented by formula (5) after the reaction, it becomes necessary to make the conditions of heating, decompression, extraction, etc. stricter in proportion to the increase in the amount of unreacted compounds.
上記式（４）で示される化合物と、上記式（６）で示される化合物の反応割合は、式（４）で示される化合物のアルケニル基の総モル数に対して、式（６）で示される化合物をモル当量として過剰量、すなわち２～２０倍モル、特に４～１０倍モル使用して反応させることが望ましい。式（６）で示される化合物がこれより少なすぎると式（６）で示される化合物の両末端ＳｉＨ基が式（４）で示される化合物のアルケニル基と反応した化合物が副生成物として発生し、目的物を得ることができない。式（６）で示される化合物がこれより多すぎると反応溶液の均一性が低下して反応速度が不安定となる。また反応後に未反応の式（６）で示される化合物の除去を行う場合に、加熱、減圧、抽出等の条件を未反応分が増える分だけ厳しくする必要が出てくる。 The reaction ratio of the compound represented by formula (4) and the compound represented by formula (6) is preferably such that the compound represented by formula (6) is used in excess, i.e., 2 to 20 times, particularly 4 to 10 times, of the total number of moles of the alkenyl groups in the compound represented by formula (4) in molar equivalents. If the amount of the compound represented by formula (6) is less than this amount, a compound in which the SiH groups at both ends of the compound represented by formula (6) react with the alkenyl groups of the compound represented by formula (4) is generated as a by-product, and the target product cannot be obtained. If the amount of the compound represented by formula (6) is too much, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when removing the unreacted compound represented by formula (6) after the reaction, it becomes necessary to make the conditions of heating, decompression, extraction, etc. stricter in proportion to the increase in the amount of unreacted compounds.
上記一般式（４）で示される分子鎖両末端にそれぞれ２個ずつ（分子中に４個の）アルケニル基を有するフルオロポリエーテルアミド化合物と上記一般式（６）で示される化合物とを反応させて得られる上記一般式（７）で示される化合物としては、例えば、下記に示すものが例示できる。
また、上記一般式（７）と反応させる上記一般式（８）で示されるアルケニル基含有加水分解性シラン化合物としては、例えば、下記に示すものが例示できる。
上記式（７）で示される化合物と上記式（８）で示される化合物との反応は、公知のヒドロシリル化反応によってなされる。このヒドロシリル化（付加）反応は、上記式（７）で示される化合物と上記式（８）で示される化合物とを混合し、白金族金属系の付加反応触媒存在下、反応温度５０～１５０℃、好ましくは６０～１２０℃で、１分～４８時間、特に１０分～１２時間反応を行うことが望ましい。反応温度が低すぎると反応が十分に進行しないまま停止してしまう場合があり、高すぎるとヒドロシリル化の反応熱による温度上昇で反応が制御できなくなり、突沸や原料の分解などが起こる場合がある。 The reaction between the compound represented by formula (7) and the compound represented by formula (8) is carried out by a known hydrosilylation reaction. This hydrosilylation (addition) reaction is carried out by mixing the compound represented by formula (7) and the compound represented by formula (8) in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 48 hours, and particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the heat of the hydrosilylation reaction, and bumping or decomposition of the raw materials may occur.
上記式（７）で示される化合物と、上記式（８）で示される化合物の反応割合は、式（７）で示される化合物のＳｉＨ基の総モル数に対して、式（８）で示される化合物を１～５倍モル、特に１～１．５倍モル使用して反応させることが望ましい。式（８）で示される化合物がこれより少なすぎると、ＳｉＨ基が残存した化合物が副生成物として発生し、目的物を得ることができない。式（８）で示される化合物がこれより多すぎると反応溶液の均一性が低下して反応速度が不安定となる。また反応後に未反応の式（８）で示される化合物の除去を行う場合に、加熱、減圧、抽出等の条件を未反応分が増える分だけ厳しくする必要が出てくる。 The reaction ratio of the compound represented by formula (7) and the compound represented by formula (8) is preferably 1 to 5 times, and particularly 1 to 1.5 times, the molar amount of the compound represented by formula (8) relative to the total number of moles of the SiH groups in the compound represented by formula (7). If the amount of the compound represented by formula (8) is less than this amount, a compound with remaining SiH groups will be generated as a by-product, and the target product cannot be obtained. If the amount of the compound represented by formula (8) is more than this amount, the uniformity of the reaction solution will decrease and the reaction rate will become unstable. In addition, when removing the unreacted compound represented by formula (8) after the reaction, it will be necessary to make the conditions of heating, decompression, extraction, etc. stricter in proportion to the increase in the amount of unreacted compounds.
上記ヒドロシリル化（付加）反応に用いる付加反応触媒は、例えば、白金、ロジウム又はパラジウム等の白金族金属を含む化合物を使用することができる。中でも白金を含む化合物が好ましく、ヘキサクロロ白金（ＩＶ）酸六水和物などの塩化白金酸、白金カルボニルビニルメチル錯体、塩化白金酸（白金）－ジビニルテトラメチルジシロキサン錯体、塩化白金酸（白金）－シクロビニルメチルシロキサン錯体、塩化白金酸（白金）－オクチルアルデヒド／オクタノール錯体などの塩化白金酸とアルコールやビニルシロキサンとの錯体、あるいは活性炭に担持された白金を用いることができる。
付加反応触媒の配合量は、式（４）又は式（７）で示される化合物に対し、含まれる金属量が０．１～５，０００質量ｐｐｍとなる量であることが好ましく、より好ましくは０．２～１，０００質量ｐｐｍとなる量である。
The addition reaction catalyst used in the hydrosilylation (addition) reaction may be, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium. Of these, a compound containing platinum is preferred, and examples of the catalyst that can be used include chloroplatinic acid such as hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, chloroplatinic acid (platinum)-divinyltetramethyldisiloxane complex, chloroplatinic acid (platinum)-cyclovinylmethylsiloxane complex, and chloroplatinic acid (platinum)-octylaldehyde/octanol complex, as well as platinum supported on activated carbon.
The amount of the addition reaction catalyst to be added is preferably an amount such that the amount of metal contained is 0.1 to 5,000 ppm by mass, and more preferably 0.2 to 1,000 ppm by mass, relative to the compound represented by formula (4) or formula (7).
上記ヒドロシリル化（付加）反応は、溶剤が存在しなくても実施可能であるが、必要に応じて溶剤で希釈してもよい。このとき希釈溶剤は、トルエン、キシレン、イソオクタンなど、広く一般に用いられている有機溶剤を利用することができるが、沸点が目的とする反応温度以上でかつ反応を阻害せず、反応に使用する化合物と生成物が、上記反応温度において可溶であるものが好ましい。このような溶剤としては、例えば、ｍ－キシレンヘキサフロライド、ベンゾトリフロライド等のフッ素変性芳香族炭化水素系溶剤、メチルパーフルオロブチルエーテル等のフッ素変性エーテル系溶剤等の部分フッ素変性された溶剤が望ましく、特にｍ－キシレンヘキサフロライドが好ましい。
溶剤を使用する場合、その使用量は、式（４）又は式（７）で示される化合物１００質量部に対して、好ましくは５～２，０００質量部であり、より好ましくは４０～５００質量部である。これより少なければ溶剤による希釈の効果が薄くなり、多ければ希釈度が高くなりすぎて反応速度の低下を招く場合がある。
The hydrosilylation (addition) reaction can be carried out in the absence of a solvent, but may be diluted with a solvent as necessary. In this case, the dilution solvent may be any of the commonly used organic solvents such as toluene, xylene, and isooctane, but it is preferable to use a solvent that has a boiling point equal to or higher than the target reaction temperature, does not inhibit the reaction, and is soluble in the compounds used in the reaction and the product at the reaction temperature. As such a solvent, for example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride, or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is preferable, and m-xylene hexafluoride is particularly preferable.
When a solvent is used, the amount of the solvent used is preferably 5 to 2,000 parts by mass, and more preferably 40 to 500 parts by mass, based on 100 parts by mass of the compound represented by formula (4) or formula (7). If the amount is less than this range, the effect of dilution by the solvent becomes weak, and if the amount is more than this range, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.
上記ヒドロシリル化（付加）反応終了後、それぞれ未反応の式（５）、式（６）あるいは式（８）で示される化合物、触媒残渣、及び希釈溶剤等を減圧留去、抽出、吸着等の公知の方法で除去することが好ましい。 After the hydrosilylation (addition) reaction is completed, it is preferable to remove the unreacted compound represented by formula (5), formula (6), or formula (8), catalyst residue, and dilution solvent by a known method such as vacuum distillation, extraction, or adsorption.
特に、最終的に式（１）で示されるフルオロポリエーテル変性アミドシラン化合物として単離する際に、常圧における沸点２６０℃以下の含フッ素溶剤、例えば、ｍ－キシレンヘキサフロライド、ベンゾトリフルオライド、メチルノナフルオロブチルエーテル、メチルノナフルオロイソブチルエーテル、エチルノナフルオロブチルエーテル、エチルノナフルオロイソブチルエーテル、３－メトキシパーフルオロ（３－メチルペンタン）、２－（トリフルオロメチル）－３－エトキシドデカフルオロヘキサン等を含む場合は、該含フッ素溶剤が式（１）で示されるフルオロポリエーテル変性アミドシラン化合物全体の１質量％未満となるように除去することが好ましい。 In particular, when the fluoropolyether-modified amidosilane compound represented by formula (1) is finally isolated, if the compound contains a fluorine-containing solvent having a boiling point of 260°C or less at normal pressure, such as m-xylene hexafluoride, benzotrifluoride, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 3-methoxyperfluoro(3-methylpentane), 2-(trifluoromethyl)-3-ethoxydodecafluorohexane, etc., it is preferable to remove the fluorine-containing solvent so that it accounts for less than 1 mass% of the entire fluoropolyether-modified amidosilane compound represented by formula (1).
ここで、常圧における沸点２６０℃以下の含フッ素溶剤の含有量は、例えば反応に使用した各溶剤の19Ｆ－ＮＭＲスペクトル又は1Ｈ－ＮＭＲスペクトルを元に、必要によって上記一般式（１）で示されるフルオロポリエーテル変性アミドシラン化合物に内部標準物質を加えたＮＭＲ測定結果から算出できる。また簡易的にはそれぞれの溶剤の不揮発分が１質量％未満となる条件下での加熱減量試験によって判断することもできる。 Here, the content of the fluorine-containing solvent having a boiling point of 260° C. or less at normal pressure can be calculated, for example, from the NMR measurement results obtained by adding an internal standard substance to the fluoropolyether-modified amidosilane compound represented by the above general formula (1) based on the 19 F-NMR spectrum or 1 H-NMR spectrum of each solvent used in the reaction. Alternatively, it can be simply determined by a heat loss test under conditions in which the non-volatile content of each solvent is less than 1 mass%.
以上のようにして得られる上記一般式（１）で示されるフルオロポリエーテル変性アミドシラン化合物としては、以下の化合物を例示できる。
上記式において、Ｒｆaは上記Ｒｆと同様のものが例示できるが、以下の式のいずれかで示されるものであることが好ましい。
（式中、ｓ１＋ｔ１の平均値は１５～１００であり、ｐ１＋ｑ１の平均値は１５～８０であり、かつｑ１／ｐ１は０．８～１．２である。なお、ｐ１、ｑ１が付された括弧内に示される各繰り返し単位の配列はランダムである。）
In the above formula, Rf a can be exemplified as the same as Rf above, but is preferably one represented by any of the following formulae.
(In the formula, the average value of s1+t1 is 15 to 100, the average value of p1+q1 is 15 to 80, and q1/p1 is 0.8 to 1.2. The arrangement of each repeating unit shown in parentheses with p1 and q1 is random.)
本発明の式（１）で示されるフルオロポリエーテル変性アミドシラン化合物は、以上に示した通りであり、これらの化合物は常圧（大気圧中）で沸点を持たない高分子量化合物であり、本発明の表面処理組成物の使用において不揮発性を示す。 The fluoropolyether-modified amidosilane compounds of the present invention represented by formula (1) are as described above, and these compounds are high molecular weight compounds that do not have a boiling point at normal pressure (atmospheric pressure) and are non-volatile when used in the surface treatment composition of the present invention.
本発明のさらなる実施形態は、式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を含む表面処理剤組成物を各種表面に塗工し、その表面に撥水性、撥油性、防汚性、耐指紋性、指紋除去性、滑り性、耐摩耗性、耐擦傷性、耐溶剤性、耐薬品性、液滴滑落性、着雪滑落性、着氷滑落性、防曇性、表面レベリング性、離型性、低屈折率性、反射防止性等の優れた性質を与える不揮発性フッ素含有有機化合物を含有する表面処理剤組成物としての使用法である。 A further embodiment of the present invention is a method of using a surface treatment composition containing a fluoropolyether-modified amidosilane compound represented by formula (1) and/or a partial hydrolysis condensate thereof, by applying the surface treatment composition to various surfaces and providing the surfaces with excellent properties such as water repellency, oil repellency, antifouling properties, fingerprint resistance, fingerprint removability, slipperiness, abrasion resistance, scratch resistance, solvent resistance, chemical resistance, droplet sliding properties, snow adhesion sliding properties, ice adhesion sliding properties, antifogging properties, surface leveling properties, release properties, low refractive index, and antireflection properties.
本発明の表面処理剤組成物は、各種基材表面に式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の特性を付与するものである。本発明の表面処理剤組成物は、不揮発性フッ素含有有機化合物を含有する表面処理剤組成物であって、該不揮発性フッ素含有有機化合物が、上記式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を含むものであることを特徴とする。ここで、不揮発性とは、大気圧中２６０℃の加熱では揮発しないことを意味する。該表面処理剤組成物には、例えば、原料に含まれる不純物や製造プロセスで発生した副生成物が残存、混入することが考えられる。 The surface treatment composition of the present invention imparts the properties of the fluoropolyether-modified amidosilane compound represented by formula (1) and/or its partial hydrolysis condensate to the surface of various substrates. The surface treatment composition of the present invention is a surface treatment composition containing a non-volatile fluorine-containing organic compound, characterized in that the non-volatile fluorine-containing organic compound contains the fluoropolyether-modified amidosilane compound represented by formula (1) and/or its partial hydrolysis condensate. Here, non-volatile means that it does not volatilize when heated at 260°C under atmospheric pressure. For example, impurities contained in the raw materials and by-products generated in the manufacturing process may remain or be mixed into the surface treatment composition.
このような混入されうる不純物及び副生成物として、具体的には使用した各原料、各中間体及びこれらに含まれた不純物や、Ｒｆ基の一部がフッ素化されていない構造を有するもの、下記一般式（１１）
で示される片末端官能化合物、更に式（１）で示されるフルオロポリエーテル変性アミドシラン化合物あるいは上記式（１１）で示される化合物の－［Ｚ－Ｓｉ－ＭaＲ3-a］基の一つ以上が他の官能基に置き換わったもの等が挙げられる。
Specific examples of impurities and by-products that may be mixed in include the raw materials and intermediates used, impurities contained therein, and those having a structure in which a portion of the Rf group is not fluorinated, and those having the following general formula (11):
and further, a fluoropolyether-modified amidosilane compound represented by formula (1) or a compound represented by formula (11) in which one or more of the -[Z-Si-M a R 3-a ] groups have been replaced with other functional groups.
これら混入物は、式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の溶解性や付与できる表面特性に大きな影響を与えない範囲で存在することは実用上問題にならないが、本発明の表面処理剤組成物は、その付与特性を維持するため、不揮発成分中に式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物が８０質量％以上含まれることが望ましい。同様の理由から、不揮発成分中のフッ素含有量を測定した際に４０～６５質量％であることが望ましい。フッ素含有率は標準物質等を使用した不揮発分の19Ｆ－ＮＭＲから計算で求める。あるいは不揮発分の元素分析を行うことで求めることができる。 It is not a practical problem if these contaminants are present to the extent that they do not significantly affect the solubility of the fluoropolyether-modified amidosilane compound represented by formula (1) and/or its partial hydrolysis condensate or the surface properties that can be imparted, but in order to maintain the imparting properties of the surface treatment agent composition of the present invention, it is desirable that the non-volatile components contain 80% by mass or more of the fluoropolyether-modified amidosilane compound represented by formula (1) and/or its partial hydrolysis condensate. For the same reason, it is desirable that the fluorine content in the non-volatile components is 40 to 65% by mass when measured. The fluorine content is calculated from 19F -NMR of the non-volatile components using standard substances, etc. Alternatively, it can be determined by performing elemental analysis of the non-volatile components.
本発明の表面処理剤組成物は、予め溶剤によって希釈しておくことが望ましく、該溶剤としては、式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を均一に溶解させるものであれば特に限定されないが、保存安定性と塗工後の乾燥における利便性から沸点が２５～２６０℃、特に４５～１５０℃の範囲にあることが望ましい。これより沸点が低いと、保存性が低下し、作業者の揮発分対策も難しくなり、これより高いと乾燥工程が困難になる。 It is desirable to dilute the surface treatment composition of the present invention with a solvent in advance. The solvent is not particularly limited as long as it can uniformly dissolve the fluoropolyether-modified amidosilane compound represented by formula (1) and/or its partial hydrolysis condensate, but it is desirable for the solvent to have a boiling point in the range of 25 to 260°C, particularly 45 to 150°C, in terms of storage stability and convenience in drying after application. If the boiling point is lower than this, the storage stability is reduced and it becomes difficult for workers to take measures against volatile components, and if it is higher than this, the drying process becomes difficult.
このような溶剤として、具体的には、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタンなど）、フッ素変性芳香族炭化水素系溶剤（ｍ－キシレンヘキサフロライドなど）、フッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、エチルパーフルオロブチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）など）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミンなど）、あるいはフッ素原子を含まない溶剤、具体的には炭化水素系溶剤（ヘキサン、ヘプタン、オクタン、イソオクタン、イソノナン、イソデカン、ペンタメチルヘプタン、石油ベンジン、トルエン、キシレンなど）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトンなど）、エーテル系溶剤（ジイソプロピルエーテル、ジブチルエーテル、モノグライム、ジグライム、テトラヒドロフラン、２－メチルテトラヒドロフラン、シクロペンチルメチルエーテル）、エステル系溶剤（酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル）、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル等が挙げられる。 Specific examples of such solvents include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylene hexafluoride, etc.), fluorine-modified ether solvents (methyl perfluorobutyl ether, ethyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), and solvents that do not contain fluorine atoms, specifically hydrocarbon solvents (hexane, heptane, octane, isopropyl alcohol, etc.). ethane, isononane, isodecane, pentamethylheptane, petroleum benzine, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, etc.), ether solvents (diisopropyl ether, dibutyl ether, monoglyme, diglyme, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether), ester solvents (ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate), propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, etc.
これらの中でも、本発明の式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の特性を十分に活用するために、フッ素原子を含まない溶剤であることが好ましい。上記溶剤は１種を単独で使用しても２種以上を混合して使用してもよい。 Among these, in order to fully utilize the properties of the fluoropolyether-modified amidosilane compound represented by formula (1) of the present invention and/or its partial hydrolysis condensate, it is preferable to use a solvent that does not contain fluorine atoms. The above solvents may be used alone or in combination of two or more.
溶剤に溶解させる式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の最適濃度は、処理方法により異なり、秤量し易い量であればよく、溶剤に溶解させる場合、表面処理剤組成物中における式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の含有率が０．０１～９５質量％であることが好ましい。これらのうち、直接塗工する場合は、溶剤とフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の合計質量に対して式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の含有率が０．０１～１０質量％、特に０．０５～５質量％であることが好ましく、蒸着処理をする場合は、溶剤に溶解させなくてもよいし、溶剤に溶解させる場合は溶剤とフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の合計質量に対して式（１）で示されるフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物の含有率が１～９５質量％、特に３～３０質量％であることが好ましい。またこれらの希釈は事前に一定濃度に希釈されたものを、使用の度に必要な濃度に希釈して用いてもよい。 The optimal concentration of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate represented by formula (1) to be dissolved in a solvent varies depending on the treatment method, and an amount that is easy to weigh may be used. When dissolved in a solvent, it is preferable that the content of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate represented by formula (1) in the surface treatment agent composition is 0.01 to 95 mass%. Of these, in the case of direct coating, the content of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate represented by formula (1) is preferably 0.01 to 10 mass%, particularly 0.05 to 5 mass%, based on the total mass of the solvent and the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate. In the case of vapor deposition treatment, it is not necessary to dissolve in a solvent, and in the case of dissolving in a solvent, the content of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate represented by formula (1) is preferably 1 to 95 mass%, particularly 3 to 30 mass%, based on the total mass of the solvent and the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate. In addition, these dilutions may be used by diluting a solution diluted to a certain concentration in advance to the required concentration each time it is used.
本発明の表面処理剤組成物は、刷毛塗り、ディッピング、スプレー、蒸着処理など公知の方法で基材に施与することができる。蒸着処理時の加熱方法は、抵抗加熱方式でも、電子ビーム加熱方式のどちらでもよく、特に限定されるものではない。また、硬化温度は、硬化方法によって異なるが、例えば、ディッピング処理や蒸着処理で施与する場合は、２０～２００℃の範囲が望ましい。また、加湿下で硬化させてもよい。硬化被膜の膜厚は、基材の種類により適宜選定されるが、通常０．１～１００ｎｍ、特に１～２０ｎｍである。 The surface treatment composition of the present invention can be applied to a substrate by known methods such as brushing, dipping, spraying, and vapor deposition. The heating method during vapor deposition may be either resistance heating or electron beam heating, and is not particularly limited. The curing temperature differs depending on the curing method, but is preferably in the range of 20 to 200°C when applied by dipping or vapor deposition. Curing may also be performed under humid conditions. The thickness of the cured coating is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, particularly 1 to 20 nm.
また、本発明の表面処理剤組成物の一般的な使用形態としては、本発明の表面処理剤組成物層が硬化後に密着又は接着するものであればいかなる基材上に塗布することもできるが、紙、布、金属及びその酸化物、皮、合成皮革、樹脂、木材、ガラス、ＳｉＯ2処理されたガラス及び樹脂フィルム、セラミック（陶器）、石英、サファイア基材、石材など各種材質、これら基材に各種塗料によって塗装された塗膜表面などが挙げられる。これらは、フィルム、板状、及び成形部材等任意の形態をとるものに対してその表面に使用できる。 In addition, the general form of use of the surface treatment composition of the present invention can be applied to any substrate as long as the layer of the surface treatment composition of the present invention adheres or bonds after curing, and examples of such substrates include paper, cloth, metals and their oxides, leather, synthetic leather, resin, wood, glass, SiO2- treated glass and resin films, ceramics (pottery), quartz, sapphire substrates, stone materials, and other various materials, as well as coating surfaces formed by coating these substrates with various paints, etc. These can be used on the surfaces of any form, such as films, plates, and molded members.
本発明の表面処理剤組成物によって得られる硬化被膜（硬化樹脂層）は、具体的には、タブレット型コンピュータ、ノートＰＣ、携帯電話・スマートフォン等の携帯（通信）情報端末、デジタルメディアプレイヤー、デジタルカメラ、デジタルビデオカメラ、電子ブックリーダーなど各種機器の筐体及び表示部、操作部、時計型・眼鏡型ウェアラブルコンピュータ、心拍計・、脈拍系等の人体あるいは動物向けウェアラブルセンサー、ヘッドマウントディスプレイ、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬ（エレクトロルミネッセンス）ディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、フィールドエミッションプロジェクションディスプレイ、ＣＲＴ、トナー系ディスプレイ、量子ドット（ＱＤ）ディスプレイなどの各種フラットパネルディスプレイ及びＴＶの画面などの表示操作機器表面及びこれらの内部に使用される各種光学フィルム類、ＧＰＳ表示記録機器、自動車用等のナビゲーション装置、自動車用等の制御パネル、自動現金引出し預け入れ装置、現金自動支払機、自動販売機、デジタルサイネージ（電子看板）、セキュリティーシステム端末、ＰＯＳ端末、リモートコントローラなど各種コントローラ、車載装置用パネルスイッチなどの表示入力装置、ピアノや家具の光沢表面、大理石等の建築用石材表面、家具調度の表面、トイレ、風呂、洗面所等の水周りの装飾建材、衛生陶器、美術品展示用保護ガラス、ショーウインドー、ショーケース、フォトフレーム用カバー、腕時計、化粧品容器の外装及び内装、装飾品の外装、装飾品容器の外装、自動車及び列車等の各種車両の窓用ガラス、自動車及び列車等の各種車両の内装外装用の樹脂及び金属部分、車両用塗装のオーバーコート、屋内屋外の看板、広告表示、道路標識、案内板、屋内外の照明器具の発光部、各種信号機及びＬＥＤ標識の表示部のコーティング、自動車用電子ミラーの表示部、各種建造物の屋外塗装、列車航空機等の輸送装置の窓ガラス及び内装外装、各種印刷用プリンターのインクノズル周辺部品、各種３Ｄプリンターの材料吐出ノズル周辺部品、自動車ヘッドライト・テールランプなどの透明なガラス製又は透明なプラスチック製（アクリル、ポリカーボネートなど）部材、ミリ波レーダー等の車用センサーのカバー部材、各種ミラー部材等の塗装膜及び表面保護膜として使用である。 The cured coating (cured resin layer) obtained by the surface treatment composition of the present invention can be used in a wide variety of applications, including: tablet computers, notebook PCs, mobile phones, smartphones and other portable (communication) information terminals, digital media players, digital cameras, digital video cameras, electronic book readers and other devices' housings and display and operating parts; watch-type and eyeglasses-type wearable computers; wearable sensors for the human body or animals, such as heart rate monitors and pulse rate monitors; head-mounted displays; liquid crystal displays; plasma displays; organic electroluminescence (EL) displays; rear projection displays; fluorescent display tubes (VFDs); field emission projection displays; CRTs; toner-based displays; quantum dot (QD) displays and other flat panel displays; and TV screens; various optical films used on the surfaces and interiors of display and operating devices; GPS display and recording devices; navigation devices for automobiles; control panels for automobiles; automatic cash withdrawal and deposit devices; automatic cash dispensers; vending machines; digital signage (electronic billboards); security system terminals; POS terminals; relays; and other devices. Various controllers such as remote controllers, display input devices such as panel switches for in-vehicle devices, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, surfaces of furniture, decorative building materials for wet areas such as toilets, baths and washrooms, sanitary ware, protective glass for displaying art works, show windows, showcases, covers for photo frames, wristwatches, exteriors and interiors of cosmetic containers, exteriors of decorative items, exteriors of decorative item containers, window glass for various vehicles such as automobiles and trains, resin and metal parts for the interior and exterior of various vehicles such as automobiles and trains, overcoats for vehicle paint, indoor and outdoor signs, advertising displays It is used as a coating and surface protection film for signs, road signs, guide plates, light-emitting parts of indoor and outdoor lighting fixtures, display parts of various traffic lights and LED signs, display parts of electronic mirrors for automobiles, outdoor painting of various buildings, window glass and interior and exterior decoration of transportation devices such as trains and aircraft, peripheral parts of ink nozzles for various printing printers, peripheral parts of material discharge nozzles for various 3D printers, transparent glass or transparent plastic (acrylic, polycarbonate, etc.) parts such as automobile headlights and taillights, cover parts for automotive sensors such as millimeter wave radar, various mirror parts, etc.
更にメガネレンズ、プリズム、レンズシート、ペリクル膜、偏光板、光学フィルター、レンチキュラーレンズ、フレネルレンズ、反射防止膜、各種カメラ用レンズ、各種レンズ用フィルター、光ファイバーや光カプラーなどの光学部品・光デバイスの表面保護被膜としても使用できる。 It can also be used as a surface protective coating for optical components and optical devices such as eyeglass lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, various camera lenses, various lens filters, optical fibers, and optical couplers.
本発明の表面処理剤組成物は、基材表面に塗布して硬化させることにより、表面に優れた防汚性、撥水性、撥油性、及び耐指紋性を有する硬化被膜を提供する。これによって各種基材に、雨、砂塵、花粉、生物の糞、虫の衝突による汚れ、各種工業オイル、食品オイル、調味料、指紋や皮脂あるいは汗等の人脂、化粧品などの付着、インクや塗料による落書き等により汚れ難くなり、汚れが付着した場合であっても拭き取り性に優れ、またガム、シール等粘着物が貼り付いた場合も容易に除去できる表面を与える。このため、本発明のフルオロポリエーテル変性アミドシラン化合物及び／又はその部分加水分解縮合物を８０質量％以上含む表面処理剤組成物は、各種基材への保護膜を形成するために有用である。 The surface treatment composition of the present invention, when applied to a substrate surface and cured, provides a cured coating having excellent antifouling, water repellency, oil repellency, and fingerprint resistance on the surface. This makes various substrates less susceptible to stains caused by rain, sand dust, pollen, animal droppings, and insect collisions, various industrial oils, food oils, seasonings, fingerprints, sebum, sweat, and other human oils, cosmetics, and graffiti with ink or paint, and even if stains do adhere, the surface is easy to wipe off, and adhesives such as gum and stickers can be easily removed. For this reason, the surface treatment composition of the present invention containing 80% by mass or more of the fluoropolyether-modified amidosilane compound and/or its partial hydrolysis condensate is useful for forming a protective film on various substrates.
以下、合成例、合成実施例、合成比較例、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の合成実施例、実施例に制限されるものではない。 The present invention will be specifically explained below with reference to synthesis examples, synthesis examples, synthesis comparative examples, and examples and comparative examples, but the present invention is not limited to the synthesis examples and examples below.
［合成例１］
攪拌装置と還流装置を備えた４つ口フラスコに、下記式（１２）
で示される化合物１，５００ｇ（－ＣＯＦ基として０．５１５モル）、ジアリルアミン６７．６ｇ（０．７０モル）、及びトリエチルアミン５２．４ｇ（０．５２モル）を仕込み、５０℃で攪拌混合した。４時間後に行った反応液のＩＲ測定で、１，７８０ｃｍ-1の酸フロライドのカルボニル基の吸収が消失し、新たに１，６８５ｃｍ-1にアミド基のカルボニル基由来の吸収が発生したことを確認した。次いで、炭酸カルシウム３６．８ｇを投入し、攪拌を継続しながら９５℃まで昇温し、９５℃に到達後１時間攪拌を継続し、そののち冷却した。室温まで冷却した反応溶液を、ロータリーエバポレーターで１５０℃／０．８ｋＰａで留出液が無くなるまで加熱減圧した。フラスコを冷却後に得られた成分を、スリーエムジャパン製フッ素溶剤 ＰＦ－５０６０ １，０００ｇ、活性炭１５ｇ、及び共和界面科学製吸着剤 キョーワード７００ １５ｇと共に２時間攪拌し、アドバンテック東洋（株）製のＮＡ－５００濾過板で加圧ろ過した。得られたろ液をロータリーエバポレーターで１２０℃／０．８ｋＰａで減圧留去を行い、１，４４５ｇの無色透明液体を得た。得られた化合物は、19Ｆ－ＮＭＲ、1Ｈ－ＮＭＲ、ＩＲ測定の結果から下記式（Ｉ）で示される化合物であることを確認した。
Into a four-neck flask equipped with a stirrer and a reflux device, the following compound represented by formula (12) was added:
1,500 g of the compound represented by the formula (0.515 mol as -COF group), 67.6 g (0.70 mol) of diallylamine, and 52.4 g (0.52 mol) of triethylamine were charged and mixed with stirring at 50 ° C. In the IR measurement of the reaction solution performed after 4 hours, it was confirmed that the absorption of the carbonyl group of the acid fluoride at 1,780 cm -1 disappeared, and a new absorption derived from the carbonyl group of the amide group occurred at 1,685 cm -1 . Next, 36.8 g of calcium carbonate was added, and the temperature was raised to 95 ° C. while continuing stirring, and after reaching 95 ° C., stirring was continued for 1 hour, and then cooled. The reaction solution cooled to room temperature was heated and reduced in pressure at 150 ° C. / 0.8 kPa in a rotary evaporator until no distillate was left. The flask was cooled, and the resulting components were stirred for 2 hours with 1,000 g of PF-5060 fluorine solvent manufactured by 3M Japan, 15 g of activated carbon, and 15 g of Kyowa Interface Science adsorbent Kyoward 700, and pressure filtered with an NA-500 filter plate manufactured by Advantec Toyo Co., Ltd. The resulting filtrate was distilled under reduced pressure at 120°C/0.8 kPa using a rotary evaporator, yielding 1,445 g of a colorless, transparent liquid. The resulting compound was confirmed to be the compound represented by the following formula (I) based on the results of 19 F-NMR, 1 H-NMR, and IR measurements.
［合成例２］
仕込み量を、下記式（１３）
で示される化合物１，５００ｇ（－ＣＯＦ基として０．７７モル）、ジアリルアミン９２．５ｇ（０．９５モル）、及びトリエチルアミン９５．３ｇ（０．９４モル）とした以外は合成例１と同様にして、１，５１３ｇの無色透明液体である下記式（ＩＩ）で示される化合物を得た。
The amount of the mixture is calculated according to the following formula (13).
The same procedure as in Synthesis Example 1 was repeated, except that 1,500 g (0.77 mol as -COF group) of the compound represented by the following formula (II) was used, and 92.5 g (0.95 mol) of diallylamine and 95.3 g (0.94 mol) of triethylamine were used, to obtain 1,513 g of a colorless, transparent liquid compound represented by the following formula (II).
［合成実施例１］
攪拌装置と還流装置を備えた４つ口フラスコに、上記式（Ｉ）の化合物６００ｇ（アリル基として０．４０モル）、ｍ－キシレンヘキサフロライド２４０ｇ、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．６ｇ（Ｐｔ単体として１．５×１０-6モルを含有）を仕込み、窒素雰囲気下で攪拌しながら８５℃まで昇温した。ここに、下記式（ＩＩＩ）
In a four-neck flask equipped with a stirrer and a reflux device, 600 g of the compound of formula (I) above (0.40 mol as allyl group), 240 g of m-xylene hexafluoride, and 0.6 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 1.5×10 −6 mol as Pt alone) were charged, and the mixture was heated to 85° C. under a nitrogen atmosphere while stirring.
［合成実施例２］
上記式（Ｉ）の化合物の代わりに上記式（ＩＩ）の化合物６００ｇ（アリル基として０．６０モル）を使用し、上記式（ＩＩＩ）の化合物の仕込み量を１７４ｇ（０．６２モル）とした以外は、合成実施例１と同様の手順で、７０１ｇの淡黄色の透明液体を得た。得られた化合物の19Ｆ－ＮＭＲ、1Ｈ－ＮＭＲ、ＩＲ測定の結果から、上記（ＩＩＩ）で示される化合物及び溶媒のｍ－キシレンヘキサフロライドは残存せず、下記式（Ｖ）で示される化合物のみであることを確認した。
Except for using 600 g (0.60 mol as allyl group) of the compound of formula (II) instead of the compound of formula (I) and changing the amount of the compound of formula (III) to 174 g (0.62 mol), 701 g of a pale yellow transparent liquid was obtained in the same manner as in Synthesis Example 1. From the results of 19 F-NMR, 1 H-NMR and IR measurements of the obtained compound, it was confirmed that the compound represented by formula (III) and the solvent m-xylene hexafluoride did not remain, and only the compound represented by formula (V) below was present.
［合成比較例１］
攪拌装置と還流装置を備えた４つ口フラスコに、上記式（Ｉ）の化合物６０ｇ（アリル基として０．０４０モル）、ｍ－キシレンヘキサフロライド１００ｇ、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．２ｇ（Ｐｔ単体として０．５×１０-6モルを含有）を仕込み、窒素雰囲気下で攪拌しながら８０℃まで昇温した。ここにトリメトキシシラン１３ｇ（０．１１モル）を滴下し、８時間攪拌を継続したのちに、反応液の1Ｈ－ＮＭＲを測定した。1Ｈ－ＮＭＲ測定の結果、上記式（Ｉ）の化合物のアリル基が消失したことを確認し、加熱を停止して冷却した。冷却後の溶液を孔径０．２ｍのＰＴＦＥフィルターでろ過したのちに、窒素バブリング下で１００℃／１．３ｋＰａで減圧留去を行い、６１ｇの淡黄色の透明液体を得た。得られた化合物の19Ｆ－ＮＭＲ、1Ｈ－ＮＭＲ、ＩＲ測定の結果から、上記トリメトキシシラン及び溶媒のｍ－キシレンヘキサフロライドは残存せず、下記式（ＶＩ）で示される化合物のみであることを確認した。
In a four-neck flask equipped with a stirrer and a reflux device, 60 g of the compound of formula (I) (0.040 moles as allyl group), 100 g of m-xylene hexafluoride, and 0.2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.5×10 −6 moles as Pt alone) were charged, and the temperature was raised to 80° C. while stirring under a nitrogen atmosphere. 13 g (0.11 moles) of trimethoxysilane was added dropwise thereto, and stirring was continued for 8 hours, after which the 1 H-NMR of the reaction solution was measured. As a result of the 1 H-NMR measurement, it was confirmed that the allyl group of the compound of formula (I) had disappeared, and the heating was stopped and the solution was cooled. The cooled solution was filtered through a PTFE filter with a pore size of 0.2 m, and then distilled under reduced pressure at 100° C./1.3 kPa under nitrogen bubbling to obtain 61 g of a pale yellow transparent liquid. From the results of 19 F-NMR, 1 H-NMR and IR measurements of the obtained compound, it was confirmed that neither the above trimethoxysilane nor the solvent m-xylenehexafluoride remained, and that only the compound represented by the following formula (VI) was present.
［実施例１、２及び比較例１］
溶解性の確認：
合成実施例１、２及び合成比較例１で得られた上記式（ＩＶ）、（Ｖ）、（ＶＩ）で示される各化合物１６ｇと表１に示す脱水した各溶剤６４ｇを密閉した１００ｍｌの透明バイアル瓶の中で均一に攪拌混合し、２０℃で静置したのちに外観を目視で確認した。透明均一に溶解したものを「○」、相溶せず分離したものを「×」で評価した。結果を表１に示す。
[Examples 1 and 2 and Comparative Example 1]
Solubility check:
16 g of each of the compounds represented by the above formulae (IV), (V), and (VI) obtained in Synthesis Examples 1 and 2 and Synthesis Comparative Example 1 and 64 g of each of the dehydrated solvents shown in Table 1 were uniformly mixed by stirring in a sealed 100 ml transparent vial, and the mixture was allowed to stand at 20° C., after which the appearance was visually confirmed. Transparent and uniformly dissolved compounds were evaluated as "○", and compounds that were not compatible and separated were evaluated as "×". The results are shown in Table 1.
［実施例３、４及び比較例２］
合成実施例１、２で得られた上記式（ＩＶ）、（Ｖ）で示される各化合物をそれぞれ脱水した酢酸イソプロピルで０．１質量％に希釈した溶液（表面処理剤組成物）に、スライドガラスを１０秒間浸漬し、１５０ｍｍ／ｍｉｎで引き上げたのちに、８０℃、湿度８０％の恒温恒湿器内で４時間保持して上記化合物の硬化被膜（膜厚：６ｎｍ）を得た。得られたコーティング表面（硬化被膜）及び未塗工ガラスの水接触角（撥水性）及び防汚性（マジックハジキ性、マジック拭き取り性）を以下に示す方法で評価した。
[Examples 3 and 4 and Comparative Example 2]
A slide glass was immersed in a solution (surface treatment agent composition) prepared by diluting each of the compounds represented by the above formulae (IV) and (V) obtained in Synthesis Examples 1 and 2 to 0.1% by mass with dehydrated isopropyl acetate for 10 seconds, and then lifted at 150 mm/min., and then held in a thermohygrostat at 80° C. and 80% humidity for 4 hours to obtain a cured coating of the above compound (film thickness: 6 nm). The water contact angle (water repellency) and antifouling properties (marker repelling property, marker wipeability) of the obtained coating surface (cured coating) and uncoated glass were evaluated by the following method.
［撥水性の評価］
接触角計（協和界面科学（株）製 ＤｒｏｐＭａｓｔｅｒ）を用い、水２μＬの液滴を硬化被膜又はガラス表面上に滴下して１秒後の水接触角を測定した。Ｎ＝５の平均値を測定値とした。結果を表２に示す。
[Evaluation of water repellency]
A contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the water contact angle 1 second after a 2 μL droplet of water was dropped onto the cured coating or glass surface. The average value of N=5 was taken as the measured value. The results are shown in Table 2.
［マジックハジキ性の評価］
硬化被膜又はガラス表面にマジックペン（ゼブラ（株）製 ハイマッキー太字）で直線を描き、そのはじき具合を目視観察によって評価した。結果を表２に示す。
[Evaluation of marker repelling properties]
A straight line was drawn on the cured coating or the glass surface with a magic marker (Zebra Co., Ltd., Hi-Mackie Bold) and the degree of repellency was evaluated by visual observation. The results are shown in Table 2.
［マジック拭き取り性の評価］
硬化被膜又はガラス表面にマジックペン（ゼブラ（株）製 ハイマッキー太字）で直線を描き、１分後にティッシュペーパーで軽く３回擦って、マジックの跡が残らなかったものを「拭き取れる」、跡が残ったものを「拭き取れない」で評価した。結果を表２に示す。
[Evaluation of Marker Wipeability]
A straight line was drawn on the cured coating or on the glass surface with a marker pen (Zebra Co., Ltd., Hi-Mackie Bold), and after one minute, the surface was lightly rubbed three times with tissue paper. The results were evaluated as "can be wiped off" if no trace of the marker remained, and "cannot be wiped off" if a trace remained. The results are shown in Table 2.
Claims (12)
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物。 The following general formula (1)
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The fluoropolyether-modified amidosilane compound is represented by the formula:
－ＣＦ（Ｙ）－Ｏ－Ｒｆ1－ＣＦ（Ｙ）－ （２）
（式中、ＹはＦ又はＣＦ3であり、Ｒｆ1は以下のパーフルオロオキシアルキレン単位の１種又は２種以上から選ばれる繰り返し単位からなる。）
－ＣＦ2Ｏ－
－ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ（ＣＦ3）ＣＦ2Ｏ－
－ＣＦ2ＣＦ（ＣＦ3）Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－
－ＣＦ2ＣＦ2ＯＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ－ 2. The fluoropolyether-modified amidosilane compound according to claim 1, wherein in the above general formula (1), Rf is represented by the following general formula (2):
-CF(Y)-O-Rf 1 -CF(Y)- (2)
(In the formula, Y is F or CF3 , and Rf1 is a repeating unit selected from one or more of the following perfluorooxyalkylene units.)
-CF2O-
-CF2CF2O-
-CF 2 CF 2 CF 2 O-
-CF( CF3 ) CF2O-
-CF 2 CF(CF 3 )O-
-CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O-
-CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 O-
－ＣＦ2Ｏ（ＣＦ2Ｏ）p（ＣＦ2ＣＦ2Ｏ）qＣＦ2－
（式中、ｐは１０～３００の整数、ｑは５～１７０の整数であり、かつｐ＋ｑは１５～４７０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数であり、各繰り返し単位の配列はランダムである。）
－ＣＦ2ＣＦ2Ｏ［ＣＦ2ＣＦ2ＣＦ2Ｏ］wＣＦ2ＣＦ2－
（式中、ｗは８～１１９の整数である。）
－ＣzＦ2zＯ（ＣＦ2ＣＦ2Ｏ）x（ＣＦ2ＣＦ2ＣＦ2ＣＦ2Ｏ）yＣzＦ2z－
（式中、ｘは２～３００の整数、ｙは２～８０の整数であり、かつｘ＋ｙは４～３８０の整数のうち、Ｒｆの数平均分子量が１，５００～２０，０００を満たす数である。ｚは単位毎に独立に１又は２である。各繰り返し単位の配列はランダムである。） 3. The fluoropolyether-modified amidosilane compound according to claim 1, wherein in the general formula (1), Rf is any one of the following:
-CF 2 O (CF 2 O) p (CF 2 CF 2 O) q CF 2 -
(In the formula, p is an integer of 10 to 300, q is an integer of 5 to 170, and p+q is an integer of 15 to 470 such that the number average molecular weight of Rf is 1,500 to 20,000, and the arrangement of each repeating unit is random.)
-CF 2 CF 2 O [CF 2 CF 2 CF 2 O] w CF 2 CF 2 -
(In the formula, w is an integer from 8 to 119.)
-C z F 2z O (CF 2 CF 2 O) x (CF 2 CF 2 CF 2 CF 2 O) y C z F 2z -
(In the formula, x is an integer of 2 to 300, y is an integer of 2 to 80, and x+y is an integer of 4 to 380 such that the number average molecular weight of Rf is 1,500 to 20,000. z is independently 1 or 2 for each unit. The arrangement of each repeating unit is random.)
で示されるフルオロポリエーテルアミド化合物の４個のアルケニル基に、それぞれ下記一般式（５）
で示されるオルガノシロキサン化合物のＳｉＨ基をヒドロシリル化付加反応により付加して、下記一般式
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物を得るものであるフルオロポリエーテル変性アミドシラン化合物の合成方法。 The following general formula (4)
The four alkenyl groups of the fluoropolyether amide compound represented by the following general formula (5) are
The SiH group of the organosiloxane compound represented by the following general formula is added by hydrosilylation addition reaction to obtain a compound represented by the following general formula:
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The present invention relates to a method for synthesizing a fluoropolyether-modified amidosilane compound, the method comprising the steps of:
で示されるフルオロポリエーテルアミド化合物の４個のアルケニル基に、モル当量として過剰量の下記一般式（６）
で示されるオルガノシロキサン化合物の片方のＳｉＨ基をヒドロシリル化付加反応によって付加させたのちに、残存する上記一般式（６）で示される化合物を取り除き、得られた下記一般式（７）
で示される化合物の分子鎖両末端のＳｉＨ基に、下記一般式（８）
で示されるアルケニル基含有加水分解性シラン化合物のアルケニル基をヒドロシリル化付加反応によって付加して、下記一般式
で示される２価の連結基であり、Ｍはそれぞれ独立に、炭素数１～１０のアルコキシ基、炭素数２～１０のアルコキシアルコキシ基、炭素数２～１０のアシロキシ基、炭素数２～１０のアルケニルオキシ基及びハロゲン原子からなる群より選ばれる加水分解性基であり、Ｒはそれぞれ独立に炭素数１～６の１価炭化水素基であり、ａは２又は３である。）
で示されるフルオロポリエーテル変性アミドシラン化合物を得るものであるフルオロポリエーテル変性アミドシラン化合物の合成方法。 The following general formula (4)
and an excess amount of a compound represented by the following general formula (6) in terms of molar equivalent to four alkenyl groups of a fluoropolyetheramide compound represented by the following general formula (6):
The remaining compound represented by the above general formula (6) is removed to obtain an organosiloxane compound represented by the following general formula (7):
to the SiH groups at both ends of the molecular chain of a compound represented by the following general formula (8):
The alkenyl group of the alkenyl-containing hydrolyzable silane compound represented by the following general formula is added by hydrosilylation addition reaction to obtain a compound represented by the following general formula:
each M is independently a hydrolyzable group selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, and a halogen atom; each R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms; and a is 2 or 3.
The present invention relates to a method for synthesizing a fluoropolyether-modified amidosilane compound, the method comprising the steps of:
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| JP2002121277A (en) | 2000-10-16 | 2002-04-23 | Shin Etsu Chem Co Ltd | Pereluoropolyether-modified aminosilane and surface treatment agent, and article provided with cured coating film of the aminosilane |
| JP2008088412A (en) | 2006-09-08 | 2008-04-17 | Shin Etsu Chem Co Ltd | Perfluoropolyether-polyorganosiloxane copolymer, and surface treating agent containing the same |
| JP2012072272A (en) | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article subjected to surface treatment using the surface treatment agent |
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| JP2002121277A (en) | 2000-10-16 | 2002-04-23 | Shin Etsu Chem Co Ltd | Pereluoropolyether-modified aminosilane and surface treatment agent, and article provided with cured coating film of the aminosilane |
| JP2008088412A (en) | 2006-09-08 | 2008-04-17 | Shin Etsu Chem Co Ltd | Perfluoropolyether-polyorganosiloxane copolymer, and surface treating agent containing the same |
| JP2012072272A (en) | 2010-09-28 | 2012-04-12 | Shin-Etsu Chemical Co Ltd | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article subjected to surface treatment using the surface treatment agent |
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