JP5251801B2 - Surface treatment agent - Google Patents
Surface treatment agent Download PDFInfo
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- JP5251801B2 JP5251801B2 JP2009215238A JP2009215238A JP5251801B2 JP 5251801 B2 JP5251801 B2 JP 5251801B2 JP 2009215238 A JP2009215238 A JP 2009215238A JP 2009215238 A JP2009215238 A JP 2009215238A JP 5251801 B2 JP5251801 B2 JP 5251801B2
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- aqueous solution
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- emulsifier
- perfluoropolyether oil
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- 239000012756 surface treatment agent Substances 0.000 title claims description 12
- 239000000839 emulsion Substances 0.000 claims description 42
- 239000003921 oil Substances 0.000 claims description 42
- 239000010702 perfluoropolyether Substances 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000003995 emulsifying agent Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000006082 mold release agent Substances 0.000 description 7
- DEXIXSRZQUFPIK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylphosphonic acid Chemical compound OP(O)(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DEXIXSRZQUFPIK-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- -1 amine salt Chemical class 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 150000003863 ammonium salts Chemical group 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 4
- 231100000693 bioaccumulation Toxicity 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DMFIXDNZBSRKRU-UHFFFAOYSA-N CCOP(OC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)=O Chemical compound CCOP(OC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)=O DMFIXDNZBSRKRU-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Chemical group 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- PFQOXCOCJHNXRP-UHFFFAOYSA-N diazanium;dioxido-oxo-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-$l^{5}-phosphane Chemical compound [NH4+].[NH4+].[O-]P([O-])(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PFQOXCOCJHNXRP-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004991 fluoroalkenyl group Chemical group 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- FXDLNDFSCHYHJA-UHFFFAOYSA-N n,n-diethylethanamine;3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylphosphonic acid Chemical compound CCN(CC)CC.OP(O)(=O)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FXDLNDFSCHYHJA-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical class OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
本発明は、表面処理剤に関する。さらに詳しくは、パーフルオロポリエーテル油のエマルジョンよりなる表面処理剤に関する。 The present invention relates to a surface treatment agent . More specifically, the present invention relates to a surface treatment agent comprising an emulsion of perfluoropolyether oil.
ポリフルオロアルキルホスホン酸エステルは、離型剤の合成原料として広く用いられている。離型剤としたときの離型性能は、パーフルオロアルキル基の炭素数が8〜12である化合物において最も発現し易く、特にC8のテロマー化合物である
CF3(CF2)7CH2CH2P(O)(OC2H5)2
が、この種の用途に好んで使用されている(特許文献1〜4参照)。
Polyfluoroalkylphosphonic acid esters are widely used as raw materials for synthesizing release agents. The mold release performance when used as a mold release agent is most easily manifested in compounds having 8 to 12 carbon atoms in the perfluoroalkyl group, and is particularly a C 8 telomer compound.
CF 3 (CF 2 ) 7 CH 2 CH 2 P (O) (OC 2 H 5 ) 2
However, it is preferably used for this kind of application (see Patent Documents 1 to 4).
ところで、炭素数8〜12のパーフルオロアルキル基を有するテロマー化合物は、環境中で生物分解されて、生体蓄積性、環境濃縮性が比較的高い化合物に変化することが報告されており、処理工程での暴露や廃棄物、処理基材等からの環境への放出、拡散などが懸念されている。また、パーフルオロアルキル基の炭素数が14以上の化合物では、それの物理的、化学的性状からそれの取扱いが非常に困難であり、実際には殆ど使用されていない。 By the way, it has been reported that a telomer compound having a perfluoroalkyl group having 8 to 12 carbon atoms is biodegraded in the environment and converted into a compound having a relatively high bioaccumulation property and environmental concentration property. exposure and waste, the discharge, diffusion and the like are environmental concerns from the treated substrate or the like. In addition, compounds having a perfluoroalkyl group with 14 or more carbon atoms are very difficult to handle because of their physical and chemical properties, and are rarely used in practice.
さらに、炭素数8以上のパーフルオロアルキル基を有するテロマー化合物は、その製造プロセスにおいて、生体蓄積性の高いパーフルオロオクタン酸類の発生や混入が避けられない。そのため、このようなテロマー化合物の製造各社は、それの製造からの撤退や炭素数6以下のパーフルオロアルキル基を有する化合物への代替などを進めている。 Furthermore, telomer compounds having a perfluoroalkyl group having 8 or more carbon atoms cannot avoid the generation or contamination of perfluorooctanoic acids having high bioaccumulation potential in the production process. For this reason, manufacturers of such telomer compounds are proceeding withdrawing from the production or replacing them with compounds having a perfluoroalkyl group having 6 or less carbon atoms.
一方、パーフルオロアルキル基の炭素数が6以下の化合物では、処理基材表面での配向性が著しく低下し、また融点、ガラス転移点Tgなどが炭素数8の化合物に比べて著しく低いため、温度、湿度、応力、有機溶剤の接触などの使用環境条件に大きな影響を受けることとなる。そのため、求められる十分な性能が得られず、また耐久性などにも影響がみられる。 On the other hand , in the compound having 6 or less carbon atoms in the perfluoroalkyl group, the orientation on the surface of the treated substrate is remarkably lowered, and the melting point, the glass transition point Tg, etc. are remarkably lower than the compound having 8 carbon atoms. It will be greatly affected by environmental conditions such as temperature, humidity, stress, and contact with organic solvents. Therefore, the required sufficient performance cannot be obtained, and the durability is also affected.
パーフルオロアルキルアルキルホスホン酸のアンモニウム塩またはアミン塩とポリエーテル変性オルガノポリシロキサンとを水に溶解または分散させた水性離型剤組成物も提案されており(特許文献5参照)、この場合にもパーフルオロオクチルエチルホスホン酸塩が用いられ、透明な離型剤溶液が得られるとされている。 Aqueous mold release agent composition of the ammonium salt or amine salt and a polyether-modified organopolysiloxane is dissolved or dispersed in water perfluoroalkyl alkyl phosphonic acids have also been proposed (see Patent Document 5), also in this case Perfluorooctyl ethyl phosphonate is used, and it is said that a transparent release agent solution is obtained.
また、撥水撥油剤、潤滑剤等として広く用いられているパーフルオロポリエーテル油は、撥水撥油性、潤滑性などにはすぐれているが、他の化合物との相溶性に欠けるため、用途が限定される。 Perfluoropolyether oils widely used as water and oil repellents and lubricants are excellent in water and oil repellency and lubricity, but lack compatibility with other compounds. Is limited.
パーフルオロポリエーテル油は、これに加脂剤を加えることにより、皮革処理剤としての利用も図られている(特許文献6参照)。加脂剤としては、その一般的な記載において、フルオロアルキル基、フルオロアルケニル基またはフルオロエーテル基を有するホスホン酸誘導体またはそのアンモニウム塩、アルカリ金属塩またはアルカリ土類金属塩等が用いられるとされているが、加脂剤の使用割合はフッ素系オイルに対して10〜0.5、好ましくは5〜1の重量比とされている。 Perfluoropolyether oil is also used as a leather treatment agent by adding a greasing agent to the perfluoropolyether oil (see Patent Document 6). As the greasing agent, in a general description thereof, a phosphonic acid derivative having a fluoroalkyl group, a fluoroalkenyl group or a fluoroether group or an ammonium salt, an alkali metal salt or an alkaline earth metal salt thereof is used. However, the use ratio of the greasing agent is 10 to 0.5, preferably 5 to 1, with respect to the fluorinated oil.
このような重量比で用いられるフッ素オイルと加脂剤とは、通常エマルジョンの形態で含まれる皮革処理剤によって、加脂工程でなめし革処理されると述べられているが、加脂剤リッチで用いられる処理剤では、用いられる乳化剤量に比例して、エマルジョンの平均粒子径は小さくなり、また経時的な安定性も確保されるが、過剰に配合される親水性の加脂剤によって、被処理物が親水性化して、撥水性が低下したり、これを離型剤として用いたときの離型性能の低下を避けることができない(後記比較例参照)。 Fluorine oil and greasing agent used in such a weight ratio are said to be tanned leather treated in the greasing process by a leather treating agent usually contained in the form of an emulsion. In the processing agent to be used, the average particle size of the emulsion is reduced in proportion to the amount of emulsifier used, and the stability over time is ensured. The product becomes hydrophilic and water repellency is lowered, and it is not possible to avoid a drop in mold release performance when this is used as a mold release agent (see Comparative Examples below).
本出願人は先に、パーフルオロアルキルエチルホスホン酸ジエステルを熱分解や加水分解させることにより、パーフルオロアルキルエチルホスホン酸を製造する方法を提案している(特許文献7参照)。ここで得られるパーフルオロアルキルエチルホスホン酸は、水等の水性媒体には溶解しないため、乳化剤水溶液等として使用することはできない。 The present applicant has previously proposed a method for producing perfluoroalkylethylphosphonic acid by thermally decomposing or hydrolyzing perfluoroalkylethylphosphonic acid diester (see Patent Document 7). Since the perfluoroalkylethylphosphonic acid obtained here does not dissolve in an aqueous medium such as water, it cannot be used as an aqueous emulsifier solution.
一方、パーフルオロポリエーテル油は、これをエマルジョン化することで表面処理剤としての利用が可能となり、撥水撥油剤、離型剤等への応用が可能となる。また、エマルジョン化することにより、医学的な用途、化粧品用途への適用も可能となる。化粧品への配合は、例えば口紅に配合することにより、口紅が他に転写されるのを防ぐ作用を呈する。 On the other hand, perfluoropolyether oils, which enables use as a surface treatment agent by emulsifying, water- and oil-repellent, and can be applied to the release agent or the like. Moreover, by emulsifying, it can be applied to medical use and cosmetic use. For example, by blending into cosmetics, for example, by blending with lipstick, the effect of preventing the lipstick from being transferred to others is exhibited.
しかるに、特許文献6に記載される如きエマルジョンにおいては、フッ素系オイルに対して大過剰量の加脂剤(パーフルオロアルキルアルキルホスホン酸のアンモニウム塩または金属塩)が配合されて用いられるため、皮革処理方法としては好適であっても、パーフルオロポリエーテル油のエマルジョンに適用した場合には、これらの化合物自体の特性が十分に発揮されないことになる。 However, in an emulsion as described in Patent Document 6, since a large excess of a greasing agent (ammonium salt or metal salt of perfluoroalkylalkylphosphonic acid) is used in combination with fluorine-based oil, leather is used. Even if it is suitable as a treatment method, when it is applied to an emulsion of perfluoropolyether oil , the properties of these compounds themselves are not sufficiently exhibited.
本発明の目的は、生体蓄積性が低いといわれる炭素数6以下のパーフルオロアルキル基を有する化合物であって、乳化性能にすぐれたペンタデカフルオロオクタン酸アンモニウムに匹敵する乳化性能を有するものを乳化剤として用いた、パーフルオロポリエーテル油のエマルジョンよりなる表面処理剤を提供することにある。 An object of the present invention is to provide a compound having a perfluoroalkyl group having a carbon number of 6 or less, which is said to have low bioaccumulation, and having an emulsifying performance comparable to ammonium pentadecafluorooctanoate having excellent emulsifying performance. It is to provide a surface treatment agent comprising an emulsion of perfluoropolyether oil used as.
かかる本発明の目的は、一般式
RfO〔CF(CF3)CF2O〕mRf′ 〔I〕
(ここで、Rf、Rf′は炭素数1〜5のパーフルオロ低級アルキル基であり、mは2〜200の整数である)で表わされるパーフルオロポリエーテル油100重量部に対し、乳化剤として一般式
CnF2n+1CH2CH2P(O)(OM1)(OM2) 〔II〕
(ここで、M1は水素原子またはNH 4 基であり、M2はNH 4 基であり、nは1〜6の整数である)で表わされるパーフルオロアルキルエチルホスホン酸塩0.01〜30重量部を含有する水溶液を用いて形成させたエマルジョンを水でさらに希釈した水溶液よりなる成形金型面に適用される表面処理剤または基質上に適用される表面処理剤によって達成される。
The object of the present invention is to provide a general formula
RfO [CF (CF 3 ) CF 2 O] m Rf ′ (I)
(Wherein, Rf, Rf 'is a perfluoroalkyl lower alkyl group of 1 to 5 carbon atoms, m is an integer of 2 to 200) with respect to the perfluoropolyether oil 100 parts by weight represented by the general as an emulsifier formula
C n F 2n + 1 CH 2 CH 2 P (O) (OM 1 ) (OM 2 ) (II)
(Wherein M 1 is a hydrogen atom or an NH 4 group , M 2 is an NH 4 group , and n is an integer of 1 to 6) 0.01 to 30 parts by weight of perfluoroalkylethylphosphonate This is achieved by a surface treatment agent applied to a molding die surface comprising an aqueous solution obtained by further diluting an emulsion formed using an aqueous solution containing a surface treatment agent or a surface treatment agent applied onto a substrate.
本発明で用いられるパーフルオロアルキルエチルホスホン酸アンモニウム塩乳化剤は、生体蓄積性が低いといわれる炭素数6以下のパーフルオロアルキル基を有する化合物であって、乳化性能にすぐれたペンタデカフルオロオクタン酸アンモニウムに匹敵する乳化性能を有しており、この乳化剤の水溶液とパーフルオロポリエーテル油とからなるエマルジョンは、安定なエマルジョンを形成させることができる。その乳化安定性は、室温条件下または40℃で1ヶ月間放置した後においても良好に維持されている。 The ammonium perfluoroalkylethylphosphonate emulsifier used in the present invention is a compound having a perfluoroalkyl group having a carbon number of 6 or less, which is said to have low bioaccumulation, and is an ammonium pentadecafluorooctanoate having excellent emulsifying performance. The emulsion composed of an aqueous solution of this emulsifier and perfluoropolyether oil can form a stable emulsion. Its emulsification stability is well maintained even after standing at room temperature or at 40 ° C. for 1 month.
パーフルオロポリエーテル油とのエマルジョンは、その良好な乳化安定性を保持したまま、表面処理剤、離型剤、粘着防止剤、化粧品等の用途に好適に用いられる。 Emulsions with perfluoropolyether oils are suitably used for applications such as surface treatment agents, mold release agents, anti-tacking agents, cosmetics, etc. while maintaining good emulsion stability .
乳化剤として用いられるパーフルオロアルキルエチルホスホン酸アンモニウム塩
CnF2n+1CH2CH2P(O)(OM1)(OM2) 〔II〕
は、特許文献7に記載されるパーフルオロアルキルエチルホスホン酸
CnF2n+1CH2CH2P(O)(OH)2 〔III〕
に、アンモニア水溶液を反応させることにより得られる。
Perfluoroalkylethylphosphonic acid ammonium salt used as emulsifier
C n F 2n + 1 CH 2 CH 2 P (O) (OM 1 ) (OM 2 ) (II)
Perfluoroalkylethylphosphonic acid described in Patent Document 7
C n F 2n + 1 CH 2 CH 2 P (O) (OH) 2 (III)
To be obtained by reacting an aqueous ammonia solution.
アンモニアは、パーフルオロアルキルエチルホスホン酸に対して等モル量用いられた場合にはモノ塩を形成させ、また2倍モル量用いられた場合にはジ塩を形成させる。一般には、必要理論モル数以上で用いられ、等モル量以上2倍モル量未満で用いられた場合には、モノ塩とジ塩との混合物を形成させる。 Ammonia forms a mono-salt when used in equimolar amounts relative to perfluoroalkylethylphosphonic acid, and forms a di-salt when used in double molar amounts. Generally, it is used in the required theoretical number of moles or more, and when used in an equimolar amount or more and less than twice the molar amount, a mixture of a mono salt and a di salt is formed.
パーフルオロアルキルエチルホスホン酸アンモニウム塩は、水に溶解させた水溶液として用いられる。 Perfluoroalkylethylphosphonic acid ammonium salt is used as an aqueous solution dissolved in water .
パーフルオロアルキルエチルホスホン酸塩の乳化能力は、例えば2-(パーフルオロヘキシル)エチルホスホン酸アンモニウム水溶液の場合、その臨界ミセル濃度〔CMC〕は乳化剤濃度が0.8重量%付近にみられ、乳化剤濃度が2.0重量%程度迄一定の低い表面張力が示される。 The emulsifying capacity of perfluoroalkylethylphosphonate is, for example, in the case of aqueous 2- (perfluorohexyl) ethylphosphonate ammonium solution, the critical micelle concentration [CMC] is found at an emulsifier concentration of about 0.8% by weight. A constant low surface tension is shown up to about 2.0% by weight.
乳化剤の水性溶液または有機溶媒溶液は、パーフルオロポリエーテル油100重量部当り、その有効成分量が約0.01〜30重量部、好ましくは約0.1〜15重量部の割合でパーフルオロポリエーテル油に添加され、乳化処理されて、パーフルオロポリエーテル油エマルジョンを形成させる。乳化剤をこれ以上の割合で用いると、パーフルオロポリエーテル油自体の特性が十分に発揮されないようになる。乳化処理は、ホモジナイザ等を用い、約500〜10,000rpmの回転数で予備乳化を行った後、さらに高圧ホモジナイザを用い、圧力約100〜800kgf/cm2(約9.8〜78.4MPa)で乳化処理されて行われる。 An aqueous solution or an organic solvent solution of the emulsifier is added to the perfluoropolyether oil in an amount of about 0.01 to 30 parts by weight, preferably about 0.1 to 15 parts by weight, based on 100 parts by weight of the perfluoropolyether oil. And emulsified to form a perfluoropolyether oil emulsion. When the emulsifier is used in a proportion higher than this, the characteristics of the perfluoropolyether oil itself are not sufficiently exhibited. The emulsification treatment is performed by pre-emulsification using a homogenizer or the like at a rotational speed of about 500 to 10,000 rpm, and further emulsified at a pressure of about 100 to 800 kgf / cm 2 (about 9.8 to 78.4 MPa) using a high-pressure homogenizer. Done.
エマルジョン化されるパーフルオロポリエーテル油としては、一般式
RfO〔CF(CF 3 )CF 2 O〕 m Rf′ 〔I〕
で表わされるものが使用される。ここで、Rf、Rf′はパーフルオロメチル基、パーフルオロエチル基等の炭素数1〜5のパーフルオロ低級アルキル基であり、mは2〜200である。また、その数平均分子量Mnが約300〜50000、好ましくは約500〜20000のものが用いられる。
The perfluoropolyether oil to be emulsified has a general formula
RfO [CF (CF 3 ) CF 2 O] m Rf ′ (I)
The one represented by is used. Here, Rf and Rf ′ are perfluoro lower alkyl groups having 1 to 5 carbon atoms such as perfluoromethyl group and perfluoroethyl group, and m is 2 to 200 . Further, those having a number average molecular weight Mn of about 300 to 50000, preferably about 500 to 20000 are used.
これはヘキサフルオロプロペンの光酸化重合で生成した先駆体を完全にふっ素化することにより、あるいはふっ化セシウム触媒の存在下にヘキサフルオロプロペンオキシドをアニオン重合させ、得られた末端−CF(CF3)COF基を有する酸フロリド化合物をふっ素ガス処理することにより得られる。 This by completely fluorinating the precursor produced by photooxidation polymerization of hexafluoropropene, or a hexafluoropropene oxide was subjected to anionic polymerization in the presence of cesium fluoride catalyst, resulting terminal -CF (CF 3 ) It can be obtained by treating an acid fluoride compound having a COF group with a fluorine gas.
パーフルオロポリエーテル油〔I〕としては、どのような値の動粘度のものでも使用できるが、潤滑剤としては5〜2000mm2/秒(40℃)、高温条件下での使用を考慮すると好ましくは100〜1500mm2/秒(40℃)のものが用いられる。すなわち、約5mm2/秒以下のものは蒸発量が多く、耐熱用グリースの規格であるJIS転がり軸受用グリース3種で規定されている蒸発量1.5%以下という条件を満たさなくなる。また、2000mm2/秒以上の動粘度のものは、流動点(JIS K-2283)が10℃以上となり、通常の方法では低温起動時に軸受が回転せず、それを使用可能とするには加熱する必要がある。 Perfluoropolyether oil [I] can be used with any value of kinematic viscosity, but as a lubricant, it is preferably 5 to 2000 mm 2 / sec (40 ° C.), considering use under high temperature conditions. Is 100 to 1500 mm 2 / sec (40 ° C.). In other words, those with about 5 mm 2 / sec or less have a large evaporation amount and do not satisfy the condition of an evaporation amount of 1.5% or less stipulated in the JIS rolling bearing grease type 3 which is a standard for heat-resistant grease. Also, those with a kinematic viscosity of 2000 mm 2 / sec or higher have a pour point (JIS K-2283) of 10 ° C or higher, and the bearing does not rotate at low temperature startup in the normal method. There is a need to.
また、パーフルオロポリエーテル油エマルジョンは、さらにその固形分(パーフルオロポリエーテル油)濃度が約0.01〜30重量%、好ましくは約0.05〜10重量%を占める量となるように水で希釈した水溶液として用いることにより、良好な乳化安定性を保持したまま、撥水撥油剤、離型剤等の表面処理剤としても用いられる。離型剤として用いられる場合には、成形金型面にこれが適用され、成形品等の基質上に適用される場合には、粘着防止剤として用いられる。 Further, the perfluoropolyether oil emulsion is an aqueous solution diluted with water so that the solid content (perfluoropolyether oil) concentration is about 0.01 to 30% by weight, preferably about 0.05 to 10% by weight. By using as a surface treatment agent such as a water / oil repellent and a release agent, while maintaining good emulsification stability. When it is used as a mold release agent, it is applied to a molding die surface, and when it is applied to a substrate such as a molded product, it is used as an anti-sticking agent.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例1
(1) 攪拌装置および滴下装置を備えた容量200mlに反応装置内に、40℃に加熱された水50gを保温しながら仕込み、そこに2-(パーフルオロヘキシル)エチルホスホン酸(ユニマテック製品CHEMINOX FHP-2-OH)5g(11.7ミリモル)を加えた後、濃度1.4重量%のアンモニア水溶液20.5g(16.9ミリモル)を加え、1時間攪拌を続けて中和反応を行った。これにより、pH8の2-(パーフルオロヘキシル)エチルホスホン酸アンモニウム塩の水溶液(有効成分濃度6.9重量%)が得られた〔乳化剤水溶液I〕。
Example 1
(1) A 200 ml capacity equipped with a stirrer and a dripping device was charged into a reactor while keeping 50 g of water heated to 40 ° C. while keeping 2- (perfluorohexyl) ethylphosphonic acid (Unimatec CHEMINOX FHP). After adding 2 g (11.7 mmol) of 2-OH), 20.5 g (16.9 mmol) of an aqueous ammonia solution having a concentration of 1.4% by weight was added, and stirring was continued for 1 hour to carry out a neutralization reaction. As a result, an aqueous solution of 2- (perfluorohexyl) ethylphosphonic acid ammonium salt having a pH of 8 (active ingredient concentration: 6.9% by weight) was obtained [Emulsifier aqueous solution I].
この乳化剤水溶液Iを水中に少量ずつ添加し、その水溶液の表面張力を測定した。図1のグラフに○印で示される如く、それの臨界ミセル濃度〔CMC〕は0.8重量%で、最低表面張力は17mN/mであった。表面張力の測定は、SITA製動的表面張力計を用い、20℃で、最大気泡法で測定した。 This aqueous emulsifier solution I was added little by little in water, and the surface tension of the aqueous solution was measured. As indicated by a circle in the graph of FIG. 1, the critical micelle concentration [CMC] was 0.8% by weight and the minimum surface tension was 17 mN / m. The surface tension was measured at 20 ° C. by the maximum bubble method using a SITA dynamic surface tension meter.
なお、2-(パーフルオロヘキシル)エチルホスホン酸に、アンモニア水溶液を加えることなく1時間攪拌した場合には、添加した2-(パーフルオロヘキシル)エチルホスホン酸は水に溶解せずに分離し、水溶液は得られなかった。 When stirring for 1 hour without adding an aqueous ammonia solution to 2- (perfluorohexyl) ethylphosphonic acid, the added 2- (perfluorohexyl) ethylphosphonic acid was separated without dissolving in water, An aqueous solution was not obtained.
(2) 攪拌装置および滴下装置を備えた容量1,000mlの反応装置内に、40℃に加熱された水182gを保温しながら仕込み、そこに乳化剤水溶液I 218gおよび一般式
C3F7O〔CF(CF3)CF2O〕mC2F5 (m:2〜100)
で表わされるパーフルオロポリエーテル油(NOKクリューバー製品BARRIERTA J 25 FLUID;動粘度(40℃)25mm2/秒)100g(以上合計量500g)を加えた後、ホモジナイザを用いて回転数3000rpmで2分間の予備乳化を行い、さらに高圧ホモジナイザ(日本精機製)を用いて圧力600kgf/cm2(58.8MPa)で乳化処理し、パーフルオロポリエーテル油エマルジョンA(パーフルオロポリエーテル油100重量部に対して、パーフルオロアルキルエチルホスホン酸アンモニウム塩は15.0重量部)を485g(回収率97%)得た。
(2) In a 1,000 ml reactor equipped with a stirrer and a dropping device, 182 g of water heated to 40 ° C. was charged while being kept therein, and 218 g of an emulsifier aqueous solution I and a general formula
C 3 F 7 O [CF (CF 3 ) CF 2 O] m C 2 F 5 (m: 2 to 100)
After adding 100 g (overall amount 500 g) of perfluoropolyether oil (NOK Kluber product BARRIERTA J 25 FLUID; kinematic viscosity (40 ° C.) 25 mm 2 / sec) represented by 2 at a rotational speed of 3000 rpm using a homogenizer Pre-emulsification for 5 minutes, and further emulsified with a high pressure homogenizer (manufactured by Nippon Seiki Co., Ltd.) at a pressure of 600 kgf / cm 2 (58.8 MPa), and perfluoropolyether oil emulsion A (per 100 parts by weight of perfluoropolyether oil) As a result, 485 g (97% recovery rate) of 15.0 parts by weight of perfluoroalkylethylphosphonic acid ammonium salt was obtained.
得られたパーフルオロポリエーテル油エマルジョンAの平均粒子径は、151nmであった。このエマルジョンAを、室温条件下および40℃でそれぞれ1ヶ月間静置した後の平均粒子径を測定すると、それぞれ153nm、155nmという値が得られ、いずれも安定なエマルジョンが形成されていることが確認された。なお、平均粒子径の測定は、日機装製マイクロドラック粒度分布計UPA150を用い、動的光散乱法によって行われた。 The average particle diameter of the obtained perfluoropolyether oil emulsion A was 151 nm. When the average particle diameter of this emulsion A after standing at room temperature and at 40 ° C. for 1 month was measured, values of 153 nm and 155 nm were obtained, respectively, indicating that stable emulsions were formed. confirmed. The average particle size was measured by a dynamic light scattering method using a Nikkiso Microdrug Particle Size Distribution Analyzer UPA150.
なお、水量を385gに変更し、また乳化剤水溶液Iの代りに2-(パーフルオロヘキシル)エチルホスホン酸15gを用いると、混合液は直ちに液-液分離を起こしてしまい、エマルジョンは形成されなかった。 When the amount of water was changed to 385 g, and when 15 g of 2- (perfluorohexyl) ethylphosphonic acid was used in place of the emulsifier aqueous solution I, the liquid mixture immediately caused liquid-liquid separation, and no emulsion was formed. .
参考例1
実施例1(1)において、2-(パーフルオロヘキシル)エチルホスホン酸およびアンモニア水溶液の代りに、ペンタデカフルオロオクタン酸アンモニウム塩(ジエムコ製品エフトップEF204)5gを用い、それの水溶液(有効成分濃度9.1重量%)を得た〔乳化剤水溶液II〕。
Reference example 1
In Example 1 (1), instead of 2- (perfluorohexyl) ethylphosphonic acid and an aqueous ammonia solution, 5 g of pentadecafluorooctanoic acid ammonium salt (Diemco product F-top EF204) was used. 9.1 wt%) was obtained [Emulsifier aqueous solution II].
この乳化剤水溶液IIについて、同様に表面張力を測定すると、図1のグラフに■印で示される如く、それのCMCは0.8重量%で、最低表面張力は18mN/mであった。 When the surface tension of this aqueous emulsifier II was measured in the same manner, as shown by the black square in the graph of FIG. 1, its CMC was 0.8% by weight and the minimum surface tension was 18 mN / m.
実施例2
実施例1(2)において、同じ一般式で表わされるパーフルオロポリエーテル油(NOKクリューバー製品BARRIERTA J 100 FLUID;動粘度(40℃)95mm2/秒)が同量(100g)用いられ(合計量500g)、パーフルオロポリエーテル油エマルジョンBを486g(回収率97%)得た。このエマルジョンBの平均粒子径は131nm、室温1ヶ月経過後の平均粒子径は136nm、40℃1ヶ月経過後の平均粒子径は140nmであり、安定なエマルジョンが形成されていることが確認された。
Example 2
In Example 1 (2), the same amount (100 g) of perfluoropolyether oil represented by the same general formula (NOK Kluber product BARRIERTA J 100 FLUID; kinematic viscosity (40 ° C.) 95 mm 2 / sec) was used (total) 500 g), and 486 g of perfluoropolyether oil emulsion B (recovery rate 97%) was obtained. The average particle size of this emulsion B was 131 nm, the average particle size after one month at room temperature was 136 nm, the average particle size after one month at 40 ° C. was 140 nm, and it was confirmed that a stable emulsion was formed. .
実施例3
実施例1(2)において、同じ一般式で表わされるパーフルオロポリエーテル油(NOKクリューバー製品BARRIERTA J 400 FLUID;動粘度(40℃)390mm2/秒)が同量(100g)用いられ(合計量500g)、パーフルオロポリエーテル油エマルジョンCを485g(回収率97%)得た。このエマルジョンCの平均粒子径は145nm、室温1ヶ月経過後の平均粒子径は146nm、40℃1ヶ月経過後の平均粒子径は150nmであり、比較的安定なエマルジョンが形成されていることが確認された。
Example 3
In Example 1 (2), the same amount (100 g) of perfluoropolyether oil represented by the same general formula (NOK Kluber product BARRIERTA J 400 FLUID; kinematic viscosity (40 ° C.) 390 mm 2 / sec) was used (total) 500 g) and 485 g of Perfluoropolyether oil emulsion C (97% recovery rate). The average particle size of this emulsion C is 145 nm, the average particle size after one month at room temperature is 146 nm, the average particle size after one month at 40 ° C. is 150 nm, and it is confirmed that a relatively stable emulsion is formed. It was done.
参考例2
実施例2において、乳化剤水溶液Iの代りにペンタデカフルオロオクタン酸アンモニウム塩水溶液である乳化剤水溶液IIが165g用いられ、また水量を235gに変更して用いられ(合計量500g)、パーフルオロポリエーテル油エマルジョンDを482g(回収率96%)得た。このエマルジョンDの平均粒子径は140nm、室温1ヶ月経過後の平均粒子径は143nm、40℃1ヶ月経過後の平均粒子径は145nmであり、安定なエマルジョンが形成された。
Reference example 2
In Example 2, 165 g of an emulsifier aqueous solution II which is an aqueous solution of pentadecafluorooctanoic acid ammonium salt is used in place of the emulsifier aqueous solution I, and the amount of water is changed to 235 g (total amount 500 g). 482 g of emulsion D (96% recovery rate) was obtained. The average particle size of this emulsion D was 140 nm, the average particle size after one month at room temperature was 143 nm, the average particle size after one month at 40 ° C. was 145 nm, and a stable emulsion was formed.
比較例1
(1) 実施例1(1)において、濃度1.4重量%のアンモニア水溶液20.5g(16.9ミリモル)の代りに、トリエチルアミン1.71g(16.9ミリモル)を用い、2-(パーフルオロヘキシル)エチルホスホン酸トリエチルアミン塩の水溶液(有効成分濃度8.9重量%)を得た〔乳化剤水溶液III〕。
Comparative Example 1
(1) In Example 1 (1), 1.71 g (16.9 mmol) of triethylamine was used instead of 20.5 g (16.9 mmol) of an aqueous ammonia solution having a concentration of 1.4% by weight, and 2- (perfluorohexyl) ethylphosphonic acid triethylamine salt was used. (Emulsifier aqueous solution III) was obtained.
この乳化剤水溶液IIIの臨界ミセル濃度〔CMC〕および最低表面張力を同様にして測定すると、それぞれ1.2重量%および27.7mN/mという値が得られた。 When the critical micelle concentration [CMC] and the minimum surface tension of this aqueous emulsifier solution III were measured in the same manner, values of 1.2% by weight and 27.7 mN / m were obtained, respectively.
(2) 実施例1(2)において、40℃に加熱された水量を231gに、乳化剤水溶液Iの代りに用いられた乳化剤水溶液III量を169gに、パーフルオロポリエーテル油(BARRIERTA J 100 FLUID)量を100gに、それぞれ種類および量を変更し(合計量500g)、パーフルオロポリエーテル油エマルジョンEを483g(回収率97%)得た。 (2) In Example 1 (2), the amount of water heated to 40 ° C. was changed to 231 g, the amount of the emulsifier aqueous solution III used instead of the emulsifier aqueous solution I was changed to 169 g, and the perfluoropolyether oil (BARRIERTA J 100 FLUID) The amount and amount were changed to 100 g (total amount 500 g), respectively, and 483 g (97% recovery rate) of perfluoropolyether oil emulsion E was obtained.
得られたパーフルオロポリエーテル油エマルジョンEの平均粒子径は405nmであった。また、このエマルジョンEを、室温条件下および40℃でそれぞれ1ヶ月間静置すると、いずれも沈殿が生成し、分離していることが確認された。 The average particle diameter of the obtained perfluoropolyether oil emulsion E was 405 nm. Further, it was confirmed that when this emulsion E was allowed to stand at room temperature and at 40 ° C. for 1 month, a precipitate was formed and separated.
実施例4
イオン交換水97.5重量部に、攪拌しながらパーフルオロポリエーテル油エマルジョンA 2.5重量部を添加して希釈し、離型剤乳液を調製した。
Example 4
A release agent emulsion was prepared by adding 2.5 parts by weight of perfluoropolyether oil emulsion A to 97.5 parts by weight of ion-exchanged water while stirring.
この離型剤乳液を用いてのウレタンゴム成形時の離型試験を、次のように実施した。
直径45mm、深さ50mmのアルミニウム製カップを成形型とし、この型を80℃に加熱した後離型剤を塗布して、80℃で乾燥させた。この離型剤塗布型内に、80℃に加熱したウレタンプレポリマー(日本ポリウレタン製品コロネート4090)100重量部と120℃に加熱させたメチレンビス(o-クロロアニリン)硬化剤(イハラケミカル製品イハラキュアミンMT)12.8重量部との混合物10gを注入し、120℃で1時間加熱硬化させた。
A mold release test at the time of molding urethane rubber using this mold release agent emulsion was carried out as follows .
An aluminum cup having a diameter of 45 mm and a depth of 50 mm was used as a mold, the mold was heated to 80 ° C., a release agent was applied, and the mold was dried at 80 ° C. In this release agent coating mold, 100 parts by weight of urethane prepolymer (Japan polyurethane product Coronate 4090) heated to 80 ° C and methylene bis (o-chloroaniline) curing agent (Ihara Chemical product Iharacamine) heated to 120 ° C MT) 10 g of a mixture of 12.8 parts by weight was injected and cured at 120 ° C. for 1 hour.
硬化前に、注入部中央に硬化成形品取出し用のフックを設置させておき、硬化後にそのフックを引っ張って成形品を型から取出す際の荷重を上方に位置するバネ秤で求めると、8Nという値(離型性能)が得られた。また離型剤を最初1回塗布した後、50N以下の離型荷重で何回迄離型できるかの回数を測定すると、9回という値(離型寿命)が得られた。 Before curing, the hook for curing demolding the injection unit center is installed in advance, when determining the load when retrieving later from the mold a molded product by pulling the hook curing a spring weigher located above referred 8N The value (release performance) was obtained. When the number of times the mold can be released with a release load of 50 N or less was measured after first applying the mold release agent, a value of 9 times (mold release life) was obtained.
一方、この離型剤乳液を塗布しないで、離型性能および離型寿命の測定を行ったが、成形品が金型から剥がれず、測定不能であり、したがって離型寿命は0回という結果であった。 On the other hand, the release performance and release life were measured without applying the release agent emulsion, but the molded product did not peel off from the mold and could not be measured. Therefore, the release life was 0 times. there were.
比較例2
(1) 実施例1(1)において、2-(パーフルオロヘキシル)エチルホスホン酸量を10g(23.4ミリモル)に、また濃度1.4重量%のアンモニア水溶液量を40g(32.9ミリモル)にそれぞれ変更し、それの水溶液(有効成分濃度10.0重量%)を得た〔乳化剤水溶液IV〕。
Comparative Example 2
(1) In Example 1 (1), the amount of 2- (perfluorohexyl) ethylphosphonic acid was changed to 10 g (23.4 mmol), and the amount of aqueous ammonia solution having a concentration of 1.4% by weight was changed to 40 g (32.9 mmol). An aqueous solution thereof (active ingredient concentration 10.0% by weight) was obtained [emulsifier aqueous solution IV].
(2) 実施例1(2)において、乳化剤水溶液IV 250g、パーフルオロポリエーテル油(BARRIERTA J 100 FLUID)5gおよび水245g(以上合計500g)が用いられ、パーフルオロポリエーテル油エマルジョンFを486g(回収率97%)得た。このエマルジョンFの平均粒子径は61nm、室温1ヶ月経過後の平均粒子径は65nm、40℃1ヶ月経過後の平均粒子径は66nmであり、比較的安定なエマルジョンが形成されていることが確認された。 (2) In Example 1 (2), 250 g of emulsifier aqueous solution IV, 5 g of perfluoropolyether oil (BARRIERTA J 100 FLUID) and 245 g of water (over 500 g in total) were used, and 486 g of perfluoropolyether oil emulsion F was used. (97% recovery). The average particle size of this emulsion F is 61 nm, the average particle size after one month at room temperature is 65 nm, the average particle size after one month at 40 ° C. is 66 nm, and it is confirmed that a relatively stable emulsion is formed. It was done.
(3) 実施例4において、パーフルオロポリエーテル油エマルジョンAの代りに、同量(2.5重量部)のパーフルオロポリエーテル油エマルジョンFを用いて離型剤乳液を調製し、それを用いてウレタンゴム成形時の離型試験を行うと、離型性能20N、離型寿命2回という測定結果であった。 (3) In Example 4 , instead of perfluoropolyether oil emulsion A, a release agent emulsion was prepared using the same amount (2.5 parts by weight) of perfluoropolyether oil emulsion F, and then using that as a urethane When a mold release test at the time of rubber molding was performed, the measurement result was a mold release performance of 20 N and a mold release life of 2 times.
Claims (3)
RfO〔CF(CF3)CF2O〕mRf′ 〔I〕
(ここで、Rf、Rf′は炭素数1〜5のパーフルオロ低級アルキル基であり、mは2〜200の整数である)で表わされるパーフルオロポリエーテル油100重量部に対し、乳化剤として一般式
CnF2n+1CH2CH2P(O)(OM1)(OM2) 〔II〕
(ここで、M1は水素原子またはNH 4 基であり、M2はNH 4 基であり、nは1〜6の整数である)で表わされるパーフルオロアルキルエチルホスホン酸塩0.01〜30重量部を含有する水溶液を用いて形成させたエマルジョンを水でさらに希釈した水溶液よりなる成形金型面に適用される表面処理剤。 General formula
RfO [CF (CF 3 ) CF 2 O] m Rf ′ (I)
(Wherein, Rf, Rf 'is a perfluoroalkyl lower alkyl group of 1 to 5 carbon atoms, m is an integer of 2 to 200) with respect to the perfluoropolyether oil 100 parts by weight represented by the general as an emulsifier formula
C n F 2n + 1 CH 2 CH 2 P (O) (OM 1 ) (OM 2 ) (II)
(Wherein M 1 is a hydrogen atom or an NH 4 group , M 2 is an NH 4 group , and n is an integer of 1 to 6) 0.01 to 30 parts by weight of perfluoroalkylethylphosphonate A surface treatment agent to be applied to a molding die surface comprising an aqueous solution obtained by further diluting an emulsion formed with an aqueous solution containing an aqueous solution.
RfO〔CF(CF3)CF2O〕mRf′ 〔I〕
(ここで、Rf、Rf′は炭素数1〜5のパーフルオロ低級アルキル基であり、mは2〜200の整数である)で表わされるパーフルオロポリエーテル油100重量部に対し、乳化剤として一般式
CnF2n+1CH2CH2P(O)(OM1)(OM2) 〔II〕
(ここで、M1は水素原子またはNH 4 基であり、M2はNH 4 基であり、nは1〜6の整数である)で表わされるパーフルオロアルキルエチルホスホン酸塩0.01〜30重量部を含有する水溶液を用いて形成させたエマルジョンを水でさらに希釈した水溶液よりなる基質上に適用される表面処理剤。 General formula
RfO [CF (CF 3 ) CF 2 O] m Rf ′ (I)
(Wherein, Rf, Rf 'is a perfluoroalkyl lower alkyl group having 1-5 carbon atoms, m is an integer of 2 to 200) with respect to the perfluoropolyether oil 100 parts by weight represented by the general as an emulsifier formula
C n F 2n + 1 CH 2 CH 2 P (O) (OM 1 ) (OM 2 ) (II)
(Wherein M 1 is a hydrogen atom or an NH 4 group , M 2 is an NH 4 group , and n is an integer of 1 to 6) 0.01 to 30 parts by weight of perfluoroalkylethylphosphonate A surface treatment agent to be applied onto a substrate comprising an aqueous solution obtained by further diluting an emulsion formed with an aqueous solution containing a water.
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KR1020127004331A KR101413015B1 (en) | 2009-09-17 | 2010-09-10 | Emulsion and mold release agent comprising the emulsion |
EP10817116.6A EP2479216B1 (en) | 2009-09-17 | 2010-09-10 | Emulsion and mold release agent comprising the emulsion |
PCT/JP2010/065620 WO2011034003A1 (en) | 2009-09-17 | 2010-09-10 | Emulsion and mold release agent comprising the emulsion |
CN201080042036.6A CN102510880B (en) | 2009-09-17 | 2010-09-10 | Emulsion and mold release agent comprising the emulsion |
US13/496,581 US9610634B2 (en) | 2009-09-17 | 2010-09-10 | Emulsion and mold-releasing agent using the same |
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