JP2013151648A - Mixed solvent and surface-treating agent - Google Patents
Mixed solvent and surface-treating agent Download PDFInfo
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- JP2013151648A JP2013151648A JP2012236516A JP2012236516A JP2013151648A JP 2013151648 A JP2013151648 A JP 2013151648A JP 2012236516 A JP2012236516 A JP 2012236516A JP 2012236516 A JP2012236516 A JP 2012236516A JP 2013151648 A JP2013151648 A JP 2013151648A
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- 239000012046 mixed solvent Substances 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 74
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 44
- 239000011737 fluorine Substances 0.000 claims abstract description 44
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 42
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000012756 surface treatment agent Substances 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 19
- -1 phosphoric acid ester compound Chemical class 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 229910000679 solder Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000006082 mold release agent Substances 0.000 claims description 5
- 230000002265 prevention Effects 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims 1
- 238000004078 waterproofing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 abstract description 5
- 229920002313 fluoropolymer Polymers 0.000 description 15
- 239000004811 fluoropolymer Substances 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
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- 238000000034 method Methods 0.000 description 6
- BRWBDEIUJSDQGV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxyhexane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BRWBDEIUJSDQGV-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 4
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
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- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- XJSRKJAHJGCPGC-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XJSRKJAHJGCPGC-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 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
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、混合溶剤およびそれを用いた表面処理剤に関する。 The present invention relates to a mixed solvent and a surface treatment agent using the same.
従来、各種基材表面には、撥水性、撥油性およびフラックス等の溶剤（２−プロパノール：ＩＰＡ）に対する撥ＩＰＡ性を付与するためのフッ素系重合体、特に多くの場合パーフルオロアルキル基を有するフッ素系重合体を乾燥性溶剤中に含む表面処理剤が適用される。この表面処理剤に使用される溶剤は、乾燥性が良好であって、かつフッ素系重合体の溶剤となり得るものである。フッ素系重合体は、本質的に通常の有機溶剤に対する溶解性が貧しいことから、フッ素系重合体の溶剤は、実質的にフッ素系溶剤である。 Conventionally, various base materials have a fluorine-based polymer for imparting IPA repellency to a solvent (2-propanol: IPA) such as water repellency, oil repellency, and flux, and in many cases has a perfluoroalkyl group in many cases. A surface treatment agent containing a fluoropolymer in a drying solvent is applied. The solvent used for this surface treating agent has good drying properties and can be a solvent for a fluoropolymer. Since the fluorine-based polymer has essentially poor solubility in ordinary organic solvents, the solvent of the fluorine-based polymer is substantially a fluorine-based solvent.
これまで使用されてきたフッ素系溶剤の典型例は、いわゆるフロン溶剤であり、たとえばジクロロペンタフルオロプロパンおよびジクロロフルオロエタン等のハイドロクロロフルオロカーボン（ＨＣＦＣ）などである。これらの溶剤は、フッ素系重合体の溶解性の他にも、低表面張力を持つため、表面処理剤の溶剤として非常に有用であった。 A typical example of the fluorine-based solvent that has been used so far is a so-called chlorofluorocarbon solvent such as hydrochlorofluorocarbon (HCFC) such as dichloropentafluoropropane and dichlorofluoroethane. Since these solvents have a low surface tension in addition to the solubility of the fluoropolymer, they have been very useful as solvents for surface treatment agents.
しかし、ＨＣＦＣはオゾン破壊係数を有するため、先進国においては２０２０年に生産が全廃されることが決まっている。また、代替フロンとして使用されてきたトリデカフルオロヘキサンやデカフルオロペンタン等の一部のハイドロフルオロカーボン（ＨＦＣ）、パーフルオロヘキサン等のパーフルオロカーボン（ＰＦＣ）も、温暖化係数が高いため、地球温暖化防止の目的から京都議定書の規制対象物質となっている。 However, since HCFC has an ozone depletion coefficient, it is decided that production will be completely abolished in 2020 in developed countries. In addition, some hydrofluorocarbons (HFC) such as tridecafluorohexane and decafluoropentane, which have been used as alternative chlorofluorocarbons, and perfluorocarbons (PFC) such as perfluorohexane have a high global warming potential. It is a regulated substance of the Kyoto Protocol for the purpose of prevention.
そこで、上記に代わり得るフッ素系溶剤の開発が進められているものの一つに、ハイドロフルオロエーテル（ＨＦＥ）がある。その中には、（パーフルオロブトキシ）メタン（Ｃ4Ｆ9ＯＣＨ3）、（パーフルオロブトキシ）エタン（Ｃ4Ｆ9ＯＣ2Ｈ5）、（パーフルオロヘキソキシ）メタン（Ｃ6Ｆ13ＯＣＨ3）、２，２，２−トリフルオロエトキシ−１，１，２，２−テトラフルオロエタン（ＣＦ3ＣＨ2ＯＣＦ2ＣＦ2Ｈ）など既に市販されているものもある。しかしながら、これらＨＦＥは溶解性に乏しいものが多い。 Thus, hydrofluoroether (HFE) is one of the developments of fluorinated solvents that can be used instead of the above. Among them, (perfluorobutoxy) methane (C 4 F 9 OCH 3 ), (perfluorobutoxy) ethane (C 4 F 9 OC 2 H 5 ), (perfluorohexoxy) methane (C 6 F 13 OCH 3 ), 2,2,2-trifluoroethoxy-1,1,2,2-tetrafluoroethane (CF 3 CH 2 OCF 2 CF 2 H) and others are already commercially available. However, many of these HFEs have poor solubility.
一方、溶解性の高い溶剤として、ベンゼン骨格を有するフッ素系溶剤として、たとえばビス（トリフルオロメチル）ベンゼンなどがある。これらのベンゼン骨格を有するフッ素系溶剤は、非フッ素化合物にも高い溶解性も持ち合わせており、非常に有用な溶剤である。しかしながら、これらのベンゼン骨格を有するフッ素系溶剤は引火性がある。 On the other hand, examples of the highly soluble solvent include bis (trifluoromethyl) benzene as a fluorine-based solvent having a benzene skeleton. These fluorinated solvents having a benzene skeleton have high solubility in non-fluorine compounds and are very useful solvents. However, these fluorinated solvents having a benzene skeleton are flammable.
溶解性の高いベンゼン骨格を有するフッ素系溶剤を、非引火性フッ素系溶剤と混合してフッ素系重合体の溶剤とする開示がある。たとえば、１，３−ジ（トリフルオロメチル）ベンゼンを上記ＨＦＥ、ＨＦＣなどとの混合溶剤として全溶剤中５重量％または４９.７５重量％の量で含ませた例や（特許文献１参照）、１０質量％、２０質量％または５５質量％の量で含ませた例（特許文献２参照）がある。 There is a disclosure that a fluorine-based solvent having a highly soluble benzene skeleton is mixed with a non-flammable fluorine-based solvent to form a solvent for a fluorine-based polymer. For example, an example in which 1,3-di (trifluoromethyl) benzene is contained as a mixed solvent with the above HFE, HFC or the like in an amount of 5 wt% or 49.75 wt% in the total solvent (see Patent Document 1) There is an example (see Patent Document 2) containing 10% by mass, 20% by mass or 55% by mass.
このように、ＨＦＥやＨＦＣなどの溶解性の乏しい溶剤にベンゼン骨格を有するフッ素系溶剤を混合して、より有益な混合溶剤とすることは、以前から検討されてきている。しかしながら、ＨＦＥやＨＦＣなどの非引火性フッ素系溶剤は、通常の溶剤と比べ蒸気圧が高く、混合溶剤として用いると、非引火性フッ素系溶剤が先に気化してしまう。工業的に溶剤を使用する場合は、長期にわたり使用されることが多く、溶剤の揮発により溶剤組成が著しく変化することは、各種トラブルの原因となる（溶質の析出、引火特性の変化など）。 Thus, it has been studied for a long time that a fluorine-based solvent having a benzene skeleton is mixed with a solvent having poor solubility such as HFE or HFC to obtain a more useful mixed solvent. However, non-flammable fluorine-based solvents such as HFE and HFC have a higher vapor pressure than ordinary solvents, and when used as a mixed solvent, the non-flammable fluorine-based solvent vaporizes first. When a solvent is used industrially, it is often used for a long period of time, and a significant change in the solvent composition due to the volatilization of the solvent causes various troubles (e.g., precipitation of solute, change in flammability).
既に開示されているベンゾトリフルオライド類と非引火性フッ素系溶剤であるＨＦＥやＨＦＣとの混合溶剤（特許文献１及び特許文献２参照）は、いずれも蒸気圧が高く、ベンゾトリフルオライド類より先に、非引火性フッ素系溶剤が揮発してしまい、混合溶剤の組成変化が著しく工業的に使用することは非常に難しい。 Already disclosed mixed solvents of benzotrifluorides and non-flammable fluorine-based solvents such as HFE and HFC (see Patent Documents 1 and 2) have a higher vapor pressure and are ahead of benzotrifluorides. In addition, the non-flammable fluorine-based solvent volatilizes and the composition change of the mixed solvent is remarkably difficult to use industrially.
表面処理剤が引火性で、消防法上危険物に該当する場合には、取り扱い場所や保管場所および保管数量に非常に大きく制限を受けるだけではなく、使用設備を防爆対応することが義務付けられ、莫大な経済的負担が必要となる。このため、表面処理剤の大部分を占める溶剤は、安価でかつ非引火性であることが望まれる。 If the surface treatment agent is flammable and falls under the category of dangerous goods under the Fire Service Act, not only is the handling place, storage place, and storage quantity extremely limited, but the equipment used must be explosion-proof, A huge economic burden is required. For this reason, the solvent which occupies most surface treatment agents is desired to be inexpensive and non-flammable.
本発明は、溶解性の高いベンゾトリフルオライド類と非引火性フッ素系溶剤との混合溶剤で、その組成が非常に安定に維持できる混合溶剤の提供を目的とする。また、該混合溶剤の使用により、各種基材表面に撥水性、撥油性および撥ＩＰＡ性を充分に付与し得るフッ素系表面処理剤の提供も目的とする。また、組成比を調整することにより非引火性とした該混合溶剤の提供も目的とする。 An object of the present invention is to provide a mixed solvent of a highly soluble benzotrifluoride and a non-flammable fluorine-based solvent, the composition of which can be maintained very stably. Another object of the present invention is to provide a fluorine-based surface treating agent that can sufficiently impart water repellency, oil repellency and IPA repellency to the surfaces of various substrates by using the mixed solvent. Another object of the present invention is to provide a mixed solvent that is non-flammable by adjusting the composition ratio.
本発明者は、上記課題を解決すべく検討するうちに、汎用のビス（トリフルオロメチル）ベンゼン（引火点２６℃）を、（パーフルオロヘキソキシ）メタン（Ｃ6Ｆ13ＯＣＨ3）(引火点なし)と混合した場合に、広範囲の混合比で組成の変化が非常に少ない混合溶剤の提供できることを見出した。さらに、キシレンヘキサフルオライドと（パーフルオロヘキソキシ）メタンとの質量比で、（パーフルオロヘキソキシ）メタンを少量含むだけで引火点を持たない、つまり非引火性であることも見出した。なお、この引火点は、実施例では、混合溶剤の引火点とほぼ同等とみなすことができる０.２質量％の希薄なフッ素系重合体濃度溶液（表面処理剤）について測定している。したがって、本発明では、（Ａ）引火性溶剤成分と（Ｂ）非引火性溶剤成分との混合溶剤であって、それぞれの成分として以下に特定される（１）および（２）を含む混合溶剤を提供する。 While the present inventor studied to solve the above-mentioned problems, general-purpose bis (trifluoromethyl) benzene (flash point 26 ° C.) was changed to (perfluorohexoxy) methane (C 6 F 13 OCH 3 ) (flash point). It was found that a mixed solvent having a very small change in composition can be provided over a wide range of mixing ratios. Further, it was found that the mass ratio of xylene hexafluoride and (perfluorohexoxy) methane contains only a small amount of (perfluorohexoxy) methane and has no flash point, that is, nonflammable. In the Examples, the flash point is measured for a 0.2% by mass diluted fluoropolymer concentration solution (surface treatment agent) that can be regarded as substantially equivalent to the flash point of the mixed solvent. Therefore, in the present invention, a mixed solvent of (A) a flammable solvent component and (B) a non-flammable solvent component, which includes (1) and (2) specified below as the respective components. I will provide a.
本発明は、（１）ビス（トリフルオロメチル）ベンゼンと（２）Ｃ6Ｆ13ＯＲ（ＲはＣＨ3またはＣ2Ｈ5）とを、（１）／（２）＝１／９９〜９９／１の質量比で、かつ両者の合計で溶剤全量中８０質量％以上の量で含む混合溶剤を提供する。 The present invention relates to (1) bis (trifluoromethyl) benzene and (2) C 6 F 13 OR (where R is CH 3 or C 2 H 5 ), (1) / (2) = 1/99 to 99. A mixed solvent is provided that is a mass ratio of / 1 and that the sum of the two is 80% by mass or more of the total amount of the solvent.
上記（１）／（２）質量比は、好ましくは５０／５０〜９７／３である。さらに好ましくは、７０／３０〜９７／３、特に好ましくは７０／３０〜９５／５である。
上記（２）は、Ｃ2Ｆ5ＣＦ（ＯＣＨ3）Ｃ3Ｆ7であることが好ましい。
The mass ratio (1) / (2) is preferably 50/50 to 97/3. More preferably, it is 70/30 to 97/3, and particularly preferably 70/30 to 95/5.
The above (2) is preferably C 2 F 5 CF (OCH 3 ) C 3 F 7 .
上記混合溶剤は、溶剤全量中２０質量％以下の量で、上記（１）および（２）以外の溶剤成分を含むことができる。
この場合、混合溶剤中の（１）以外の（Ａ）引火性溶剤成分の量は、溶剤全量中１質量％以下であることが好ましい。
他の（Ｂ）非引火性溶剤成分としては、上記（２）以外のハイドロフルオロエーテルまたはハイドロフルオロカーボンが好ましい。
The mixed solvent may contain a solvent component other than (1) and (2) in an amount of 20% by mass or less in the total amount of the solvent.
In this case, the amount of the flammable solvent component (A) other than (1) in the mixed solvent is preferably 1% by mass or less based on the total amount of the solvent.
Other (B) non-flammable solvent components are preferably hydrofluoroethers or hydrofluorocarbons other than the above (2).
上記のような混合溶剤と、溶質としての含フッ素化合物とを含む表面処理剤。
上記含フッ素化合物は、含フッ素重合体またはポリフルオロアルキル基含有のリン酸エステル化合物であることが好ましい。
A surface treatment agent comprising the above mixed solvent and a fluorine-containing compound as a solute.
The fluorine-containing compound is preferably a fluorine-containing polymer or a phosphoric acid ester compound containing a polyfluoroalkyl group.
表面処理剤の溶質濃度は２０質量％以下であることが好ましい。
表面処理剤の動粘度は、１.０×１０−５ｍ２／ｓ以下であることが好ましい。
The solute concentration of the surface treatment agent is preferably 20% by mass or less.
The kinematic viscosity of the surface treatment agent is preferably 1.0 × 10 −5 m 2 / s or less.
本発明の表面処理剤は、はんだ用フラックス這い上がり防止剤、潤滑オイルの染み出し防止剤、防水・防湿コーティング剤、電子部品用樹脂付着防止剤等および離型剤に使用することができる。
本発明では、上記のような表面処理剤で被覆された基材も提供することができる。
また、本発明は、上記離型剤を使用して成型した成型部品も提供することができる。
The surface treatment agent of the present invention can be used as a solder flux creep-up preventive agent, a lubricant ooze-out preventive agent, a waterproof / moisture-proof coating agent, a resin adhesion preventive agent for electronic parts, and a mold release agent.
In this invention, the base material coat | covered with the above surface treating agents can also be provided.
Moreover, this invention can also provide the molded component shape | molded using the said mold release agent.
本発明は、含フッ素重合体の溶剤として、組成変化が非常に少ないフッ素系混合溶剤を提供し得る。また、一部の混合溶剤組成においては非引火性の混合溶剤の提供も可能とした。これらの混合溶剤を使用することで、各種基材表面に撥水性、撥油性および撥ＩＰＡ性を充分に付与することができる優れたフッ素系表面処理剤の提供を可能とした。 INDUSTRIAL APPLICABILITY The present invention can provide a fluorine-based mixed solvent with very little composition change as a solvent for a fluoropolymer. Further, in some mixed solvent compositions, it is possible to provide a non-flammable mixed solvent. By using these mixed solvents, it was possible to provide an excellent fluorine-based surface treating agent capable of sufficiently imparting water repellency, oil repellency and IPA repellency to various substrate surfaces.
本発明で使用される（１）ビス（トリフルオロメチル）ベンゼンは、別名キシレンヘキサフルオライドとも称され、市販品として入手可能である。以下、「ＸＨＦ」とも記す。なお、ＸＨＦは、位置異性体であるｏ−ＸＨＦ（１，２−ジ（トリフルオロメチル）ベンゼン）、ｍ−ＸＨＦ（１，３−ジ（トリフルオロメチル）ベンゼン）およびｐ−ＸＨＦ（１，４−ジ（トリフルオロメチル）ベンゼン）のいずれか１種でもよく、これら２種以上の混合物でも構わない。本発明において、ＸＨＦとしては、ｍ−ＸＨＦが好ましい。 (1) Bis (trifluoromethyl) benzene used in the present invention is also called as xylene hexafluoride and is available as a commercial product. Hereinafter, it is also referred to as “XHF”. XHF represents regioisomers o-XHF (1,2-di (trifluoromethyl) benzene), m-XHF (1,3-di (trifluoromethyl) benzene) and p-XHF (1, Any one of 4-di (trifluoromethyl) benzene) or a mixture of two or more of these may be used. In the present invention, as XHF, m-XHF is preferable.
また、本発明で使用される（２）Ｃ6Ｆ13ＯＲ（ＲはＣＨ3またはＣ2Ｈ5）としては、Ｃ2Ｆ5ＣＦ（ＯＣＨ3）Ｃ3Ｆ7が好ましい。また、Ｃ2Ｆ5ＣＦ（ＯＣＨ3）Ｃ3Ｆ7は、（パーフルオロヘキソキシ）メタン（Ｃ6Ｆ13ＯＣＨ3）とも記載されることがあり、ノベック７３００の商品名（３Ｍ株式会社）の市販品としても入手可能である。 Also, as used in the present invention (2) C 6 F 13 OR (R is CH 3 or C 2 H 5) Examples, C 2 F 5 CF (OCH 3) C 3 F 7 is preferred. In addition, C 2 F 5 CF (OCH 3 ) C 3 F 7 is sometimes described as (perfluorohexoxy) methane (C 6 F 13 OCH 3 ), and the trade name of Novec 7300 (3M Corporation) It is also available as a commercial product.
本発明の混合溶剤において、上記（１）／（２）の質量比は、好ましくは５０／５０〜９７／３、より好ましくは７０／３０〜９７／３、特に好ましくは７０／３０〜９５／５である。この範囲であると、安全面が維持できるだけでなく、経済性にも優れる。また、（１）と（２）の質量合計を１００としたとき、（２）の質量比が５以上であると混合溶剤が非引火性となる。上記（１）／（２）の質量比により、高価な（２）Ｃ6Ｆ13ＯＲ（ＲはＣＨ3またはＣ2Ｈ5）の使用量を著しく低減することができる。
なお、（２）としてＣ6Ｆ13ＯＣ2Ｈ5とＣ6Ｆ13ＯＣＨ3を併用する場合は、その合計量が上記範囲内であることが好ましい。
In the mixed solvent of the present invention, the mass ratio (1) / (2) is preferably 50/50 to 97/3, more preferably 70/30 to 97/3, and particularly preferably 70/30 to 95 /. 5. Within this range, not only can the safety be maintained, but the economy is also excellent. When the total mass of (1) and (2) is 100, the mixed solvent becomes non-flammable when the mass ratio of (2) is 5 or more. The mass ratio of (1) / (2) described above can significantly reduce the amount of expensive (2) C 6 F 13 OR (R is CH 3 or C 2 H 5 ).
In the case of combination of C 6 F 13 OC 2 H 5 and C 6 F 13 OCH 3 as (2), it is preferable that the total amount is within the above range.
本発明の目的を損なわない範囲であれば、上記特定成分（１）および（２）の混合溶剤に、他の溶剤成分を加えることができる。その場合、（１）および（２）の合計質量が、溶剤全量中の８０質量％以上であることが好ましく、９０質量％以上がより好ましく、９５質量％以上がさらに好ましい。これらの範囲では、混合溶剤の溶質の含フッ素化合物の溶解性が良好で、高価な他の溶剤たとえばＨＦＥなどの使用量が抑えられる。 If it is a range which does not impair the objective of this invention, another solvent component can be added to the mixed solvent of the said specific component (1) and (2). In that case, the total mass of (1) and (2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in the total amount of the solvent. Within these ranges, the solubility of the fluorine-containing compound as the solute of the mixed solvent is good, and the amount of other expensive solvent such as HFE used can be suppressed.
他の溶剤成分が、（１）以外の（Ａ）引火性溶剤成分である場合には、溶剤全量中２０質量％以下であって引火性に影響を与えない範囲であれば特に限定されないが、好適範囲としては、溶剤全量中１質量％以下である。 When the other solvent component is (A) a flammable solvent component other than (1), it is not particularly limited as long as it is 20% by mass or less in the total amount of the solvent and does not affect the flammability. A preferable range is 1% by mass or less based on the total amount of the solvent.
他の溶剤成分としては、溶質の含フッ素化合物の均一溶解性から、（２）以外の（Ｂ）非引火性溶剤が好ましく、たとえばＨＦＣおよび（２）以外のＨＦＥなどが好ましく用いられる。特に後者のＨＦＥが好ましい。 Other solvent components are preferably (B) non-flammable solvents other than (2), for example, HFC and HFE other than (2), because of the uniform solubility of the solute fluorine-containing compound. The latter HFE is particularly preferable.
（２）以外のＨＦＥとしては、具体的に以下のものが挙げられる。
Ｃ4Ｆ9ＯＣＨ3
Ｃ4Ｆ9ＯＣ2Ｈ5
Ｃ3Ｆ7ＯＣＨ3
Ｃ3Ｆ7ＯＣ2Ｈ5
ＣＦ2ＨＣＦ2ＣＨ2ＯＣＦ2ＣＦ2Ｈ
ＣＦ3（ＯＣＦ2ＣＦ2）n（ＯＣＦ2）mＯＣＦ2Ｈ
Ｃ8Ｆ17ＯＣＨ3
Ｃ7Ｆ15ＯＣＨ3
ＣＦ3ＣＨ2ＯＣＦ2ＣＦ2Ｈ
ＣＦ3ＣＨ2ＯＣＦ2ＣＨＦ2
およびこれらの混合物。
上記例示中、添字ｍおよびｎは各々１〜２０の整数を表し、アルキル骨格基は直鎖または分岐の態様を含む。
Specific examples of HFE other than (2) include the following.
C 4 F 9 OCH 3
C 4 F 9 OC 2 H 5
C 3 F 7 OCH 3
C 3 F 7 OC 2 H 5
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
CF 3 (OCF 2 CF 2 ) n (OCF 2 ) m OCF 2 H
C 8 F 17 OCH 3
C 7 F 15 OCH 3
CF 3 CH 2 OCF 2 CF 2 H
CF 3 CH 2 OCF 2 CHF 2
And mixtures of these.
In the above examples, the subscripts m and n each represent an integer of 1 to 20, and the alkyl skeleton group includes linear or branched embodiments.
（２）以外の（Ｂ）非引火性溶剤成分は、溶剤全量中２０質量％以下であれば特に限定されないが、環境への影響および高価なＨＦＥなどの使用量を抑えることから１０質量％以下がより好ましい。 (B) Non-flammable solvent component other than (2) is not particularly limited as long as it is 20% by mass or less in the total amount of the solvent, but it is 10% by mass or less because it suppresses the environmental impact and the amount of expensive HFE used. Is more preferable.
本発明において、「引火性」とは、以下の手順で引火点測定を実施し引火点を持つことと定義する。各引火点測定方法はＪＩＳ−Ｋ−２２６５に定められている方法に従うものとする。
＜引火点の測定手順＞
（ａ）タグ密閉法による引火点測定の実施。
（ｂ）（ａ）において、引火点が８０℃以下の温度で引火点が測定できない場合にあっては、クリーブランド開放法による引火点測定の実施。
In the present invention, “flammability” is defined as having a flash point by performing flash point measurement according to the following procedure. Each flash point measurement method shall follow the method defined in JIS-K-2265.
<Flash point measurement procedure>
(A) Implementation of flash point measurement by tag sealing method.
(B) When the flash point cannot be measured at a temperature of 80 ° C. or lower in (a), the flash point is measured by the Cleveland open method.
本発明の表面処理剤は、上記のような混合溶剤と、溶質とから形成される。ここで、溶剤とは、室温において動粘度が１.０×１０-５ｍ２／ｓ未満の液体成分と定義し、溶質とは、室温において固体もしくは動粘度が１.０×１０-５ｍ２／ｓ以上の液体成分と定義する。 The surface treating agent of the present invention is formed from the above mixed solvent and a solute. Here, the solvent is defined as a liquid component having a kinematic viscosity of less than 1.0 × 10 −5 m 2 / s at room temperature, and the solute is a solid or kinematic viscosity at room temperature of 1.0 × 10 −5 m. It is defined as a liquid component of 2 / s or more.
本発明に係る表面処理剤は、溶質として少なくとも含フッ素化合物を含む。この含フッ素化合物は、通常、ポリフルオロアルキル基を含有する化合物であり、具体的には、該基を含有する含フッ素重合体または含フッ素リン酸エステルが挙げられる。 The surface treating agent according to the present invention contains at least a fluorine-containing compound as a solute. This fluorine-containing compound is usually a compound containing a polyfluoroalkyl group, and specific examples thereof include a fluorine-containing polymer or a fluorine-containing phosphate ester containing the group.
含フッ素重合体は、少なくともポリフルオロアルキル基含有化合物（ａ）から導かれる構成単位を含む。この化合物（ａ）は、典型的に（メタ）アクリル酸化合物であり、具体的には（メタ）アクリル酸エステルまたは（メタ）アクリルアミドなどである。
化合物（ａ）としては、下記構造が挙げられる。
ＣＨ2＝ＣＲ１−ＣＯＸ−Ｑ１−Ｒｆ１
該式中のＲ１は水素原子またはメチル基であり、Ｘは−Ｏ−または−ＮＨ−であり、Ｑ１は単結合または２価の連結基であり、Ｒｆ１は炭素数１〜２０のポリフルオロアルキル基である。２価の連結基としては炭素数１〜５のアルキレン基が好ましい。
なお、本発明において、「（メタ）アクリル」の語は、アクリルおよびメタクリルの両方またはどちらか一方を意味する。このような化合物（ａ）を具体的に（メタ）アクリル酸エステルで例示すれば、
ＣＨ2＝ＣＨ−ＣＯＯ−（ＣＨ2）n−（ＣＦ2）ｍＦ、
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）n−（ＣＦ2）ｍＦ
（上記例示中、添字ｎは０〜４、添字ｍは１〜１６の整数である。）
などが挙げられるが、化合物（ａ）は、これらに限定されるものではない。
これらのうちでも、ｍが１〜６であるものが好ましい。
なお、（メタ）アクリル酸エステルは、表面処理剤に求める性能により適宜選択できる。例えば、撥水性を特に重視する場合はメタクリル酸エステルが好ましく、撥油性や撥ＩＰＡ性を特に重視する場合や、被膜の耐熱性を特に重視する場合は、アクリル酸エステルである場合が好ましい。
The fluoropolymer contains at least a structural unit derived from the polyfluoroalkyl group-containing compound (a). This compound (a) is typically a (meth) acrylic acid compound, specifically, (meth) acrylic acid ester or (meth) acrylamide.
The following structure is mentioned as a compound (a).
CH 2 = CR 1 -COX-Q 1 -Rf 1
In the formula, R 1 is a hydrogen atom or a methyl group, X is —O— or —NH—, Q 1 is a single bond or a divalent linking group, and Rf 1 has 1 to 20 carbon atoms. It is a polyfluoroalkyl group. The divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms.
In the present invention, the term “(meth) acryl” means both or one of acrylic and methacrylic. If such a compound (a) is specifically exemplified by (meth) acrylic acid ester,
CH 2 = CH-COO- (CH 2) n - (CF 2) m F,
CH 2 = C (CH 3) -COO- (CH 2) n - (CF 2) m F
(In the above examples, the subscript n is an integer of 0 to 4, and the subscript m is an integer of 1 to 16.)
The compound (a) is not limited to these.
Among these, what m is 1-6 is preferable.
In addition, (meth) acrylic acid ester can be suitably selected by the performance calculated | required by a surface treating agent. For example, methacrylic acid ester is preferable when water repellency is particularly important, and acrylic acid ester is preferable when oil repellency and IPA repellency are particularly important, or when heat resistance of the film is particularly important.
含フッ素重合体は、化合物（ａ）から導かれる構成単位を、通常５０質量％以上、好ましくは８０質量％以上、より好ましくは９０質量％以上含有する。なお本発明において、重合体における構成単位の質量％は、重合に使用した原料化合物がすべて構成単位を構成するとみなした値である。
含フッ素重合体が、化合物（ａ）のみの重合体である場合には、化合物（ａ）の１種の単独重合体でも２種以上の共重合体でもよい。
The fluoropolymer usually contains 50 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more of the structural unit derived from the compound (a). In addition, in this invention, the mass% of the structural unit in a polymer is the value considered that all the raw material compounds used for superposition | polymerization comprise a structural unit.
When the fluorinated polymer is a polymer composed solely of the compound (a), it may be a single homopolymer or two or more copolymers of the compound (a).
また、含フッ素重合体が共重合体である場合には、他の化合物（ｂ）から導かれる構成単位を１種または複数種含むことができる。化合物（ｂ）は、通常、ポリフルオロアルキル基を含有しない化合物であり、たとえば（メタ）アクリル酸、炭素数１〜１８のアルキル基を有する（メタ）アクリル酸エステル、反応性を有する官能基を含む化合物、例えば、マレイン酸、無水イタコン酸、無水コハク酸等のエチレン性不飽和カルボン酸類、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−ブトキシ（メタ）アクリルアミド等のアミド化合物、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ヒドロキシプロピル等の水酸基含有化合物、γ-（メタ）アクリロキシプロピルトリメトキシシラン等のアルコキシシリル基含有化合物、（メタ）アクリル酸グリシジル等のエポキシ基含有化合物、２−（メタ）アクリロイロキシエチルコハク酸などのカルボキシル基含有化合物などであるが、これらに限られない。 Moreover, when a fluorine-containing polymer is a copolymer, 1 type or multiple types of structural units derived | led-out from another compound (b) can be included. The compound (b) is usually a compound that does not contain a polyfluoroalkyl group. For example, (meth) acrylic acid, a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms, a reactive functional group. Compounds containing, for example, ethylenically unsaturated carboxylic acids such as maleic acid, itaconic anhydride, succinic anhydride, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxy (meta) ) Amide compounds such as acrylamide, hydroxyl-containing compounds such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate, alkoxysilyl group-containing compounds such as γ- (meth) acryloxypropyltrimethoxysilane, (meth) Epoxy group-containing compounds such as glycidyl acrylate, 2- (meth) Carboxyl group-containing compounds such as methacryloyloxyethyl succinate and the like, but not limited to.
含フッ素リン酸エステルとしては、下記構造が挙げられる。
（Ｒｆ２−Ｑ２−Ｏ−）ｒ−Ｐ（Ｏ）（ＯＭ）ｓ
該式中のＲｆ２は炭素数１〜２０のポリフルオロアルキル基であり、Ｑ２は単結合または２価の連結基であり、Ｍは水素原子、アンモニウム基、置換アンモニウム基またはアルカリ金属原子であり、ｒは１〜３の整数であり、ｓは０〜２の整数であり、ｒ＋ｓは３である。２価の連結基としてはＯＨ基で置換されていてもよい炭素数１〜５のアルキレン基が好ましい。
含フッ素リン酸エステルの具体例としては、以下の化合物が挙げられるが、これらに限定されるものではない。
Ｆ（ＣＦ2）m-ＣＨ2ＣＨ2-Ｐ（Ｏ）（ＯＨ）2
（Ｆ（ＣＦ2）m-ＣＨ2ＣＨ2）2Ｐ（Ｏ）（ＯＨ）
Ｆ（ＣＦ2）m-ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ-Ｐ（Ｏ）（ＯＨ）2
（Ｆ（ＣＦ2）m-ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ）2Ｐ（Ｏ）（ＯＨ）
Ｆ（ＣＦ2）m-ＣＨ2ＣＨ2Ｏ-Ｐ（Ｏ）（ＯＨ）2
（Ｆ（ＣＦ2）m-ＣＨ2ＣＨ2Ｏ）2-Ｐ（Ｏ）（ＯＨ）
上記例示中、添字ｍは１〜１６の整数であり、好ましくは１〜６である。
含フッ素リン酸エステルは、表面処理剤として金属表面を処理する場合に特に好適である。また、離型剤として用いる場合にも特に好適である。
Examples of the fluorine-containing phosphate ester include the following structures.
(Rf 2 -Q 2 -O-) r -P (O) (OM) s
Rf 2 in the formula is a polyfluoroalkyl group having 1 to 20 carbon atoms, Q 2 is a single bond or a divalent linking group, M is a hydrogen atom, an ammonium group, a substituted ammonium group or an alkali metal atom. Yes, r is an integer from 1 to 3, s is an integer from 0 to 2, and r + s is 3. The divalent linking group is preferably an alkylene group having 1 to 5 carbon atoms which may be substituted with an OH group.
Specific examples of the fluorine-containing phosphate ester include the following compounds, but are not limited thereto.
F (CF 2 ) m —CH 2 CH 2 —P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH 2 ) 2 P (O) (OH)
F (CF 2 ) m —CH 2 CH (OH) CH 2 O—P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH (OH) CH 2 O) 2 P (O) (OH)
F (CF 2 ) m —CH 2 CH 2 O—P (O) (OH) 2
(F (CF 2 ) m —CH 2 CH 2 O) 2 —P (O) (OH)
In the above examples, the subscript m is an integer of 1 to 16, preferably 1 to 6.
The fluorine-containing phosphate ester is particularly suitable for treating a metal surface as a surface treatment agent. It is also particularly suitable when used as a release agent.
本発明の表面処理剤は、上記溶剤に溶解もしくは分散させることが可能で、本発明の目的を損なわず、安定性、性能および外観等に悪影響を与えない範囲であれば上記のような含フッ素化合物以外にも他の溶質を特に制限なく含むことができる。
たとえば、ジメチルメチルシリコーンやポリエチレングリコールアルキルアミンなどが挙げられる。さらに、被膜表面の腐食を防止するためのｐＨ調整剤、防錆剤、表面処理剤を希釈して使用する場合に液中の重合体の濃度管理をする目的や未処理部品との区別をするための染料、染料の安定剤、難燃剤、消泡剤および帯電防止剤等の他の成分が挙げられる。
The surface treatment agent of the present invention can be dissolved or dispersed in the above-mentioned solvent, and does not impair the purpose of the present invention and does not adversely affect stability, performance, appearance, etc. In addition to the compound, other solutes can be contained without particular limitation.
Examples thereof include dimethylmethyl silicone and polyethylene glycol alkylamine. Furthermore, when diluting pH adjusters, rust inhibitors, and surface treatment agents to prevent coating surface corrosion, the purpose is to control the concentration of the polymer in the liquid and to distinguish it from untreated parts. Other components such as dyes, dye stabilizers, flame retardants, antifoaming agents and antistatic agents.
本発明の表面処理剤は、溶質濃度が２０質量％以下であることが好ましい。この溶質とは、表面処理剤における溶質全体、すなわち上記含フッ素化合物だけでなく、他の溶質および他の成分も含むことを意味する。 The surface treatment agent of the present invention preferably has a solute concentration of 20% by mass or less. This solute means not only the whole solute in the surface treatment agent, that is, not only the fluorine-containing compound but also other solutes and other components.
本発明の表面処理剤の含フッ素化合物の濃度は、用途によって適宜設定されることが好ましい。防水・防湿コート剤では、１〜２０質量％であるのが好ましい。潤滑オイルの染み出し防止剤や電子部品用樹脂付着防止剤では、１〜５質量％であるのが好ましい。はんだ用フラックス這い上がり防止剤では、濃度が０.０１〜１質量％であるのが好ましい。離型剤では、０.１〜１０質量％であるのが好ましい。 The concentration of the fluorine-containing compound of the surface treatment agent of the present invention is preferably set as appropriate depending on the application. In the waterproof / moisture-proof coating agent, the content is preferably 1 to 20% by mass. In the lubricant preventing seepage agent and the resin component preventing agent for electronic parts, the content is preferably 1 to 5% by mass. In the solder flux creep-up preventing agent, the concentration is preferably 0.01 to 1% by mass. In a mold release agent, it is preferable that it is 0.1-10 mass%.
上記含フッ素化合物の濃度は、各用途での最終的な濃度であればよい。各用途に供するには高濃度、たとえばはんだ用フラックス這い上がり防止剤である場合の１質量％を超えていてもなんら差し支えなく、希釈等により適宜調整すればよい。また、含フッ素化合物が含フッ素重合体である場合には、重合体を高濃度（固形分濃度）で含む重合溶液をそのまま各用途での好適濃度に希釈して使用することができる。 The concentration of the fluorine-containing compound may be a final concentration for each application. For use in each application, even if it exceeds the high concentration, for example, 1% by mass in the case of the solder flux scooping-up inhibitor, there is no problem. When the fluorine-containing compound is a fluorine-containing polymer, a polymerization solution containing the polymer at a high concentration (solid content concentration) can be used as it is after being diluted to a suitable concentration for each application.
溶質全量中の含フッ素化合物の量は、用途により異なっていても構わない。例えば、防水・防湿コート剤、潤滑オイルの染み出し防止剤、電子部品用樹脂付着防止剤およびはんだ用フラックス這い上がり防止剤では、溶質成分の９０質量％以上が含フッ素化合物であることが好ましいが、離型剤では、含フッ素化合物が溶質成分の５０質量％以下であっても構わない。 The amount of the fluorine-containing compound in the total amount of the solute may be different depending on the application. For example, in a waterproof / moisture-proof coating agent, a lubricant preventing bleeding agent, an electronic component resin adhesion preventing agent, and a solder flux creeping-up preventing agent, it is preferable that 90% by mass or more of the solute component is a fluorine-containing compound. In the mold release agent, the fluorine-containing compound may be 50% by mass or less of the solute component.
本発明の表面処理剤の動粘度は、１.０×１０-５ｍ２／ｓ未満であることが好ましく、より好ましくは５.０×１０-６ｍ２／ｓ以下である。これらの動粘度範囲であれば、表面処理剤の作業性が良好である。 The kinematic viscosity of the surface treatment agent of the present invention is preferably less than 1.0 × 10 −5 m 2 / s, more preferably 5.0 × 10 −6 m 2 / s or less. Within these kinematic viscosity ranges, the workability of the surface treatment agent is good.
本発明の表面処理剤は、撥水性、撥油性および撥ＩＰＡ性等の性能を付与したい部分に塗布して被膜を形成して利用することができる。該被膜は、本発明の表面処理剤から溶剤が除去されて形成されるものであり、主として、本発明の溶質成分からなるものである。被覆方法としては一般的な被覆加工方法が採用できる。例えば浸漬塗布、スプレー塗布、ローラー塗布等の方法がある。 The surface treating agent of the present invention can be used by applying it to a portion to which performance such as water repellency, oil repellency and IPA repellency is to be imparted to form a film. The coating is formed by removing the solvent from the surface treatment agent of the present invention, and is mainly composed of the solute component of the present invention. As a coating method, a general coating method can be adopted. For example, there are methods such as dip coating, spray coating, and roller coating.
本発明の表面処理剤の塗布後は、溶剤の沸点以上の温度で乾燥を行うことが好ましい。無論、被処理部品の材質などにより加熱乾燥が困難な場合には、加熱を回避して乾燥すべきである。なお、熱処理の条件は、塗布する表面処理剤の組成や、塗布面積等に応じて選択すればよい。 After application of the surface treatment agent of the present invention, it is preferable to perform drying at a temperature equal to or higher than the boiling point of the solvent. Of course, when it is difficult to heat and dry due to the material of the part to be processed, it should be dried while avoiding heating. In addition, what is necessary is just to select the conditions of heat processing according to the composition of the surface treating agent to apply | coat, an application area, etc.
本発明の表面処理剤は、各種材料の処理に適用可能であるが、中でも精密機器部品や摺動部品（モーター、時計、ＨＤＤ）、電気部品（電子回路や基板、電子部品等）および各種樹脂製系のモールドの処理に用いるのが好ましい。中でも、本発明の表面処理剤を、はんだ用フラックス這い上がり防止剤、潤滑オイルのにじみ出し防止剤、防水コート剤、防湿コート剤、電子部品用樹脂付着防止剤および離型剤として用いることが好ましい。 The surface treatment agent of the present invention can be applied to the treatment of various materials, among which precision equipment parts, sliding parts (motors, watches, HDDs), electrical parts (electronic circuits, substrates, electronic parts, etc.) and various resins. It is preferable to use it for the processing of molds for production. Among these, it is preferable to use the surface treatment agent of the present invention as a solder flux creeping-up inhibitor, a lubricant oozing-out preventing agent, a waterproof coating agent, a moisture-proof coating agent, an electronic component resin adhesion preventing agent, and a release agent. .
以下に本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。以下の実施例で使用した化合物は、市場から試薬として入手することができるものまたは既知の合成法によって容易に合成できるものである。また、以下の実施例において、特に断わりのない限り「％」で表示されるものは「質量％」を表すものとする。 The present invention will be specifically described below, but the present invention is not limited to the following examples. The compounds used in the following examples can be obtained from the market as reagents or can be easily synthesized by known synthesis methods. In the following examples, unless otherwise specified, “%” indicates “% by mass”.
（合成例１）含フッ素重合体１（Ｃ６ＦＭＡ／ＨＥＭＡ共重合体）の合成
密閉容器に、ＣＨ2＝Ｃ（ＣＨ3）-ＣＯＯ-ＣＨ2ＣＨ2（ＣＦ2）6Ｆ（Ｃ６ＦＭＡ）を２９４質量部、ＣＨ2＝Ｃ（ＣＨ3）-ＣＯＯ-ＣＨ2ＣＨ2ＯＨ（ＨＥＭＡ）を６質量部、ｍ−ＸＨＦを２９９質量部および開始剤（ジメチル２，２'−アゾビス（２−メチルプロピオナート，和光純薬工業，Ｖ−６０１）を１質量部、それぞれ仕込み、７０℃で１８時間反応させた。
反応後の重合溶液に、ｍ-ＸＨＦを加えて希釈し、含フッ素重合体濃度２０％のｍ-ＸＨＦ溶液を得た。
(Synthesis Example 1) Synthesis sealed container of the fluoropolymer 1 (C6FMA / HEMA copolymer), CH 2 = C (CH 3) -COO-CH 2 CH 2 (CF 2) 6 F a (C6FMA) 294 6 parts by mass of CH 2 ═C (CH 3 ) —COO—CH 2 CH 2 OH (HEMA), 299 parts by mass of m-XHF and initiator (dimethyl 2,2′-azobis (2-methylpro) 1 part by weight of Pionate, Wako Pure Chemical Industries, V-601) was charged and reacted at 70 ° C. for 18 hours.
M-XHF was added to the polymerized solution after the reaction for dilution to obtain an m-XHF solution having a fluoropolymer concentration of 20%.
（合成例２〜３）
合成例１と同様にして、表１に示す化合物を表１に示す量で用いて、含フッ素重合体２〜３を合成した。各重合体における化合物の仕込み比を含フッ素重合体１とともに表１に示す。
In the same manner as in Synthesis Example 1, fluorinated polymers 2 to 3 were synthesized using the compounds shown in Table 1 in the amounts shown in Table 1. Table 1 shows the charge ratio of the compounds in each polymer together with the fluoropolymer 1.
以下に、溶剤成分として使用した化合物を表２に示す。
表中、７３００：３Ｍ社製ノベックTM７３００
ＡＥ３０００：旭硝子社製
The compounds used as solvent components are shown in Table 2 below.
In the table, 7300: 3M Novec TM 7300
AE3000: manufactured by Asahi Glass
（実施例１〜１０）表面処理剤の調製
合成例１で得られた含フッ素重合体溶液を、各所定量の溶剤で重合体濃度０.２％に希釈した。得られた各表面処理剤中の溶剤組成を表３に示す。
［引火点測定］
実施例４、６〜１０の各表面処理剤について、前述の引火点測定を行い、引火性の有無を試験した。結果を表３に示す。ここから、ｍ-ＸＨＦを多量に含んでいても、本発明の混合溶剤および表面処理剤は非引火性となることが分かった。
[Flash point measurement]
About each surface treating agent of Example 4, 6-10, the above-mentioned flash point measurement was performed and the presence or absence of flammability was tested. The results are shown in Table 3. From this, it was found that the mixed solvent and the surface treatment agent of the present invention are non-flammable even when a large amount of m-XHF is contained.
（比較例１〜５）表面処理剤の調製
合成例１で得られた含フッ素重合体溶液を、各所定量の溶剤で重合体濃度０.２％に希釈した。得られた各表面処理剤中の溶剤組成を表４に示す。
［組成変化の測定］
実施例２、４〜７の各表面処理剤を８０ｍＬのガラス瓶に約１００ｇ採取し、ふたを開けたまま、４０℃に設定した乾燥機中に静置させた。定期的に溶剤の揮発量と組成変化を測定した。測定の結果を表５に示す。
[Measurement of composition change]
About 100 g of each surface treating agent of Examples 2 and 4 to 7 was collected in an 80 mL glass bottle and allowed to stand in a dryer set at 40 ° C. with the lid open. The solvent volatilization amount and composition change were measured periodically. Table 5 shows the measurement results.
同様にして、比較例１〜５の４０℃での組成変化を測定した。測定の結果を表６に示す。
なお、表中の「Ｂ成分比率の推移」は、上段が「Ｂ成分比率」、下段が「相対質量」である。この「Ｂ成分比率」とは、混合溶剤中の（Ｂ）非引火性溶剤成分の質量比率である。また、「相対質量」とは、初期の混合溶剤の質量に対する、測定時の混合溶剤の質量の比率であり、「１００×測定時の質量／初期質量」である。
Similarly, the composition change at 40 ° C. of Comparative Examples 1 to 5 was measured. Table 6 shows the measurement results.
In the table, “B component ratio transition” is “B component ratio” in the upper row and “Relative mass” in the lower row. This “B component ratio” is the mass ratio of the (B) non-flammable solvent component in the mixed solvent. The “relative mass” is the ratio of the mass of the mixed solvent at the time of measurement to the mass of the initial mixed solvent, and is “100 × mass at the time of measurement / initial mass”.
表５〜６中の組成変化（Ｂ成分比率の推移）をグラフとし、図１に示す。
表５〜６および図１に示されるとおり、本発明の表面処理剤は、比較例と比較して、混合溶剤の組成変化が緩やかであった。
The composition change (transition of B component ratio) in Tables 5 to 6 is shown as a graph in FIG.
As shown in Tables 5 to 6 and FIG. 1, the surface treatment agent of the present invention showed a gradual change in the composition of the mixed solvent as compared with the comparative example.
実施例１〜１０の表面処理剤について、以下のとおり接触角、動粘度および密度を測定した。結果を表７に示す。
［接触角の測定］
実施例１〜１０の各表面処理剤に室温でガラス板を１分間浸漬した後、室温で乾燥させ、各処理剤の被膜を有する各ガラス板を得た。
次に各ガラス板の被膜上に、水、ＩＰＡまたはｎ-ヘキサデカン（ｎ-ＨＤ）を滴下し、接触角を測定した。
接触角の測定には、自動接触角計ＯＣＡ−２０［dataphysics社製］を用いた。
［動粘度の測定］
各表面処理剤について、ウベローデ粘度計を用いて、２５℃での動粘度を測定した。
［密度測定]
各表面処理剤について、室温でのメスフラスコを用いて体積２５ｍＬにおける溶液の重量を測定して密度を算出した。
About the surface treating agent of Examples 1-10, the contact angle, kinematic viscosity, and density were measured as follows. The results are shown in Table 7.
[Measurement of contact angle]
After immersing a glass plate in each surface treating agent of Examples 1-10 at room temperature for 1 minute, it was made to dry at room temperature and obtained each glass plate which has a coat of each treating agent.
Next, water, IPA or n-hexadecane (n-HD) was dropped onto the coating on each glass plate, and the contact angle was measured.
For the measurement of the contact angle, an automatic contact angle meter OCA-20 (manufactured by dataphysics) was used.
[Measurement of kinematic viscosity]
About each surface treating agent, kinematic viscosity in 25 degreeC was measured using the Ubbelohde viscometer.
[Density measurement]
About each surface treating agent, the weight of the solution in a volume of 25 mL was measured using the volumetric flask at room temperature, and the density was computed.
（実施例１１〜１３）
合成例１で得られた含フッ素重合体溶液を、溶剤成分（１）／（２）の質量比を８０／２０とした混合溶剤で表８に記載の濃度に希釈した。得られた表面処理剤１１〜１３について、実施例１〜１０と同様に接触角、動粘度および密度を測定した。結果を表８に示す。
(Examples 11 to 13)
The fluoropolymer solution obtained in Synthesis Example 1 was diluted to the concentration shown in Table 8 with a mixed solvent in which the mass ratio of the solvent components (1) / (2) was 80/20. About the obtained surface treating agents 11-13, the contact angle, kinematic viscosity, and density were measured similarly to Examples 1-10. The results are shown in Table 8.
（実施例１４〜１６）
前記重合体２の溶液を、溶剤成分（１）／（２）の質量比を８０／２０とした混合溶剤で重合体濃度０．２％に希釈した。これを表面処理剤１４とする。
重合体３も同じ条件で希釈したものを表面処理剤１５とする。
また、含フッ素リン酸エステルである化合物（Ｐ１）と添加剤である化合物（Ｚ１）を含む表面処理剤１６を調製した。
各表面処理剤について表９にまとめて示す。
(Examples 14 to 16)
The polymer 2 solution was diluted to a polymer concentration of 0.2% with a mixed solvent in which the mass ratio of the solvent components (1) / (2) was 80/20. This is referred to as a surface treatment agent 14.
The polymer 3 diluted with the same conditions is used as the surface treatment agent 15.
Moreover, the surface treating agent 16 containing the compound (P1) which is a fluorine-containing phosphate ester, and the compound (Z1) which is an additive was prepared.
Table 9 summarizes each surface treatment agent.
表面処理剤１４〜１６について、実施例１〜１０と同様に接触角、動粘度および密度を測定した。結果を表１０に示す。
以上の結果から、本発明では、広範囲の組成比において、組成がほとんど変化しない混合溶剤を得られる。さらに、非引火性溶剤成分の（２）が極少量であり、引火性である（１）が混合溶剤の大半を占めていても、（１）と（２）の混合溶剤を非引火性とすることもできる。このような特徴は、特異的でありその有用性は非常に高い。さらに、本発明の表面処理剤は、上記のような効果を有するとともに、撥水性、撥油性、撥ＩＰＡ性が、各種基材の表面処理に十分な性能である。 From the above results, in the present invention, it is possible to obtain a mixed solvent whose composition hardly changes in a wide range of composition ratios. Furthermore, even though the non-flammable solvent component (2) is extremely small and the flammable (1) occupies most of the mixed solvent, the mixed solvent of (1) and (2) is made non-flammable. You can also Such a feature is specific and its usefulness is very high. Furthermore, the surface treating agent of the present invention has the effects as described above, and water repellency, oil repellency, and IPA repellency are performance sufficient for surface treatment of various substrates.
Claims (19)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556115A (en) * | 2013-09-12 | 2014-02-05 | 深圳市特艺实业有限公司 | Waterproof film forming apparatus for daily electronic products |
| WO2018164140A1 (en) * | 2017-03-07 | 2018-09-13 | Ａｇｃ株式会社 | Water repellent oil repellent article, method for producing same, and water repellent oil repellent agent composition |
| JP7416612B2 (en) | 2019-12-16 | 2024-01-17 | Ａｇｃセイミケミカル株式会社 | surface treatment composition |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006188007A (en) * | 2005-01-07 | 2006-07-20 | Canon Inc | Releasing agent composition for plastic mold and component using the composition |
| JP2009057530A (en) * | 2007-08-30 | 2009-03-19 | Ft-Net Co Ltd | Fluorine-based surface reforming composition |
| JP2009249448A (en) * | 2008-04-03 | 2009-10-29 | Agc Seimi Chemical Co Ltd | Barrier agent composition against lubricating oil, its manufacturing method and its use |
| JP2010024381A (en) * | 2008-07-22 | 2010-02-04 | Agc Seimi Chemical Co Ltd | Resin adhesion preventing composition for electronic component |
| WO2010079687A1 (en) * | 2009-01-07 | 2010-07-15 | Ａｇｃセイミケミカル株式会社 | Resin adhesion inhibitor for electronic components, and electronic member and electronic component comprising same |
| WO2010110149A1 (en) * | 2009-03-23 | 2010-09-30 | Ａｇｃセイミケミカル株式会社 | Surface treatment agent |
| WO2010113646A1 (en) * | 2009-04-03 | 2010-10-07 | Ａｇｃセイミケミカル株式会社 | Surface treatment agent |
| WO2011021623A1 (en) * | 2009-08-20 | 2011-02-24 | Ａｇｃセイミケミカル株式会社 | Fluoroalkyl group-containing n-substituted (meth)acrylamide compound, polymer thereof, and use thereof |
| WO2011105223A1 (en) * | 2010-02-26 | 2011-09-01 | アルプス電気株式会社 | Surface treating agent for electrical contacts |
-
2012
- 2012-10-26 JP JP2012236516A patent/JP6093547B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006188007A (en) * | 2005-01-07 | 2006-07-20 | Canon Inc | Releasing agent composition for plastic mold and component using the composition |
| JP2009057530A (en) * | 2007-08-30 | 2009-03-19 | Ft-Net Co Ltd | Fluorine-based surface reforming composition |
| JP2009249448A (en) * | 2008-04-03 | 2009-10-29 | Agc Seimi Chemical Co Ltd | Barrier agent composition against lubricating oil, its manufacturing method and its use |
| JP2010024381A (en) * | 2008-07-22 | 2010-02-04 | Agc Seimi Chemical Co Ltd | Resin adhesion preventing composition for electronic component |
| WO2010079687A1 (en) * | 2009-01-07 | 2010-07-15 | Ａｇｃセイミケミカル株式会社 | Resin adhesion inhibitor for electronic components, and electronic member and electronic component comprising same |
| WO2010110149A1 (en) * | 2009-03-23 | 2010-09-30 | Ａｇｃセイミケミカル株式会社 | Surface treatment agent |
| WO2010113646A1 (en) * | 2009-04-03 | 2010-10-07 | Ａｇｃセイミケミカル株式会社 | Surface treatment agent |
| WO2011021623A1 (en) * | 2009-08-20 | 2011-02-24 | Ａｇｃセイミケミカル株式会社 | Fluoroalkyl group-containing n-substituted (meth)acrylamide compound, polymer thereof, and use thereof |
| WO2011105223A1 (en) * | 2010-02-26 | 2011-09-01 | アルプス電気株式会社 | Surface treating agent for electrical contacts |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556115A (en) * | 2013-09-12 | 2014-02-05 | 深圳市特艺实业有限公司 | Waterproof film forming apparatus for daily electronic products |
| CN103556115B (en) * | 2013-09-12 | 2017-02-01 | 深圳市特艺实业有限公司 | Waterproof film forming apparatus for daily electronic products |
| WO2018164140A1 (en) * | 2017-03-07 | 2018-09-13 | Ａｇｃ株式会社 | Water repellent oil repellent article, method for producing same, and water repellent oil repellent agent composition |
| JP7416612B2 (en) | 2019-12-16 | 2024-01-17 | Ａｇｃセイミケミカル株式会社 | surface treatment composition |
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