JP2017132830A - Water-proof and moisture-proof coating agent - Google Patents
Water-proof and moisture-proof coating agent Download PDFInfo
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- JP2017132830A JP2017132830A JP2016011405A JP2016011405A JP2017132830A JP 2017132830 A JP2017132830 A JP 2017132830A JP 2016011405 A JP2016011405 A JP 2016011405A JP 2016011405 A JP2016011405 A JP 2016011405A JP 2017132830 A JP2017132830 A JP 2017132830A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 6
- 238000005452 bending Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 239000012756 surface treatment agent Substances 0.000 abstract description 5
- 239000005871 repellent Substances 0.000 abstract description 4
- 230000002940 repellent Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012298 atmosphere Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 30
- 238000011156 evaluation Methods 0.000 description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 5
- 230000002411 adverse Effects 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- -1 acrylate ester Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-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
- SQEGLLMNIBLLNQ-UHFFFAOYSA-N 1-ethoxy-1,1,2,3,3,3-hexafluoro-2-(trifluoromethyl)propane Chemical compound CCOC(F)(F)C(F)(C(F)(F)F)C(F)(F)F SQEGLLMNIBLLNQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
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- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、各種基材に防水・撥油性および防湿性を付与する防水・防湿コーティング剤に関する。 The present invention relates to a waterproof / moisture-proof coating agent that imparts waterproof / oil repellency and moisture resistance to various substrates.
従来、フッ素系の表面処理剤として、炭素鎖長が８以上の直鎖状または末端分岐のパーフルオロアルキル基を有する（メタ）アクリル酸エステルの重合物が使用されてきた。これは、側鎖の（ＣＦ2）8Ｆ基の持つ結晶性が、高い撥水性能、撥油性能を示すためであった。 Conventionally, a polymer of (meth) acrylic acid ester having a linear or terminally branched perfluoroalkyl group having a carbon chain length of 8 or more has been used as a fluorine-based surface treatment agent. This is because the crystallinity of the (CF 2 ) 8 F group in the side chain exhibits high water repellency and oil repellency.
米国環境保護庁（ＵＳＥＰＡ）が、野生動物や人の血液を含め、種々の環境から検出されるパーフロオロオクタン酸（ＰＦＯＡ）の安全性に関する予備リスク調査報告書を２００３年３月に公開した。報告書では、ＰＦＯＡ発生の恐れのあるパーフルオロアルキル基の炭素数が８であるものについて、生体および環境への影響が指摘された。そして、２００６年１月には、ＰＦＯＡおよびその類縁物質ならびにこれらの前駆体物質の環境中への排出削減と製品中の含有量削減計画への参加をフッ素樹脂メーカー等に提唱している。
ここで対象になる構造としては、下記に示される炭素数が８の直鎖状のパーフルオロアルキル基を有する化合物などが挙げられる（特許文献１参照）。
ＣＨ2＝ＣＨ−ＣＯＯ−（ＣＨ2）2−（ＣＦ2）8Ｆ
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）2−（ＣＦ2）8Ｆ
The US Environmental Protection Agency (USEPA) published a preliminary risk study report on the safety of perfluorooctanoic acid (PFOA) detected in various environments, including wild animals and human blood, in March 2003. In the report, it was pointed out that the perfluoroalkyl group that has the possibility of generating PFOA has 8 carbon atoms and has an impact on the living body and the environment. In January 2006, PFOA, its related substances, and their precursor substances were proposed to fluororesin manufacturers and others to participate in a reduction plan in the environment and a content reduction plan in products.
Examples of the structure to be used here include compounds having a linear perfluoroalkyl group having 8 carbon atoms shown below (see Patent Document 1).
CH 2 = CH-COO- (CH 2) 2 - (CF 2) 8 F
CH 2 = C (CH 3) -COO- (CH 2) 2 - (CF 2) 8 F
このような状況において、ＰＦＯＡの発生の恐れを減らすために、パーフルオロアルキル基の炭素数を６以下に短くしたもの、具体的には、前記式中の（ＣＦ2）8Ｆを、（ＣＦ2）6Ｆまたは（ＣＦ2）4Ｆなどに置換した化合物を代替品として用いることが考えられる。しかし、本発明者等の検討において、炭素数が８の直鎖状のパーフルオロアルキル基を、そのまま６以下にしただけの場合は、重合体中のパーフルオロアルキル基に起因する結晶性が損なわれることが明らかになっている。 In such a situation, in order to reduce the possibility of the occurrence of PFOA, the carbon number of the perfluoroalkyl group is shortened to 6 or less, specifically, (CF 2 ) 8 F in the above formula is changed to (CF 2) 6 F or (CF 2) 4 F is conceivable to use a compound obtained by substituting the like as a substitute. However, in the study by the present inventors, when the linear perfluoroalkyl group having 8 carbon atoms is simply reduced to 6 or less, the crystallinity due to the perfluoroalkyl group in the polymer is impaired. It has become clear that
そのため、炭素数が６の直鎖状のパーフルオロアルキル基を有するアクリル酸エステルの重合体は、撥水撥油性能を示すものの独特の粘着性を有することが分った。 For this reason, it has been found that a polymer of an acrylate ester having a linear perfluoroalkyl group having 6 carbon atoms exhibits a water- and oil-repellent performance, but has a unique tackiness.
特に防水・防湿コーティング剤として電子部品や基板に処理された場合、独特の粘着性がトラブルの原因となる。具体的には、生産時の不具合、ほこりや異物の付着を原因とする不具合などが挙げられる。 In particular, when it is processed as a waterproof / moisture-proof coating agent on electronic parts and substrates, unique adhesiveness causes trouble. Specific examples include defects during production and defects caused by dust and foreign matter adhesion.
また、近年、部品の小型や印刷技術などの進歩により、柔軟な薄いフィルムにプリント導体回路を形成し、柔軟性と屈曲性があり大きく変形させることが可能なフレキシブル基板が普及してきている。フレキシブル基板は、空間を６０％〜９０％節約でき、しかも実装に自由度を持てることから、電子機器の小型化、軽量化のニーズに欠かせない技術になっている。 In recent years, with the progress of miniaturization of parts and printing technology, a flexible substrate that forms a printed conductor circuit on a flexible thin film and is flexible and flexible and can be greatly deformed has become widespread. The flexible substrate can save 60% to 90% of the space and has a degree of freedom in mounting, and thus has become an indispensable technology for the needs for downsizing and weight reduction of electronic devices.
電子基板の絶縁性防湿コートは、電子機器の信頼性を高める上では、必要不可欠な技術となっている。しかしながら、従来の防水・防湿コーティング剤では、基材への追従性が低くフレキシブル基板では、基板を極端に湾曲させると絶縁性防湿コートに亀裂や剥離が生じてしまう。 Insulating moisture-proof coating on electronic substrates is an indispensable technology for improving the reliability of electronic devices. However, the conventional waterproof / moisture-proof coating agent has low followability to the base material, and in the case of a flexible substrate, if the substrate is extremely curved, the insulating moisture-proof coat is cracked or peeled off.
本発明は、生体および環境への影響が少ない炭素数が６の直鎖状のパーフルオロアルキル基を有する化合物から得られる重合体を使用し、かつ撥水・撥油性能、基材への追従性に優れ、かつ被膜に不都合な粘着性のない表面処理剤の提供を目的とする。 The present invention uses a polymer obtained from a compound having a linear perfluoroalkyl group having 6 carbon atoms and has little influence on the living body and the environment, and is also water / oil repellent performance, following the substrate An object of the present invention is to provide a surface treatment agent that has excellent properties and does not have an adhesive property that is inconvenient to the coating.
本発明者は上記の課題を解決するために鋭意検討した結果、炭素数が６の直鎖状のパーフルオロアルキル基を有するメタクリル酸エステルとメタクリル酸ノルマルブチルとの共重合体が、不都合な粘着性を有さず、かつ撥水・撥油性能を有し、さらには基材への追従性が良好であり、平滑性も改善した被膜を与えることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that a copolymer of a methacrylic acid ester having a linear perfluoroalkyl group having 6 carbon atoms and normal butyl methacrylate is inconvenient. It has been found that a film having no water resistance, water / oil repellency, good followability to a substrate, and improved smoothness can be obtained.
すなわち、本発明は以下の表面処理剤を提供する。
（１）下記式（ａ）で表される化合物から導かれる単位（Ａ）、および、下記式（ｂ）で表される化合物から導かれる単位（Ｂ）を含有する共重合体、ならびに、溶媒を含む防水・防湿コーティング剤であり、
前記共重合体の全単位（１００質量％）における前記単位（Ａ）および前記単位（Ｂ）の含有量の合計が９０質量％以上であり、
前記防水・防湿コーティング剤からなる膜厚２００μｍ〜３５０μｍの被膜を形成した厚さ０．１ｍｍのアルミ板について、ＪＩＳ Ｚ ２２４８記載の押曲げ法（内側半径１ｍｍ）による１８０°曲げ試験を実施した際に前記被膜に割れや剥離を生じず、
前記防水・防湿コーティング剤からなる被膜が２０℃においてタック性を有しないことを特徴とする防水・防湿コーティング剤。
（ただし、前記被膜は、前記防水・防湿コーティング剤を１２０℃で２時間乾燥させて得たものであり、タック性を有しないとは、前記被膜に２０ｇｆ／ｃｍ2の力で薬包紙を１５秒間押しつけた後、薬包紙の剥離に要する力が０．０３ｇｆ以下であることを意味する。）
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）n−（ＣＦ2）6Ｆ 式（ａ）
（式（ａ）中、ｎは０〜４の整数である。）
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）4Ｈ 式（ｂ）
That is, the present invention provides the following surface treatment agent.
(1) A copolymer containing a unit (A) derived from a compound represented by the following formula (a), a unit (B) derived from a compound represented by the following formula (b), and a solvent Is a waterproof / moisture-proof coating containing
The total content of the unit (A) and the unit (B) in all units (100% by mass) of the copolymer is 90% by mass or more,
When an aluminum plate having a thickness of 200 mm to 350 μm formed of the waterproof / moisture-proof coating agent is subjected to a 180 ° bending test by a pressing method (inner radius: 1 mm) described in JIS Z 2248 Without cracking or peeling off the coating,
A waterproof / moisture-proof coating agent, wherein the film comprising the waterproof / moisture-proof coating agent has no tackiness at 20 ° C.
(However, the coating film was obtained by drying the waterproof / moisture-proof coating agent at 120 ° C. for 2 hours, and having no tackiness means that the coating paper was applied to the coating film with a force of 20 gf / cm 2 for 15 seconds. (After pressing, it means that the force required for peeling the medicine wrapper is 0.03 gf or less.)
CH 2 = C (CH 3) -COO- (CH 2) n - (CF 2) 6 F formula (a)
(In formula (a), n is an integer of 0-4.)
CH 2 = C (CH 3) -COO- (CH 2) 4 H formula (b)
（２）前記式（ａ）のｎが２である（１）に記載の防水・防湿コーティング剤。 (2) The waterproof / moisture-proof coating agent according to (1), wherein n in the formula (a) is 2.
（３）前記重合体において、前記単位（Ａ）および単位（Ｂ）の質量比（Ａ）／（Ｂ）が、８０／２０〜１０／９０である、（１）または（２）に記載の防水・防湿コーティング剤。 (3) In the polymer, the mass ratio (A) / (B) of the unit (A) and the unit (B) is 80/20 to 10/90, according to (1) or (2) Waterproof and moisture-proof coating agent.
（４）前記重合体において、前記単位（Ｂ）の含有量が２０〜４０質量％である、（１）〜（３）のいずれかに記載の防水・防湿コーティング剤。 (4) The waterproof / moisture-proof coating agent according to any one of (1) to (3), wherein the content of the unit (B) is 20 to 40% by mass in the polymer.
（５）前記重合体の質量平均分子量（ポリメチルメタクリレート換算）が１×１０4〜１×１０７である（１）〜（４）のいずれかに記載の防水・防湿コーティング剤。 (5) The waterproof / moisture-proof coating agent according to any one of (1) to (4), wherein the polymer has a mass average molecular weight (in terms of polymethyl methacrylate) of 1 × 10 4 to 1 × 10 7 .
（６）（１）〜（５）のいずれかに記載の防水・防湿コーティング剤からなる被膜を有する基材。 (6) A base material having a coating film comprising the waterproof / moisture-proof coating agent according to any one of (1) to (5).
（７）（６）に記載された基材を用いた製品。 (7) A product using the base material described in (6).
本発明の防水・防湿コーティング剤は、パーフルオロアルキル基の炭素数を６以下に抑えつつも、上記式（ａ）および式（ｂ）で特定されるメタクリル化合物から導かれる構成単位を含む重合体を使用することで、高い撥水性能、撥油性能を有することができる。さらに、被膜の粘着性がなく、基材への追従性に優れたまま平滑性の改善ができる防水・防湿コーティング剤を提供することができる。 The waterproof / moisture-proof coating agent of the present invention is a polymer containing structural units derived from the methacrylic compounds specified by the above formulas (a) and (b) while suppressing the carbon number of the perfluoroalkyl group to 6 or less. By using, high water repellency and oil repellency can be obtained. Furthermore, it is possible to provide a waterproof / moisture-proof coating agent that can improve the smoothness without being sticky to the film and having excellent followability to the substrate.
本明細書において、式（ａ）で表される化合物を化合物（ａ）とも記す。他の式で表される化合物も同様に表記することがある。
なお本明細書中、（メタ）アクリレートとは、アクリル酸エステルおよびメタクリル酸エステルの両方またはどちらか一方を表す。
In the present specification, the compound represented by the formula (a) is also referred to as a compound (a). The compounds represented by other formulas may be expressed similarly.
In addition, in this specification, (meth) acrylate represents both or one of acrylic ester and methacrylic ester.
本発明の防水・防湿コーティング剤の必須成分である重合体（以下、「本発明の重合体」ともいう。）は、下記化合物（ａ）から導かれる単位（Ａ）および下記化合物（ｂ）から導かれる単位（Ｂ）を含有する。
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）n−（ＣＦ2）6Ｆ 式（ａ）
式（ａ）中、ｎは０〜４の整数である。
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）4−Ｈ 式（ｂ）
The polymer which is an essential component of the waterproof / moisture-proof coating agent of the present invention (hereinafter also referred to as “polymer of the present invention”) is composed of a unit (A) derived from the following compound (a) and the following compound (b). Contains derived unit (B).
CH 2 = C (CH 3) -COO- (CH 2) n - (CF 2) 6 F formula (a)
In formula (a), n is an integer of 0-4.
CH 2 = C (CH 3) -COO- (CH 2) 4 -H formula (b)
化合物（ａ）において、ｎはいずれも０〜３であることが好ましく、２であることがより好ましい。 In the compound (a), n is preferably 0 to 3, more preferably 2.
本発明の重合体は、単位（Ａ）および単位（Ｂ）を併せ持つことにより、単位（Ａ）単独の場合と同様の高い撥水性能、撥油性能を維持しつつ、単位（Ａ）単独では不十分な被膜の平滑性を補っている。また、単位（Ｂ）単独では撥油性能が著しく低下してしまう。 The polymer of the present invention has both the unit (A) and the unit (B), thereby maintaining the same high water repellency and oil repellency as in the case of the unit (A) alone. Compensates for insufficient film smoothness. Moreover, oil repellency will fall remarkably in the unit (B) alone.
撥水性能の指標には、防水・防湿コーティング剤を用いて形成した被膜の水接触角を用いる。水の接触角は大きいほど優れており、１１０度以上であると好ましい。
撥油性能の指標には、防水・防湿コーティング剤を用いて形成した被膜のノルマルヘキサデカン（ＨＤ）接触角を用いる。ノルマルヘキサデカン（ＨＤ）の接触角は大きいほど優れており、６０度以上であると好ましく、７０度以上であると特に好ましい。
As an index of water repellency, the water contact angle of a film formed using a waterproof / moisture-proof coating agent is used. The larger the contact angle of water, the better, and it is preferably 110 ° or more.
As an index of oil repellency, the normal hexadecane (HD) contact angle of a film formed using a waterproof / moisture-proof coating agent is used. The larger the contact angle of normal hexadecane (HD), the better. It is preferably 60 ° or more, and particularly preferably 70 ° or more.
化合物（ａ）は１種でも複数種であってもよい。なお本発明において、重合体における各単位の質量比率は、重合に使用した原料がすべて単位を構成するとみなした値である。したがって、たとえば単位（Ａ）の質量比率（全単位質量に対する、そこに含まれる単位（Ａ）の質量の百分率）は、実質的に、重合に使用した化合物（ａ）質量の、重合原料化合物の全質量に対する割合として求められる。重合体において、他の単位の質量比率も同様に求められる。 Compound (a) may be one type or a plurality of types. In the present invention, the mass ratio of each unit in the polymer is a value considered that all raw materials used for polymerization constitute a unit. Therefore, for example, the mass ratio of the unit (A) (percentage of the mass of the unit (A) contained therein relative to the total unit mass) is substantially equal to the mass of the compound (a) used for the polymerization of the polymerization raw material compound. It is determined as a percentage of the total mass. In the polymer, the mass ratio of other units is also determined in the same manner.
単位（Ａ）および単位（Ｂ）の質量比（Ａ）／（Ｂ）は、前記単位（Ａ）の質量比率と、単位（Ｂ）の質量比率との合計を、１００としたときの（Ａ）、（Ｂ）それぞれの値を意味する。単位（Ａ）と単位（Ｂ）の質量比（Ａ）／（Ｂ）としては、１０／９０から９０／１０の範囲が好ましく、１０／９０から８０／２０の範囲が好ましく、６０／４０から８０／２０の範囲がより好ましい。上記の範囲内であれば、撥水撥油性能、被膜の追従性、重合体の粘着性、処理後の被膜の平滑性、これら全てにおいて良好である。 The mass ratio (A) / (B) of the unit (A) and the unit (B) is (A when the sum of the mass ratio of the unit (A) and the mass ratio of the unit (B) is 100 (A ), (B) means each value. The mass ratio (A) / (B) of the unit (A) to the unit (B) is preferably in the range of 10/90 to 90/10, preferably in the range of 10/90 to 80/20, and from 60/40. A range of 80/20 is more preferred. Within the above range, the water / oil repellency, coating followability, polymer tackiness, and smoothness of the coating after treatment are all good.
本発明の重合体において、上記単位（Ａ）および単位（Ｂ）の含有量の合計は、９０質量％以上であり、９５質量％以上であることが好ましい。
本発明の重合体において、上記単位（Ａ）の含有量は、２０〜８０質量％であることが好ましく、６０〜８０質量％であることがより好ましい。
本発明の重合体において、上記単位（Ｂ）の含有量は、２０〜８０質量％であることが好ましく、２０〜４０質量％であることがより好ましい。
In the polymer of the present invention, the total content of the unit (A) and the unit (B) is 90% by mass or more, and preferably 95% by mass or more.
In the polymer of the present invention, the content of the unit (A) is preferably 20 to 80% by mass, and more preferably 60 to 80% by mass.
In the polymer of the present invention, the content of the unit (B) is preferably 20 to 80% by mass, and more preferably 20 to 40% by mass.
本発明の重合体は、上記単位（Ａ）および単位（Ｂ）と共重合しうる化合物から導かれる単位（Ｃ）を含んでいてもよい。単位（Ｃ）の質量比率は１０質量％以下であることが好ましく、より好ましくは５重量％以下である。その他の単位（Ｃ）の質量比率が１０質量％を超えてしまうと、被膜の追従性や粘着性を著しく低下させてしまう。 The polymer of the present invention may contain a unit (C) derived from a compound that can be copolymerized with the unit (A) and the unit (B). The mass ratio of the unit (C) is preferably 10% by mass or less, more preferably 5% by weight or less. When the mass ratio of the other unit (C) exceeds 10% by mass, the followability and adhesiveness of the coating are remarkably lowered.
他の単位（Ｃ）は、上記（Ａ）、単位（Ｂ）を形成する化合物と共重合しうる化合物から導かれる単位であれば特に限定されない。これらの化合物としては、炭素数８以上の長鎖アルキルの（メタ）アクリル酸エステル、炭素数７以下の短鎖アルキルの（メタ）アクリル酸エステル、シクロヘキシル基、フェニル基、イソボルニル基、ノルボルニル基等の環状炭化水素基を有する（メタ）アクリル酸エステル等が好ましい。
なお、防水・防湿コーティング剤であるため、極性の強い水酸基、カルボキシル基、エポキシ基、ポリエチレングリコールなどの有機基をもつ単位は好ましくない。
The other unit (C) is not particularly limited as long as it is a unit derived from a compound that can be copolymerized with the compound forming the above (A) and unit (B). As these compounds, long chain alkyl (meth) acrylates having 8 or more carbon atoms, short chain alkyl (meth) acrylates having 7 or less carbon atoms, cyclohexyl groups, phenyl groups, isobornyl groups, norbornyl groups, etc. (Meth) acrylic acid ester having a cyclic hydrocarbon group is preferred.
In addition, since it is a waterproof / moisture-proof coating agent, a unit having an organic group such as a strongly polar hydroxyl group, carboxyl group, epoxy group or polyethylene glycol is not preferred.
本発明の重合体の分子量は特に限定されないが、質量平均分子量（Ｍｗ）（ポリメチルメタクリレート換算）で１×１０4〜１×１０7であることが好ましく、１×１０4〜１×１０6であることがより好ましく、５×１０4〜１×１０6であることが特に好ましい。 Polymer molecular weight of the present invention is not particularly limited, is preferably 1 × 10 4 ~1 × 10 7 in terms of mass average molecular weight (Mw) (polymethyl methacrylate equivalent), 1 × 10 4 ~1 × 10 6 Is more preferable, and 5 × 10 4 to 1 × 10 6 is particularly preferable.
本発明の重合体は、重合形態など特に制限されない。共重合体である場合の重合形態は特に制限されず、ランダム、ブロック、グラフトなどのいずれでもよいがランダム重合体であることが好ましい。 The polymer of the present invention is not particularly limited in the form of polymerization. The form of polymerization in the case of a copolymer is not particularly limited and may be any of random, block, graft and the like, but is preferably a random polymer.
重合体の製造方法も特に限定されず、各種の公知の方法を採用し得る。例えば、各化合物中の不飽和基に基づき付加重合させることができる。重合に際しては、公知の不飽和化合物の付加重合条件を適宜に採択して行うことができる。例えば重合開始源として有機過酸化物、アゾ化合物、過硫酸塩等の通常の開始剤が利用できる。 The method for producing the polymer is not particularly limited, and various known methods can be adopted. For example, addition polymerization can be performed based on an unsaturated group in each compound. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source.
本発明の防水・防湿コーティング剤から得られた被膜は高い追従性を有する。このため、フレキシブル基板に用いた際に基板を湾曲させても被膜に亀裂や剥離を生じない。追従性は、本発明の防水・防湿コーティング剤を用いて膜厚２００μｍ〜３５０μｍの被膜を形成した厚さ０．１ｍｍのアルミ板について、ＪＩＳ Ｚ ２２４８記載の押曲げ法（内側半径１ｍｍ）による１８０°曲げ試験を実施することにより評価できる。前記曲げ試験を行っても前記被膜に割れや剥離を生じないものは追従性が高いと言える。
なお、この被膜は、前記防水・防湿コーティング剤を１２０℃で２時間乾燥させて得たものである（以下、本明細書において同様）。
The film obtained from the waterproof / moisture-proof coating agent of the present invention has high followability. For this reason, even when the substrate is bent when used for a flexible substrate, the coating does not crack or peel off. The followability is 180 by the press bending method (inner radius 1 mm) described in JIS Z 2248 for an aluminum plate having a thickness of 0.1 mm in which a film having a thickness of 200 μm to 350 μm is formed using the waterproof / moisture-proof coating agent of the present invention. ° Can be evaluated by conducting a bending test. It can be said that even if the bending test is performed, the film that does not crack or peel off has high followability.
This film was obtained by drying the waterproof / moisture-proof coating agent at 120 ° C. for 2 hours (hereinafter, the same applies in this specification).
本発明の防水・防湿コーティング剤から得られた被膜は不都合な粘着性を有しない。これは「前記被膜が２０℃においてタック性を有しない」とも表記できる。タック性を有しないことは、前記被膜に２０ｇｆ／ｃｍ2の力で薬包紙を１５秒間押しつけた後、薬包紙の剥離に要する力が０．０３ｇｆ以下であることにより評価できる。前記の値である場合、粘着性が低いため、異物の付着等の不具合を防止することができる。 The film obtained from the waterproof / moisture-proof coating agent of the present invention does not have an adverse tackiness. This can also be expressed as “the coating does not have tackiness at 20 ° C.”. The absence of tackiness can be evaluated by pressing the drug-wrapping paper against the coating film with a force of 20 gf / cm 2 for 15 seconds and then the force required to peel off the drug-wrapping paper is 0.03 gf or less. In the case of the above value, since the adhesiveness is low, it is possible to prevent problems such as adhesion of foreign matters.
また、本発明の防水・防湿コーティング剤は、得られた被膜が平滑性を有することも特徴とする。これにより、均一な膜厚で被膜を形成することができ基板に均一な撥水・撥油・防湿の性能を付与することができる。平滑性は被膜の外観を確認することにより評価できる。 The waterproof / moisture-proof coating agent of the present invention is also characterized in that the obtained film has smoothness. Thereby, a film can be formed with a uniform film thickness, and uniform water repellency, oil repellency, and moisture proof performance can be imparted to the substrate. Smoothness can be evaluated by confirming the appearance of the coating.
前記単位（Ａ）のみからなる重合体を用いたコーティング剤は、高い追従性を有するとともにタック性を有しない優れたコーティング剤であるが、平滑性が著しく劣っており、均一な膜厚で被膜を得ることが非常に困難である。これに対し、本発明の重合体は単位（Ａ）と単位（Ｂ）の両方を有することにより、前記追従性とタック性を維持したまま、平滑性も改善した防水・防湿コーティング剤となる。 The coating agent using the polymer consisting only of the unit (A) is an excellent coating agent having high followability and not having tackiness, but has extremely poor smoothness and a uniform film thickness. Is very difficult to get. On the other hand, the polymer of the present invention has both a unit (A) and a unit (B), so that it becomes a waterproof / moisture-proof coating agent with improved smoothness while maintaining the followability and tackiness.
本発明の防水・防湿コーティング剤は、被膜成分として上記のような特定の重合体を含み、該重合体を溶媒中に含む液状形態である。
本発明の防水・防湿コーティング剤の製造方法も限定されない。例えば本発明の重合体を公知の溶媒に溶解させて得ることができる。また、例えば化合物（ａ）および化合物（ｂ）を溶媒に添加し、この溶媒を重合媒体とする溶液重合によって本発明の重合体を製造し、本発明の重合体を含む前記溶媒を得て、これを本発明の防水・防湿コーティング剤とすることもできる。乳化重合させることで本発明の重合体を含む溶液を得て、これを本発明の防水・防湿コーティング剤とすることもできる。ここで得られた本発明の重合体を分離し、他の溶媒に溶解させてもよい。また、重合原料の化合物がガスである場合には、圧力容器を用いて、加圧下に連続供給してもよい。
The waterproof / moisture-proof coating agent of the present invention includes a specific polymer as described above as a film component, and is in a liquid form including the polymer in a solvent.
The method for producing the waterproof / moisture-proof coating agent of the present invention is not limited. For example, it can be obtained by dissolving the polymer of the present invention in a known solvent. Further, for example, the compound (a) and the compound (b) are added to a solvent, the polymer of the present invention is produced by solution polymerization using the solvent as a polymerization medium, and the solvent containing the polymer of the present invention is obtained. This can also be used as the waterproof / moisture-proof coating agent of the present invention. A solution containing the polymer of the present invention can be obtained by emulsion polymerization, and this can be used as the waterproof / moisture-proof coating agent of the present invention. The polymer of the present invention obtained here may be separated and dissolved in another solvent. Further, when the polymerization raw material compound is a gas, it may be continuously supplied under pressure using a pressure vessel.
本発明の防水・防湿コーティング剤を形成する溶媒は、本発明の重合体を溶解または分散できるものであればよく、特に限定されず、各種有機溶剤、水またはこれらの混合媒体などが挙げられる。一般的な有機溶剤である酢酸エチル、酢酸ブチル、アセトン、メチルエチルケトンなどの極性の強い溶剤が使用可能であるが、非処理物への材質影響と重合物の溶解性の観点から、フッ素系溶剤を使用するのが好ましい。フッ素系溶剤としては、ハイドロフルオロカーボン（ＨＦＣ）またはハイドロフルオロエーテル（ＨＦＥ）が挙げられる。使用可能なフッ素系溶剤の具体例を以下に示すが、これらに限定されるものではない。 The solvent for forming the waterproof / moisture-proof coating agent of the present invention is not particularly limited as long as it can dissolve or disperse the polymer of the present invention, and examples thereof include various organic solvents, water, and mixed media thereof. Strong polar solvents such as common organic solvents such as ethyl acetate, butyl acetate, acetone, and methyl ethyl ketone can be used. However, from the viewpoint of material effects on non-treated materials and solubility of the polymer, fluorinated solvents can be used. It is preferred to use. Examples of the fluorine-based solvent include hydrofluorocarbon (HFC) or hydrofluoroether (HFE). Specific examples of usable fluorinated solvents are shown below, but are not limited thereto.
ｍ−キシレンヘキサフルオリド（以下、ｍ−ＸＨＦと記す。）
ｐ−キシレンヘキサフルオリド
ＣＦ3ＣＨ2ＣＦ2ＣＨ3
ＣＦ3ＣＨ2ＣＦ2Ｈ
Ｃ6Ｆ１3ＯＣＨ3
Ｃ6Ｆ13ＯＣ2Ｈ5
Ｃ6Ｆ13ＣＨ2ＣＨ3
Ｃ3Ｆ7ＯＣＨ3
Ｃ3Ｆ7ＯＣ2Ｈ5
Ｃ6Ｆ13Ｈ
ＣＦ2ＨＣＦ2ＣＨ2ＯＣＦ2ＣＦ2Ｈ
ＣＦ3ＣＦＨＣＦＨＣＦ2ＣＨ3
ＣＦ3（ＯＣＦ2ＣＦ2）n（ＯＣＦ2）mＯＣＦ2Ｈ
Ｃ8Ｆ17ＯＣＨ3
Ｃ7Ｆ15ＯＣＨ3
Ｃ4Ｆ9ＯＣＨ3
Ｃ4Ｆ9ＯＣ2Ｈ5
Ｃ4Ｆ9ＣＨ2ＣＨ3
ＣＦ3ＣＨ2ＯＣＦ2ＣＦ2ＣＦ2Ｈ
（上記例示中、添字ｍおよびｎは、それぞれ独立に、１〜２０の整数を表す。）
およびこれらの混合物。
たとえばＣＦ3（ＣＦ2）3ＯＣ2Ｈ5と（ＣＦ3）2ＣＦＣＦ2ＯＣ2Ｈ5とのハイドロフルオロエーテル混合物がノベックＨＦＥ７２００（３Ｍ社製）の商品名で入手可能である。
m-xylene hexafluoride (hereinafter referred to as m-XHF)
p-Xylene hexafluoride CF 3 CH 2 CF 2 CH 3
CF 3 CH 2 CF 2 H
C 6 F 13 OCH 3
C 6 F 13 OC 2 H 5
C 6 F 13 CH 2 CH 3
C 3 F 7 OCH 3
C 3 F 7 OC 2 H 5
C 6 F 13 H
CF 2 HCF 2 CH 2 OCF 2 CF 2 H
CF 3 CFHCCFHC 2 CH 3
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
C 4 F 9 OCH 3
C 4 F 9 OC 2 H 5
C 4 F 9 CH 2 CH 3
CF 3 CH 2 OCF 2 CF 2 CF 2 H
(In the above examples, the subscripts m and n each independently represent an integer of 1 to 20.)
And mixtures of these.
For example, a hydrofluoroether mixture of CF 3 (CF 2 ) 3 OC 2 H 5 and (CF 3 ) 2 CFCF 2 OC 2 H 5 is available under the trade name Novec HFE7200 (manufactured by 3M).
本発明の防水・防湿コーティング剤の濃度は、本発明の重合体の濃度が１〜２０質量％であるのが好ましい。本発明の防水・防湿コーティング剤における本発明の重合体の濃度は最終的濃度であればよく、重合直後の重合体を含む溶液中の重合体濃度（固形分濃度）が２０質量％を超えていてもなんら差し支えない。高濃度の重合体を含む溶液は、最終的に上記好ましい濃度となるように適宜に希釈することができる。希釈した溶液は、そのまま表面処理剤とすることができる。
希釈溶剤としては、前記使用可能なフッ素系溶剤が挙げられる。
The concentration of the waterproof / moisture-proof coating agent of the present invention is preferably 1 to 20% by mass of the polymer of the present invention. The concentration of the polymer of the present invention in the waterproof / moisture-proof coating agent of the present invention may be a final concentration, and the polymer concentration (solid content concentration) in the solution containing the polymer immediately after polymerization exceeds 20% by mass. There is no problem. A solution containing a high-concentration polymer can be appropriately diluted so that the final desired concentration is obtained. The diluted solution can be used as a surface treatment agent as it is.
Examples of the diluting solvent include the usable fluorine-based solvents.
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、前記した以外の他の溶剤成分を含んでいてもよい。このような助溶剤としては、アルコール系溶剤（メタノール、エタノール、イソプロピルアルコール等）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトン等）、炭化水素系溶剤（ヘキサン、ヘプタン、オクタン等）、環式炭化水素溶剤（シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等）、芳香族炭化水素溶剤（トルエン、キシレン等）、テルペン系溶剤（メンタン、テルピン、ピネン、リモネン等）がある。
これらの溶剤は、臭気、乾燥速度、濡れ性などを調整する事ができる。
Other solvent components other than those described above may be included as long as they do not adversely affect stability, performance, appearance, and the like. Such co-solvents include alcohol solvents (methanol, ethanol, isopropyl alcohol, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), hydrocarbon solvents (hexane, heptane, octane, etc.), cyclic There are hydrocarbon solvents (cyclohexane, methylcyclohexane, ethylcyclohexane, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), and terpene solvents (menthane, terpine, pinene, limonene, etc.).
These solvents can adjust odor, drying speed, wettability and the like.
本発明の防水・防湿コーティング剤は、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、前記した以外の他の成分を含んでいてもよい。このような他の成分としては、例えば被膜表面の腐食を防止するためのｐＨ調整剤、防錆剤、防水・防湿コーティング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が挙げられる。 The waterproof / moisture-proof coating agent of the present invention may contain other components other than those described above as long as the stability, performance, appearance and the like are not adversely affected. As such other components, for example, when a pH adjuster, a rust preventive, or a waterproof / moisture-proof coating agent for preventing corrosion of the coating surface is diluted, the polymer concentration in the liquid is controlled. Examples include dyes for distinguishing purposes and untreated parts, dye stabilizers, flame retardants, antifoaming agents, and antistatic agents.
本発明の防水・防湿コーティング剤は、撥水撥油防湿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、本発明の防水・防湿コーティング剤から溶媒が除去されて形成されるものであり、主として、本発明の重合体からなるものである。ここで、主としてとは、該被膜が、本発明の重合体のみから形成されていてもよく、前記のように悪影響を与えない範囲で他の成分を含んでいてもよいことを意味する。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、ローラー塗布等による塗布等の方法がある。 The waterproof / moisture-proof coating agent of the present invention can be used by forming a film by applying it to a portion where water / oil / oil / moisture resistance is desired. The film is formed by removing the solvent from the waterproof / moisture-proof coating agent of the present invention, and is mainly composed of the polymer of the present invention. Here, “mainly” means that the coating film may be formed only from the polymer of the present invention and may contain other components as long as it does not adversely affect as described above. 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.
本発明の防水・防湿コーティング剤の塗布後は、溶媒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 waterproof / moisture-proof coating agent of the present invention, drying is preferably performed 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.
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。なお、特に断わりのない限り、以下の実施例の記載において「％」で表示されるものは「質量％」を表すものとする。
以下の実施例で使用する化合物を表１に示す。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。
The present invention will be specifically described below, but the present invention is not limited to the following examples. Unless otherwise specified, what is indicated by “%” in the description of the following examples represents “mass%”.
The compounds used in the following examples are shown in Table 1. The compound used can be obtained as a reagent from the market or can be easily synthesized by a known synthesis method.
［実施例１〜１７および比較例１〜１３］
密閉容器に、モノマー濃度を３０％、開始剤濃度を０．２％、反応溶剤となるメタキシレンヘキサフロライド（ｍ-ＸＨＦ）を仕込み、７０℃で１８時間以上反応を行い、重合体１〜９および比較重合体１〜１３を得た。各重合体のモノマーの仕込みは、表２に記載の質量比で行なった。
これらの重合体は、約３０％のｍ-ＸＨＦ溶液で得られた。それを表３に示すようにｍ-ＸＨＦおよびリモネンで希釈して、重合体濃度が１０％となるように濃度調整して、防水・防湿コーティング剤である実施例１〜１７および比較例１〜１３とした。
[Examples 1 to 17 and Comparative Examples 1 to 13]
In a closed container, a monomer concentration of 30%, an initiator concentration of 0.2%, and metaxylene hexafluoride (m-XHF) as a reaction solvent were charged, and the reaction was carried out at 70 ° C. for 18 hours or more. 9 and comparative polymers 1 to 13 were obtained. Charge of the monomer of each polymer was performed by the mass ratio shown in Table 2.
These polymers were obtained with about 30% m-XHF solution. It is diluted with m-XHF and limonene as shown in Table 3, and the concentration is adjusted so that the polymer concentration becomes 10%, and Examples 1-17 and Comparative Examples 1 to 1 which are waterproof / moisture-proof coating agents are used. It was set to 13.
粘着性評価、追従性評価、重合体の分子量測定は、前記約３０％の重合体溶液を用いて評価した。平滑性評価と接触角測定は、防水・防湿コーティング剤を用いて評価した。
粘着性評価、追従性評価、平滑性評価、接触角測定、重合体の分子量測定は、以下に示す方法で実施した。
Tackiness evaluation, follow-up evaluation, and molecular weight measurement of the polymer were evaluated using the about 30% polymer solution. The smoothness evaluation and contact angle measurement were evaluated using a waterproof / moisture-proof coating agent.
Adhesion evaluation, follow-up evaluation, smoothness evaluation, contact angle measurement, and polymer molecular weight measurement were carried out by the methods shown below.
［被膜の粘着性評価］
重合体１〜９および比較重合体１〜１３の前記約３０％重合体溶液を、それぞれ、アルミカップ（φ４５ｍｍ）に約２ｇずつ採取し、１２０℃の乾燥機で２時間乾燥させた。乾燥後、形成された被膜の上に薬包紙(２５×２５ｍｍ、約０．０２５ｇ）を置き、その上に１００ｇの分銅（φ２４ｍｍ）を置いた。１５秒後、分銅を取り除き薬包紙の張り付き具合を確認した。
アルミカップをさかさまにした際に、薬包紙が落ちてくるものを○。落ちずに被膜に張り付いているものを×とした。評価結果を表２に記載した。
[Evaluation of film adhesion]
About 2 g of each of the about 30% polymer solutions of the polymers 1 to 9 and the comparative polymers 1 to 13 was collected in an aluminum cup (φ45 mm), and dried for 2 hours with a 120 ° C. drier. After drying, medicine-wrapping paper (25 × 25 mm, about 0.025 g) was placed on the formed film, and 100 g of weight (φ24 mm) was placed thereon. After 15 seconds, the weight was removed and the sticking of the medicine wrapper was confirmed.
○ When the aluminum cup is turned upside down, ○ Those that did not fall and stuck to the film were marked with x. The evaluation results are shown in Table 2.
［被膜の追従性評価］
重合体１〜９および比較重合体１〜１３の前記約３０％重合体溶液を、それぞれ、アルミカップ（φ４５ｍｍ）に約２ｇずつ採取し、１２０℃の乾燥機で２時間乾燥させた。この操作により、アルミカップに厚さ約２００〜３５０μｍのコーティング被膜を形成させた。その後、アルミカップで押曲げ法(内側半径１ｍｍ)による１８０°曲げ試験を実施し、被膜の状態を確認した。被膜の割れや剥離が確認されなかったものを○、割れや剥離が確認されたものを×とした。評価結果を表２に記載した。
[Followability evaluation of coating]
About 2 g of each of the about 30% polymer solutions of the polymers 1 to 9 and the comparative polymers 1 to 13 was collected in an aluminum cup (φ45 mm), and dried for 2 hours with a 120 ° C. drier. By this operation, a coating film having a thickness of about 200 to 350 μm was formed on the aluminum cup. Then, the 180 degree bending test by the press bending method (inner radius 1mm) was implemented with the aluminum cup, and the state of the film was confirmed. The case where cracking or peeling of the coating was not confirmed was rated as “◯”, and the case where cracking or peeling was confirmed was marked as “X”. The evaluation results are shown in Table 2.
［平滑性評価］
各防水・防湿コーティング剤を、それぞれ、２５×２５ｍｍに区切った銅板に１００μＬたらし、均一に塗り伸ばした。その後、室温で乾燥させ外観を確認した。処理液が乾燥時に収縮しながら乾燥し、薄膜部分が生じてしまったものを×、薄膜部分が発生しなかったものを○とした。評価結果を表３に記載した。
[Smoothness evaluation]
100 μL of each waterproof / moisture-proof coating agent was applied to a copper plate divided into 25 × 25 mm, and spread uniformly. Then, it dried at room temperature and confirmed the external appearance. When the treatment liquid was dried while shrinking during drying and a thin film portion was formed, “x” was given, and when the thin film portion was not generated, “◯” was given. The evaluation results are shown in Table 3.
［接触角測定］
各防水・防湿コーティング剤に、室温下で、ガラス板を浸漬した。そして１分後に取り出し、１２０℃の乾燥機で５分間乾燥させ、各被膜を有する各ガラス板を得た。
次に各々の種類の被膜を形成した各ガラス板の被膜上に、水、ｎ−ヘキサデカン（ＨＤ）を滴下し、接触角を測定した。
水およびＨＤの接触角の測定には、自動接触角計ＯＣＡ−２０［Ｄａｔａ Ｐｈｙｓｉｃｓ社製］を用いた。評価結果を表３に記載した。
[Contact angle measurement]
A glass plate was immersed in each waterproof / moisture-proof coating agent at room temperature. And it took out after 1 minute and made it dry for 5 minutes with a 120 degreeC dryer, and obtained each glass plate which has each film.
Next, water and n-hexadecane (HD) were dropped onto the coating of each glass plate on which each type of coating was formed, and the contact angle was measured.
An automatic contact angle meter OCA-20 [manufactured by Data Physics, Inc.] was used for measuring the contact angles of water and HD. The evaluation results are shown in Table 3.
［質量平均分子量の測定］
重合体１〜９および比較重合体１〜１３を、溶液中の重合体の濃度が約１％になるように、アサヒクリンＡＫ−２２５ＳＥＣ１（旭硝子（株）製）を用いて希釈し、測定サンプルとした。昭和電工株式会社製Ｓｈｏｄｅｘ ＧＰＣ−１０４を用いて、以下の条件でＧＰＣを測定した。評価結果を表２に記載した。
＜ＧＰＣ測定条件＞
分析カラム：ＬＦ−６０４（充填剤：スチレンジビニルベンゼン共重合体，昭和電工株式会社製）×２
リファレンスカラム：ＫＦ６００ＲＨ（充填剤：なし，昭和電工株式会社製）×２
移動層：ＡＫ−２２５ＳＥＣ１
流量：０．３ｍｌ/ｍｉｎ
カラム温度：４０℃
標準物質：ポリメチルメタクリレート
[Measurement of mass average molecular weight]
Samples 1 to 9 and Comparative polymers 1 to 13 were diluted with Asahi Clin AK-225SEC1 (Asahi Glass Co., Ltd.) so that the concentration of the polymer in the solution was about 1%. It was. GPC was measured under the following conditions using Shodex GPC-104 manufactured by Showa Denko K.K. The evaluation results are shown in Table 2.
<GPC measurement conditions>
Analytical column: LF-604 (filler: styrene divinylbenzene copolymer, manufactured by Showa Denko KK) x 2
Reference column: KF600RH (filler: none, Showa Denko KK) x 2
Moving layer: AK-225SEC1
Flow rate: 0.3ml / min
Column temperature: 40 ° C
Reference material: Polymethylmethacrylate
単位（Ａ）および単位（Ｂ）を有する本発明の防水・防湿コーティング剤のみ、撥水撥油性能を維持しつつ、被膜の追従性、粘着性、平滑性の問題点を全て解決できることが分かった。 Only the waterproof / moisture-proof coating agent of the present invention having the unit (A) and the unit (B) is found to be able to solve all the problems of the followability, tackiness and smoothness of the film while maintaining the water / oil repellency. It was.
Claims (7)
前記共重合体の全単位（１００質量％）における前記単位（Ａ）および前記単位（Ｂ）の含有量の合計が９０質量％以上であり、
前記防水・防湿コーティング剤からなる膜厚２００μｍ〜３５０μｍの被膜を形成した厚さ０．１ｍｍのアルミ板について、ＪＩＳ Ｚ ２２４８記載の押曲げ法（内側半径１ｍｍ）による１８０°曲げ試験を実施した際に前記被膜に割れや剥離を生じず、
前記防水・防湿コーティング剤からなる被膜が２０℃においてタック性を有しないことを特徴とする防水・防湿コーティング剤。
（ただし、前記被膜は、前記防水・防湿コーティング剤を１２０℃で２時間乾燥させて得たものであり、タック性を有しないとは、前記被膜に２０ｇｆ／ｃｍ2の力で薬包紙を１５秒間押しつけた後、薬包紙の剥離に要する力が０．０３ｇｆ以下であることを意味する。）
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）n−（ＣＦ2）6Ｆ 式（ａ）
（式（ａ）中、ｎは０〜４の整数である。）
ＣＨ2＝Ｃ（ＣＨ3）−ＣＯＯ−（ＣＨ2）4Ｈ 式（ｂ） A copolymer containing a unit (A) derived from a compound represented by the following formula (a) and a unit (B) derived from a compound represented by the following formula (b), and waterproofing comprising a solvent・ Moisture-proof coating agent
The total content of the unit (A) and the unit (B) in all units (100% by mass) of the copolymer is 90% by mass or more,
When an aluminum plate having a thickness of 200 mm to 350 μm formed of the waterproof / moisture-proof coating agent is subjected to a 180 ° bending test by a pressing method (inner radius: 1 mm) described in JIS Z 2248 Without cracking or peeling off the coating,
A waterproof / moisture-proof coating agent, wherein the film comprising the waterproof / moisture-proof coating agent has no tackiness at 20 ° C.
(However, the coating film was obtained by drying the waterproof / moisture-proof coating agent at 120 ° C. for 2 hours, and having no tackiness means that the coating paper was applied to the coating film with a force of 20 gf / cm 2 for 15 seconds. (After pressing, it means that the force required for peeling the medicine wrapper is 0.03 gf or less.)
CH 2 = C (CH 3) -COO- (CH 2) n - (CF 2) 6 F formula (a)
(In formula (a), n is an integer of 0-4.)
CH 2 = C (CH 3) -COO- (CH 2) 4 H formula (b)
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| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
| WO2012020735A1 (en) * | 2010-08-11 | 2012-02-16 | 旭硝子株式会社 | Water repellent composition, method for manufacturing same, hydrophobic substrate treatment agent composition and component |
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| JP2012017438A (en) * | 2010-07-09 | 2012-01-26 | Noda Screen:Kk | Fluorine-based copolymer, method for producing the same and coating agent |
| WO2012020735A1 (en) * | 2010-08-11 | 2012-02-16 | 旭硝子株式会社 | Water repellent composition, method for manufacturing same, hydrophobic substrate treatment agent composition and component |
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