JP6713340B2 - Film forming liquid composition and method for producing the same - Google Patents
Film forming liquid composition and method for producing the same Download PDFInfo
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- JP6713340B2 JP6713340B2 JP2016090230A JP2016090230A JP6713340B2 JP 6713340 B2 JP6713340 B2 JP 6713340B2 JP 2016090230 A JP2016090230 A JP 2016090230A JP 2016090230 A JP2016090230 A JP 2016090230A JP 6713340 B2 JP6713340 B2 JP 6713340B2
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- 239000007788 liquid Substances 0.000 title claims description 122
- 239000000203 mixture Substances 0.000 title claims description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002904 solvent Substances 0.000 claims description 155
- -1 silicon alkoxide Chemical class 0.000 claims description 55
- 239000011737 fluorine Substances 0.000 claims description 53
- 229910052731 fluorine Inorganic materials 0.000 claims description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229910000077 silane Inorganic materials 0.000 claims description 45
- 238000009835 boiling Methods 0.000 claims description 44
- 229910052710 silicon Inorganic materials 0.000 claims description 43
- 239000010703 silicon Substances 0.000 claims description 43
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 6
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 6
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000011248 coating agent Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 38
- 239000000758 substrate Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000002994 raw material Substances 0.000 description 18
- 230000003373 anti-fouling effect Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000013329 compounding Methods 0.000 description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000005871 repellent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical group FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000280258 Dyschoriste linearis Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Description
本発明は、複数の機能を付与し得る膜を形成するための液組成物及びその製造方法に関する。更に詳しくは、撥水性及び撥油性（以下、撥水撥油性という。）を有する防汚性膜及び金型に代表される型（以下、金型等という。）に離型性を付与し得る膜（以下、離型性付与膜という。）を形成するための液組成物及びその製造方法に関するものである。 The present invention relates to a liquid composition for forming a film capable of imparting a plurality of functions and a method for producing the same . More specifically, mold releasability can be imparted to a mold (hereinafter referred to as a mold) represented by an antifouling film and a mold having water repellency and oil repellency (hereinafter referred to as water and oil repellency). The present invention relates to a liquid composition for forming a film (hereinafter referred to as a releasability imparting film) and a method for producing the liquid composition.
従来、撥水撥油性を付与することができる化合物として、特定のペルフルオロアミン構造を有する含フッ素シラン化合物が開示されている（例えば特許文献１参照。）。この含フッ素シラン化合物は、炭素数８以上のペルフルオロアルキル基を含有せず、生体蓄積性や環境適応性の点で問題となるペルフルオロオクタンスルホン酸（ＰＦＯＳ）又はペルフルオロオクタン酸（ＰＦＯＡ）を生成する懸念がない化学構造でありながら、優れた撥水撥油性を付与することが可能であり、多種多様な用途に適用可能性を有するフッ素系シランカップリング剤として有用である特徴がある。 Conventionally, a fluorine-containing silane compound having a specific perfluoroamine structure has been disclosed as a compound capable of imparting water and oil repellency (see, for example, Patent Document 1). This fluorine-containing silane compound does not contain a perfluoroalkyl group having 8 or more carbon atoms and produces perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA) which is problematic in terms of bioaccumulation and environmental adaptability. It has a feature that it is useful as a fluorine-based silane coupling agent that can impart excellent water and oil repellency even though it has no fear of chemical structure and has applicability to a wide variety of applications.
特許文献１に示される含フッ素シラン化合物を少量だけ添加して液組成物を調製すると、この液組成物により形成した膜に撥水撥油性を付与することができる。しかしこの含フッ素シラン化合物を一般的なアルコール溶媒とを混合して液組成物を調製した場合、この含フッ素シラン化合物の表面張力がアルコール溶媒の表面張力と大きく異なってしまう。このため、この液組成物を基材上にバーコーターで塗布した場合、塗膜に水玉模様やコーター筋が生じて、成膜性に劣る。更に含フッ素シラン化合物と溶媒だけを混合した液組成物で塗膜を形成した場合、塗膜の強度が低いうえ、塗膜の基材への密着性が十分でない。 When a liquid composition is prepared by adding a small amount of the fluorine-containing silane compound disclosed in Patent Document 1, it is possible to impart water and oil repellency to a film formed by this liquid composition. However, when the liquid composition is prepared by mixing the fluorine-containing silane compound with a general alcohol solvent, the surface tension of the fluorine-containing silane compound is significantly different from the surface tension of the alcohol solvent. Therefore, when this liquid composition is applied onto a substrate with a bar coater, a polka dot pattern and coater streaks are generated in the coating film, resulting in poor film forming properties. Furthermore, when a coating film is formed from a liquid composition in which only a fluorinated silane compound and a solvent are mixed, the strength of the coating film is low and the adhesion of the coating film to the substrate is insufficient.
本発明の目的は、形成した膜に撥水撥油性の防汚機能を付与するとともに、成膜性に優れ、基材への密着性が良好で、強度の高い膜を形成可能な防汚性膜形成用液組成物及びその製造方法を提供することにある。本発明の別の目的は、形成した膜に離型性を付与するとともに、成膜性に優れ、基材への密着性が良好で、強度の高い膜を形成可能な離型性付与膜形成用液組成物及びその製造方法を提供することにある。 An object of the present invention is to impart a water- and oil-repellent antifouling function to a formed film, and also to form a film having excellent film-forming property, good adhesion to a substrate, and high strength. It is intended to provide a film forming liquid composition and a method for producing the same. Another object of the present invention is to form a releasability-imparting film capable of forming a film having excellent releasability and excellent film-forming property, good adhesion to a substrate, and high strength. An object is to provide a liquid composition and a method for producing the same.
本発明の第１の観点は、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランの第１加水分解物と、下記一般式（１）で示されるフッ素含有シランの第２加水分解物と、所定の溶媒とを含む膜形成用液組成物である。この液組成物は、前記第１加水分解物と前記第２加水分解物が合計して液組成物１００質量％に対して０．１〜１０．０質量％含まれ、前記所定の溶媒が、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒と、沸点が１２０℃未満の第３溶媒と、水とを混合した混合溶媒であり、前記第１溶媒、前記第２溶媒及び前記第３溶媒の質量比が、第１溶媒：第２溶媒：第３溶媒＝９〜１５：１〜３：８２〜９０であることを特徴とする。 A first aspect of the present invention is that a first hydrolyzate of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide, a second hydrolyzate of a fluorine-containing silane represented by the following general formula (1), and a predetermined A film forming liquid composition containing a solvent. This liquid composition contains the first hydrolyzate and the second hydrolyzate in an amount of 0.1 to 10.0 mass% with respect to 100 mass% of the liquid composition, and the predetermined solvent is A first solvent having a boiling point of 120° C. or more and less than 160° C., a second solvent having a boiling point of 160° C. or more and 220° C. or less, a third solvent having a boiling point of less than 120° C., and water, The mass ratio of the first solvent, the second solvent, and the third solvent is first solvent:second solvent:third solvent=9 to 15:1 to 3:82 to 90.
上記式（１）中、ｍ及びｎは、それぞれ同一又は互いに異なる１〜６の整数である。また、Ｒｆ１は、炭素数１〜６のペルフルオロアルキレン基であって、直鎖状又は分枝状であってもよい。また上記式（１）中、Ｘは、炭素数２〜１０の炭化水素基であって、エーテル結合、ＣＯ−ＮＨ結合及びＯ−ＣＯ−ＮＨ結合から選択される１種以上の結合を含んでいてもよい。更に上記式（１）中、Ｒ１及びＺはアルコキシ基である（ただし、ａは０〜３の整数）。 In the above formula (1), m and n are the same or different integers of 1 to 6, respectively. Rf 1 is a perfluoroalkylene group having 1 to 6 carbon atoms and may be linear or branched. Further, in the above formula (1), X is a hydrocarbon group having 2 to 10 carbon atoms, and contains at least one bond selected from an ether bond, a CO—NH bond and an O—CO—NH bond. You may stay. Further, in the above formula (1), R 1 and Z are alkoxy groups (provided that a is an integer of 0 to 3).
本発明の第２の観点は、第１ないし第３の観点のうち、いずれかの観点の膜形成用液組成物であって、前記第１溶媒が２−メトキシエタノール、２−エトキシエタノール、２−イソプロポキシエタノール、１−メトキシ−２−プロパノール及び１−エトキシ−２−プロパノールからなる群より選ばれた１種又は２種以上の溶媒であり、前記第２溶媒がジアセトンアルコール、ジエチレングリコールモノメチルエーテル、Ｎ−メチルピロリドン及び３−メトキシ−３−メチル−１−ブタノールからなる群より選ばれた１種又は２種以上の溶媒であり、前記第３溶媒が炭素数１〜３の範囲にある１種又は２種以上のアルコールであることを特徴とする。
本発明の第３の観点は、ケイ素アルコキシドの第１加水分解物を含む液に、上記一般式（１）で示されるフッ素含有シランと有機溶媒とを添加混合してフッ素含有シランの第２加水分解物を調製することにより、膜形成用液組成物を製造する方法であって、前記有機溶媒が、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒と、沸点が１２０℃未満の第３溶媒とからなり、前記ケイ素アルコキシドの第１加水分解物が、前記ケイ素アルコキシドと前記第３溶媒と水とを混合して調製された第１液と、前記第３溶媒と有機酸、無機酸又はチタン化合物からなる触媒とを混合して調製された第２液とを混合することにより、調製され、前記第１加水分解物と前記第２加水分解物の合計量１００質量％に対して前記第２加水分解物が０．１〜１０．０質量％含まれ、前記第１溶媒、前記第２溶媒及び前記第３溶媒の質量比が、第１溶媒：第２溶媒：第３溶媒＝９〜１５：１〜３：８２〜９０であることを特徴とする。
本発明の第４の観点は、第３の観点に係る発明であって、前記第１溶媒が２−メトキシエタノール、２−エトキシエタノール、２−イソプロポキシエタノール、１−メトキシ−２−プロパノール及び１−エトキシ−２−プロパノールからなる群より選ばれた１種又は２種以上の溶媒であり、前記第２溶媒がジアセトンアルコール、ジエチレングリコールモノメチルエーテル、Ｎ−メチルピロリドン及び３−メトキシ−３−メチル−１−ブタノールからなる群より選ばれた１種又は２種以上の溶媒であり、前記第３溶媒が炭素数１〜３の範囲にある１種又は２種以上のアルコールである膜形成用液組成物の製造方法である。
A second aspect of the present invention is the film forming liquid composition according to any one of the first to third aspects, wherein the first solvent is 2-methoxyethanol, 2-ethoxyethanol, -One or more solvents selected from the group consisting of isopropoxyethanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol, wherein the second solvent is diacetone alcohol, diethylene glycol monomethyl ether , N-methylpyrrolidone and 3-methoxy-3-methyl-1-butanol, and one or more solvents selected from the group consisting of the third solvent having 1 to 3 carbon atoms. It is characterized by being a kind or two or more kinds of alcohols.
A third aspect of the present invention is to add and mix a fluorine-containing silane represented by the above general formula (1) and an organic solvent to a liquid containing a first hydrolyzate of a silicon alkoxide to obtain a second hydrolysis of the fluorine-containing silane. A method for producing a film-forming liquid composition by preparing a decomposed product, wherein the organic solvent comprises a first solvent having a boiling point of 120°C or higher and lower than 160°C and a boiling point of 160°C or higher and 220°C or lower. A first liquid comprising a second solvent and a third solvent having a boiling point of less than 120° C., wherein the first hydrolyzate of the silicon alkoxide is prepared by mixing the silicon alkoxide, the third solvent and water. And a second liquid prepared by mixing the third solvent and a catalyst composed of an organic acid, an inorganic acid or a titanium compound, and the first hydrolyzate and the second hydrolyzate. The second hydrolyzate is contained in an amount of 0.1 to 10.0% by mass with respect to the total amount of decomposed products of 100% by mass, and the mass ratio of the first solvent, the second solvent and the third solvent is 1 solvent: 2nd solvent: 3rd solvent = 9-15:1-3:82-90, It is characterized by the above-mentioned.
A fourth aspect of the present invention is the invention according to the third aspect, wherein the first solvent is 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 1-methoxy-2-propanol and 1 -One or more solvents selected from the group consisting of ethoxy-2-propanol, wherein the second solvent is diacetone alcohol, diethylene glycol monomethyl ether, N-methylpyrrolidone and 3-methoxy-3-methyl- Liquid composition for film formation, which is one or more solvents selected from the group consisting of 1-butanol, and wherein the third solvent is one or more alcohols having 1 to 3 carbon atoms. It is a method of manufacturing a product.
本発明の第１の観点の膜形成用液組成物では、液組成物中のフッ素含有シランが分子内に含窒素ペルフルオロアルキル基とアルコキシシリル基とをそれぞれ１以上有する構造となっていて、窒素原子に炭素数が６以下の短鎖長のペルフルオロアルキル基が複数結合した含窒素ペルフルオロアルキル基を有しており、分子内のフッ素含有率が高いため、形成した膜に優れた撥水撥油性と離型性を付与することができる。またケイ素アルコキシドであるテトラメトキシシラン又はテトラエトキシシランを用いるため、高い強度の塗膜が得られ、かつ塗膜の基材への密着性が良好となる。更に沸点の異なる３種類の溶媒を用い、これらの溶媒を所定の質量比で配合することにより、フッ素系の溶媒を用いずに、溶媒の乾燥速度を調整して、塗膜を成膜性良く形成することができる。 In the liquid composition for forming a film according to the first aspect of the present invention, the fluorine-containing silane in the liquid composition has a structure having at least one nitrogen-containing perfluoroalkyl group and at least one alkoxysilyl group in the molecule. It has a nitrogen-containing perfluoroalkyl group in which a plurality of short-chain-length perfluoroalkyl groups having 6 or less carbon atoms are bonded to the atom, and the fluorine content in the molecule is high, resulting in excellent water and oil repellency in the formed film. And releasability can be imparted. Further, since silicon alkoxide tetramethoxysilane or tetraethoxysilane is used, a high-strength coating film can be obtained and the adhesion of the coating film to the substrate becomes good. Furthermore, by using three kinds of solvents having different boiling points and mixing these solvents in a predetermined mass ratio, the drying rate of the solvent is adjusted without using a fluorine-based solvent, and the coating film can be formed with good film forming property. Can be formed.
本発明の第２の観点の膜形成用液組成物では、第１溶媒、第２溶媒及び第３溶媒に特定の溶媒を用いる。第１溶媒は第２溶媒と第３溶媒の中間の沸点を有することから、塗膜の乾燥時に第２溶媒と第３溶媒の沸点差に伴う塗膜の乾燥速度の大きな差を緩和する作用があり、第２溶媒は第１溶媒よりも高沸点であり、塗膜の乾燥速度が遅いことから塗膜の急激な乾燥を防止して急激な乾燥に伴う膜の不均一性を防止する作用があり、第３溶媒は沸点が最も低いことから塗膜の乾燥を速くする作用がある。このように沸点の異なる３種類の溶媒を用いることにより溶媒の乾燥速度を調整して、より的確にかつ効率的に塗膜を成膜性良く形成することができる。
本発明の第３の観点の膜形成用液組成物の製造方法では、ケイ素アルコキシドの溶液である第１液に触媒を含む第２液を添加することにより、ケイ素アルコキシドの第１加水分解物を生成することができる。また、第２加水分解物を第１加水分解物及び第２加水分解物の合計量に対して所定の範囲で含有させることにより、形成した膜により優れた撥水撥油性と離型性を付与することができる。
In the film forming liquid composition according to the second aspect of the present invention, a specific solvent is used as the first solvent, the second solvent and the third solvent. Since the first solvent has a boiling point intermediate between those of the second solvent and the third solvent, it has the effect of alleviating a large difference in the drying rate of the coating film due to the difference in the boiling points of the second solvent and the third solvent during the drying of the coating film. The second solvent has a boiling point higher than that of the first solvent, and the drying speed of the coating film is slow. Therefore, the second solvent has a function of preventing rapid drying of the coating film and preventing nonuniformity of the film due to rapid drying. Since the third solvent has the lowest boiling point, it has the function of speeding up the drying of the coating film. By using the three kinds of solvents having different boiling points in this way, the drying rate of the solvent can be adjusted to form the coating film more accurately and efficiently with good film-forming property.
In the method for producing a film-forming liquid composition according to the third aspect of the present invention, a first hydrolyzate of a silicon alkoxide is obtained by adding a second liquid containing a catalyst to a first liquid that is a solution of a silicon alkoxide. Can be generated. Further, by containing the second hydrolyzate in a predetermined range with respect to the total amount of the first hydrolyzate and the second hydrolyzate, the formed film is provided with excellent water/oil repellency and releasability. You can do it .
次に本発明を実施するための形態を説明する。 Next, modes for carrying out the present invention will be described.
〔膜形成用液組成物〕
本実施の形態の膜形成用液組成物は、ケイ素アルコキシドとしてのテトラメトキシシラン又はテトラエトキシシランの第１加水分解物と、上記一般式（１）で示されるフッ素含有シランの第２加水分解物と、所定の溶媒とを含む。この液組成物中には、上記第１加水分解物と上記第２加水分解物が合計して液組成物１００質量％に対して０．１〜１０．０質量％、好ましくは０．５〜５質量％含まれる。下限値の０．１質量％未満では、形成した膜に撥水撥油性の防汚機能及び離型性を付与できず、また塗膜の基材への密着性に劣り、高い強度の塗膜が得られない。また上限値の１０．０質量％を超えると、塗膜の弾き等が発生し成膜性に劣る。
[Film-forming liquid composition]
The film-forming liquid composition according to the present embodiment includes a first hydrolyzate of tetramethoxysilane or tetraethoxysilane as a silicon alkoxide and a second hydrolyzate of a fluorine-containing silane represented by the general formula (1). And a predetermined solvent. In this liquid composition, the first hydrolyzate and the second hydrolyzate are added in a total amount of 0.1 to 10.0% by mass, preferably 0.5 to 100% by mass, relative to 100% by mass of the liquid composition. 5 mass% is contained. If the lower limit is less than 0.1% by mass, the formed film cannot be imparted with water- and oil-repellent antifouling function and releasability, and the adhesion of the coating film to the substrate is poor, resulting in a high-strength coating film. Can't get On the other hand, when the upper limit of 10.0% by mass is exceeded, the coating film is repelled and the film formability is deteriorated.
〔所定の溶媒〕
本実施の形態の液組成物に用いられる所定の溶媒は、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒と、沸点が１２０℃未満の第３溶媒と、水とを混合した混合溶媒である。これらの第１溶媒、第２溶媒及び第３溶媒は、質量比で、第１溶媒：第２溶媒：第３溶媒＝９〜１５：１〜３：８２〜９０の割合、好ましくは１０〜１４：１〜３：８３〜８８の割合で上記液組成物中に含まれる。第１溶媒は第２溶媒と第３溶媒の中間の沸点を有することから、塗膜の乾燥時に第２溶媒と第３溶媒の沸点差に伴う塗膜の乾燥速度の大きな差を緩和する作用があり、第２溶媒は第１溶媒よりも高沸点であり、塗膜の乾燥速度が遅いことから塗膜の急激な乾燥を防止して急激な乾燥に伴う膜の不均一性を防止する作用があり、第３溶媒は沸点が最も低いことから塗膜の乾燥を速くする作用がある。このように沸点の異なる３種類の溶媒を用いることにより、高価なフッ素系溶媒を用いることなく、フッ素含有シランを溶解することができるとともに、成膜時の溶媒の乾燥速度を調整して、均一な膜を形成することができる。第１溶媒を例示すれば、２−メトキシエタノール（沸点１２５℃）、２−エトキシエタノール（沸点１３６℃）、２−イソプロポキシエタノール（沸点１４２℃）、１−メトキシ−２−プロパノール（沸点１２０℃）及び１−エトキシ−２−プロパノール（沸点１３２℃）からなる群より選ばれた１種又は２種以上の溶媒が挙げられる。また第２溶媒を例示すれば、ジアセトンアルコール（沸点１６９℃）、ジエチレングリコールモノメチルエーテル（沸点１９４℃）、Ｎ−メチルピロリドン（沸点２０２℃）及び３−メトキシ−３−メチル−１−ブタノール（沸点１７３℃）からなる群より選ばれた１種又は２種以上の溶媒が挙げられる。更に第３溶媒を例示すれば、炭素数１〜３の範囲にある１種又は２種以上のアルコールが挙げられる。このアルコールとしては、例えば、メタノール（沸点６４．７℃）、エタノール（沸点約７８．３℃）、プロパノール（ｎ−プロパノール（沸点９７−９８℃）、イソプロパノール（沸点８２．４℃））が挙げられる。
[Predetermined solvent]
The predetermined solvent used for the liquid composition of the present embodiment includes a first solvent having a boiling point of 120°C or higher and lower than 160°C, a second solvent having a boiling point of 160°C or higher and 220°C or lower, and a boiling point of lower than 120°C. It is a mixed solvent obtained by mixing the third solvent and water. These 1st solvent, 2nd solvent, and 3rd solvent are the ratio of 1st solvent:2nd solvent:3rd solvent=9-15:1-3:82-90 by mass ratio, Preferably it is 10-14. It is contained in the said liquid composition in the ratio of :1-3:83-88. Since the first solvent has a boiling point intermediate between those of the second solvent and the third solvent, it has the effect of alleviating a large difference in the drying rate of the coating film due to the difference in the boiling points of the second solvent and the third solvent during the drying of the coating film. The second solvent has a boiling point higher than that of the first solvent, and the drying speed of the coating film is slow. Therefore, the second solvent has a function of preventing rapid drying of the coating film and preventing nonuniformity of the film due to rapid drying. Since the third solvent has the lowest boiling point, it has the function of speeding up the drying of the coating film. By using three kinds of solvents having different boiling points in this way, the fluorine-containing silane can be dissolved without using an expensive fluorine-based solvent, and the drying rate of the solvent at the time of film formation can be adjusted to obtain a uniform solution. Can be formed. As an example of the first solvent, 2-methoxyethanol (boiling point 125° C.), 2-ethoxyethanol (boiling point 136° C.), 2-isopropoxyethanol (boiling point 142° C.), 1-methoxy-2-propanol (boiling point 120° C.). ) And 1-ethoxy-2-propanol (boiling point 132° C.), and one or more solvents selected from the group consisting of: Moreover, if a 2nd solvent is illustrated, diacetone alcohol (boiling point 169 degreeC), diethylene glycol monomethyl ether (boiling point 194 degreeC), N-methyl pyrrolidone (boiling point 202 degreeC), and 3-methoxy-3-methyl-1-butanol (boiling point) will be mentioned. One or two or more solvents selected from the group consisting of (173° C.). Further, as an example of the third solvent, one or more alcohols having 1 to 3 carbon atoms can be mentioned. Examples of this alcohol include methanol (boiling point 64.7°C), ethanol (boiling point about 78.3°C), propanol (n-propanol (boiling point 97-98°C), isopropanol (boiling point 82.4°C)). To be
〔ケイ素アルコキシド〕
本実施の形態の液組成物に用いられるケイ素アルコキシドとしては、具体的には、テトラメトキシシラン、そのオリゴマー又はテトラエトキシシラン、そのオリゴマーが挙げられる。例えば、硬度の高い膜を得る目的には、テトラメトキシシランを用いることが好ましく、一方、加水分解時に発生するメタノールを避ける場合は、テトラエトキシシランを用いることが好ましい。
[Silicon alkoxide]
Specific examples of the silicon alkoxide used in the liquid composition of the present embodiment include tetramethoxysilane, an oligomer thereof, tetraethoxysilane, and an oligomer thereof. For example, tetramethoxysilane is preferably used for the purpose of obtaining a film having high hardness, while tetraethoxysilane is preferably used when methanol generated during hydrolysis is avoided.
〔ケイ素アルコキシドの第１加水分解物の調製〕
ケイ素アルコキシドの第１加水分解物を調製する方法について説明する。先ず、ケイ素アルコキシドに第３溶媒と水を添加して、好ましくは１０〜３０℃の温度で５〜２０分間撹拌することにより第１液を調製する。また、第３溶媒と有機酸、無機酸又はチタン化合物を触媒として混合し、好ましくは１０〜３０℃の温度で５〜２０分間撹拌することにより第２液を、第１液とは別に調製する。次に、上記調製した第１液を、好ましくは３０〜８０℃の温度に保持して、第１液に第２液を添加し、上記温度を保持した状態で好ましくは１〜２４時間撹拌する。これにより、上記ケイ素アルコキシドの第１加水分解物が生成される。第１加水分解物は、ケイ素アルコキシドを０．５〜１５質量％、第３溶媒を２０〜９８質量％、水を０．５〜４０質量％、有機酸、無機酸又はチタン化合物を触媒として０．０１〜５質量％の割合で混合してケイ素アルコキシドの加水分解反応を進行させることで得られる。
[Preparation of First Hydrolyzate of Silicon Alkoxide]
A method for preparing the first hydrolyzate of silicon alkoxide will be described. First, the first solvent is prepared by adding the third solvent and water to the silicon alkoxide and stirring the mixture at a temperature of 10 to 30° C. for 5 to 20 minutes. Further, the second solution is prepared separately from the first solution by mixing the third solvent with an organic acid, an inorganic acid or a titanium compound as a catalyst and stirring at a temperature of 10 to 30° C. for 5 to 20 minutes. .. Next, the above-prepared first liquid is preferably maintained at a temperature of 30 to 80° C., the second liquid is added to the first liquid, and the mixture is stirred preferably for 1 to 24 hours while maintaining the above temperature. .. As a result, the first hydrolyzate of the silicon alkoxide is produced. The first hydrolyzate contains silicon alkoxide in an amount of 0.5 to 15% by mass, a third solvent in an amount of 20 to 98% by mass, water in an amount of 0.5 to 40% by mass, and an organic acid, an inorganic acid or a titanium compound as a catalyst. It is obtained by mixing at a ratio of 0.01 to 5% by mass to allow the hydrolysis reaction of the silicon alkoxide to proceed.
ケイ素アルコキシドの第１加水分解物のＳｉＯ２濃度（ＳｉＯ２分）は０．５〜１５質量％であるものが好ましい。加水分解物のＳｉＯ２濃度が下限値未満では、重合が不十分であり、膜の密着性の低下やクラックの発生が起こりやすく、上限値を超えると、相対的に水の割合が高くなりケイ素アルコキシドが溶解せず、反応液がゲル化する不具合を生じる。水の割合を上記範囲に限定したのは、下限値未満では加水分解速度が遅くなるために、重合が進まず、塗布膜の密着性並びに成膜性が不十分になり、一方、上限値を超えると加水分解反応中に反応液がゲル化し、水が多過ぎるためケイ素アルコキシド化合物がアルコール水溶液に溶解せず、分離する不具合を生じるからである。水としては、不純物の混入防止のため、イオン交換水や純水等を使用するのが望ましい。 The SiO 2 concentration (SiO 2 content) of the first hydrolyzate of silicon alkoxide is preferably 0.5 to 15% by mass. If the SiO 2 concentration of the hydrolyzate is less than the lower limit value, the polymerization is insufficient and the adhesion of the film is reduced or cracks are likely to occur. The alkoxide does not dissolve and the reaction solution gels. The proportion of water is limited to the above range, because if the ratio is less than the lower limit, the hydrolysis rate becomes slow, so that the polymerization does not proceed and the adhesiveness and film formability of the coating film become insufficient, while the upper limit is set. If it exceeds, the reaction solution gels during the hydrolysis reaction, and since the amount of water is too large, the silicon alkoxide compound does not dissolve in the aqueous alcohol solution, causing a problem of separation. As water, it is desirable to use ion-exchanged water, pure water, or the like in order to prevent contamination of impurities.
有機酸、無機酸又はチタン化合物は加水分解反応を促進させるための触媒として機能する。有機酸としてはギ酸、シュウ酸が例示され、無機酸としては塩酸、硝酸、リン酸が例示され、チタン化合物としてはテトラプロポキシチタン、テトラブトキシチタン、テトライソプロポキシチタン、乳酸チタン等が例示される。触媒は上記のものに限定されない。上記触媒の割合を上記範囲に限定したのは、下限値未満では反応性に乏しく重合が不十分になるため、膜が形成されず、一方、上限値を超えても反応性に影響はないが、残留する酸による基材の腐食等の不具合を生じる。 The organic acid, inorganic acid or titanium compound functions as a catalyst for promoting the hydrolysis reaction. Examples of the organic acid include formic acid and oxalic acid, examples of the inorganic acid include hydrochloric acid, nitric acid, and phosphoric acid, and examples of the titanium compound include tetrapropoxy titanium, tetrabutoxy titanium, tetraisopropoxy titanium, and titanium lactate. .. The catalyst is not limited to those mentioned above. The ratio of the catalyst is limited to the above range, because if it is less than the lower limit value, the reactivity is poor and the polymerization is insufficient, so that a film is not formed, while if it exceeds the upper limit value, the reactivity is not affected. However, problems such as corrosion of the base material due to residual acid occur.
第３溶媒としてはメタノール又はエタノールが好ましい。これらのアルコールは、ケイ素アルコキドとの混合がしやすいためである。第３溶媒の割合を上記範囲に限定したのは、第３溶媒の割合が下限値未満では、ケイ素アルコキシドが、溶液中に溶解せず分離してしまうこと、加水分解反応中に反応液がゲル化しやすく、一方、上限値を超えると、加水分解に必要な水、触媒量が相対的に少なくなるために、加水分解の反応性が低下して、重合が進まず、膜の密着性が低下するためである。 The third solvent is preferably methanol or ethanol. This is because these alcohols are easily mixed with silicon alkoxide. The ratio of the third solvent is limited to the above range, because when the ratio of the third solvent is less than the lower limit value, the silicon alkoxide is not dissolved in the solution and is separated, and the reaction solution is gelled during the hydrolysis reaction. On the other hand, if the amount exceeds the upper limit, the amount of water and the amount of catalyst required for hydrolysis will be relatively small, and the reactivity of hydrolysis will decrease, polymerization will not proceed, and the adhesion of the film will decrease. To do so.
〔フッ素含有シラン〕
本実施の形態の液組成物に用いられるフッ素含有シランは、上記一般式（１）で示される。上記式（１）中の含窒素ペルフルオロアルキル基としては、より具体的には、下記式（２）〜（１３）で示されるペルフルオロアミン構造を挙げることができる。
[Fluorine-containing silane]
The fluorine-containing silane used in the liquid composition of the present embodiment is represented by the above general formula (1). Specific examples of the nitrogen-containing perfluoroalkyl group in the above formula (1) include perfluoroamine structures represented by the following formulas (2) to (13).
また、上記式（１）中のＸとしては、下記式（１４）〜（１７）で示される構造を挙げることができる。なお、下記式（１４）はエーテル結合、下記式（１５）はエステル結合、下記式（１６）はアミド結合、下記式（１７）はウレタン結合を含む例を示している。 Examples of X in the above formula (1) include structures represented by the following formulas (14) to (17). Note that the following formula (14) shows an example including an ether bond, the following formula (15) an ester bond, the following formula (16) an amide bond, and the following formula (17) an urethane bond.
ここで、上記式（１４）〜（１７）中、Ｒ２及びＲ３は炭素数が０から１０の炭化水素基、Ｒ４は水素原子または炭素数１から６の炭化水素基である。Ｒ３の炭化水素基の例とは、メチル基、エチル基等のアルキル基挙げられ、Ｒ４の炭化水素基の例とは、メチル基、エチル基等のアルキル基の他、フェニル基、ビニル基等も挙げられる。 Here, in the above formulas (14) to (17), R 2 and R 3 are hydrocarbon groups having 0 to 10 carbon atoms, and R 4 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group of R 3 include an alkyl group such as a methyl group and an ethyl group, and examples of the hydrocarbon group of R 4 include an alkyl group such as a methyl group and an ethyl group, a phenyl group and a vinyl group. Examples include groups.
また、上記式（１）中、Ｒ１は、加水分解基のメトキシ基、エトキシ基等が挙げられる。 Further, in the above formula (1), examples of R 1 include a methoxy group and an ethoxy group which are hydrolyzable groups.
また、上記式（１）中、Ｚは、加水分解されてＳｉ−Ｏ−Ｓｉ結合を形成可能な加水分解性基であれば特に限定されるものではない。このような加水分解性基としては、具体的には、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基、フェノキシ基、ナフトキシ基などのアリールオキシ基、ベンジルオキシ基、フェネチルオキシ基などのアラルキルオキシ基、アセトキシ基、プロピオニルオキシ基、ブチリルオキシ基、バレリルオキシ基、ピバロイルオキシ基、ベンゾイルオキシ基などのアシルオキシ基等が挙げられる。これらの中でも、メトキシ基、エトキシ基を適用することが好ましい。 Further, in the above formula (1), Z is not particularly limited as long as it is a hydrolyzable group capable of being hydrolyzed to form a Si-O-Si bond. Specific examples of such a hydrolyzable group include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group, a phenoxy group, an aryloxy group such as a naphthoxy group, a benzyloxy group and a phenethyloxy group. Examples thereof include an aralkyloxy group such as a group, an acetoxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a pivaloyloxy group, and an acyloxy group such as a benzoyloxy group. Among these, it is preferable to apply a methoxy group or an ethoxy group.
ここで、上記式（１）で表されるペルフルオロアミン構造を有するフッ素含有シランの具体例としては、例えば、下記式（１８）〜（２８）で表される構造が挙げられる。なお、下記式（１９）〜（２９）中、Ｒはメチル基又はエチル基である。 Here, specific examples of the fluorine-containing silane having the perfluoroamine structure represented by the above formula (1) include structures represented by the following formulas (18) to (28). In the formulas (19) to (29) below, R is a methyl group or an ethyl group.
上述したように、本実施の形態のフッ素含有シランは、分子内に含窒素ペルフルオロアルキル基とアルコキシシリル基とをそれぞれ１以上有する構造となっていて、窒素原子に炭素数が６以下の短鎖長のペルフルオロアルキル基が複数結合した含窒素ペルフルオロアルキル基を有しており、分子内のフッ素含有率が高いため、形成した膜に優れた撥水撥油性と離型性を付与することができる。 As described above, the fluorine-containing silane of the present embodiment has a structure having at least one nitrogen-containing perfluoroalkyl group and at least one alkoxysilyl group in the molecule, and the nitrogen atom has a short chain of 6 or less carbon atoms. Since it has a nitrogen-containing perfluoroalkyl group in which multiple long perfluoroalkyl groups are bonded and the fluorine content in the molecule is high, it is possible to impart excellent water/oil repellency and releasability to the formed film. ..
〔フッ素含有シランの第２加水分解物の調製〕
フッ素含有シランの第２加水分解物は、第１加水分解物にフッ素含有シランを混合し添加することにより生成する。第１加水分解物の調製とは別にフッ素含有シランのみで加水分解を行って第２加水分解物を生成すると、フッ素のみの塊ができてしまい、成膜性に劣るので好ましくない。また、フッ素含有シランとケイ素アルコキシドと水と有機溶媒を予め混合しておき、最後に触媒を添加する方法もある。ただし、第１加水分解物にフッ素含有シランを混合し添加する方が、ケイ素アルコキシドで骨格を形成した後、その骨格にフッ素を形成することから、膜強度並びに密着性等に優れる。
[Preparation of Second Hydrolyzate of Fluorine-Containing Silane]
The second hydrolyzate of the fluorine-containing silane is produced by mixing and adding the fluorine-containing silane to the first hydrolyzate. When the second hydrolyzate is produced by hydrolyzing only the fluorine-containing silane separately from the preparation of the first hydrolyzate, lumps of only fluorine are formed and the film formability is deteriorated, which is not preferable. There is also a method in which fluorine-containing silane, silicon alkoxide, water and an organic solvent are mixed in advance, and finally a catalyst is added. However, when the fluorine-containing silane is mixed and added to the first hydrolyzate, since the skeleton is formed by the silicon alkoxide and then the fluorine is formed in the skeleton, the film strength and the adhesion are excellent.
〔膜形成用液組成物の調製〕
防汚性膜及び離型性を付与し得る膜を形成するための液組成物を調製する方法は、ケイ素アルコキシドの第１加水分解物とフッ素含有シランの第２加水分解物とを、液組成物１００質量％に対して０．１〜１０．０質量％、好ましくは０．５〜５質量％含むように調製する。下限値の０．１質量％未満では、形成した膜に撥水撥油性の防汚性及び離型性を付与することができず、また塗膜の基材への密着性に劣り、高い強度の塗膜が得られない。また上限値の１０．０質量％を超えると、成膜性が劣るか、或いは組成物のゲル化等が生じて液組成物の安定性が悪くなる。またフッ素含有シランをケイ素アルコキシドの第１加水分解物及びフッ素含有シランの第２加水分解物の合計量に対して０．１〜１０．０質量％含むように調製することが好ましい。より確実に形成した膜に撥水撥油性の防汚性及び離型性を付与するためである。この上限値の１０．０質量％を超えると、成膜性が劣り、防汚性及び離型性の機能を発現しにくい。
[Preparation of liquid composition for film formation]
A method for preparing a liquid composition for forming an antifouling film and a film capable of imparting releasability is a liquid composition comprising a first hydrolyzate of a silicon alkoxide and a second hydrolyzate of a fluorine-containing silane. 0.1 to 10.0% by mass, preferably 0.5 to 5% by mass, relative to 100% by mass of the product. When the lower limit is less than 0.1% by mass, the formed film cannot be imparted with water- and oil-repellent antifouling property and releasability, and the adhesion of the coating film to the substrate is poor, resulting in high strength. No coating film can be obtained. On the other hand, when the upper limit of 10.0% by mass is exceeded, the film-forming property is deteriorated, or the composition is gelated and the stability of the liquid composition is deteriorated. Further, it is preferable to prepare the fluorine-containing silane so as to be contained in an amount of 0.1 to 10.0% by mass based on the total amount of the first hydrolyzate of the silicon alkoxide and the second hydrolyzate of the fluorine-containing silane. This is for imparting water- and oil-repellent antifouling properties and releasability to the formed film more reliably. If the upper limit of 10.0% by mass is exceeded, the film-forming property will be poor and the functions of antifouling property and releasability will be difficult to be exhibited.
防汚性膜及び離型性を付与し得る膜を形成するための液組成物の調製方法では、最初にケイ素アルコキシドの第１加水分解物を調製しておく。次いでこの第１加水分解物を調製した浴に、フッ素含有シランを混合しながら添加し、第２加水分解物の調製を行う。この方法では、ケイ素アルコキシドの加水分解に用いた水及び有機酸又は無機酸をフッ素含有シランの加水分解に利用する。前述したように、ケイ素アルコキシドの第１加水分解物とフッ素含有シランの第２加水分解物と別々に調製しておき、これらを混合して調製すると、フッ素の塊ができてしまい、成膜性が悪くなり、かつ、離型性と防汚性の機能を発現させることが困難になる。ケイ素アルコキシドとフッ素含有シランと水と有機溶媒を混合した液に、触媒を添加して加水分解の調整を行う方法もあるが、上述した方法が最も好ましい。 In the method of preparing a liquid composition for forming an antifouling film and a film capable of imparting releasability, a first hydrolyzate of silicon alkoxide is first prepared. Then, the fluorine-containing silane is added to the bath in which the first hydrolyzate has been prepared, while mixing, to prepare the second hydrolyzate. In this method, the water and the organic acid or inorganic acid used for the hydrolysis of the silicon alkoxide are utilized for the hydrolysis of the fluorine-containing silane. As described above, if the first hydrolyzate of the silicon alkoxide and the second hydrolyzate of the fluorine-containing silane are prepared separately, and they are mixed and prepared, a lump of fluorine is formed and the film-forming property is deteriorated. Becomes worse, and it becomes difficult to exhibit the functions of releasability and antifouling property. There is also a method of adjusting the hydrolysis by adding a catalyst to a liquid obtained by mixing silicon alkoxide, fluorine-containing silane, water and an organic solvent, but the above-mentioned method is most preferable.
〔防汚性膜及び離型性付与膜の形成方法〕
本実施の形態の防汚性膜及び離型性付与膜は、例えば、基材であるステンレス鋼（ＳＵＳ）、鉄、アルミニウム等の金属板上、窓ガラス、鏡等のガラス上、タイル上、ポリ塩化ビニル（ＰＶＣ）等のプラスチック上、又はポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム上に、上記液組成物を、スクリーン印刷法、バーコート法、ダイコート法、ドクターブレード、スピン法等により塗布した後に、室温乾燥もしくは乾燥機等により室温〜１３０℃の温度で乾燥させることにより、形成される。
[Method of forming antifouling film and releasability imparting film]
The antifouling film and the release property imparting film of the present embodiment are, for example, on a metal plate such as stainless steel (SUS), iron, and aluminum, which is a substrate, on a glass such as a window glass and a mirror, on a tile, The above liquid composition is screen-printed, bar-coated, die-coated, doctor on a plastic such as polyvinyl chloride (PVC) or a polyester film such as polyethylene terephthalate (PET), polybutylene terephthalate or polyethylene naphthalate. It is formed by coating with a blade, a spin method or the like, and then drying at room temperature or with a dryer at a temperature of room temperature to 130°C.
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１＞
ケイ素アルコキシドとしてのテトラエトキシシラン（ＴＥＯＳ）３４．６６ｇにエタノール（沸点７８．３℃）３４．５６ｇを有機溶媒として添加し、イオン交換水２９．７８ｇをセパラブルフラスコ内で２０℃の温度で１５分間撹拌することにより第１液を調製した。また、この第１液とは別に、エタノール０．５６ｇと濃度６０質量％の硝酸０．４４ｇをビーカー内に投入して混合し、２０℃の温度で１５分間撹拌することにより第２液を調製した。次に、上記調製した第１液を、ウォーターバスにて６０℃の温度に保持してから、この第１液に第２液を添加し、６０℃で２時間撹拌した。これにより、上記ケイ素アルコキシドの第１加水分解物を得た。上記ケイ素アルコキシドの第１加水分解物を生成した液に、上記式（２８）に示されるフッ素含有シラン０．１５ｇと有機溶媒としてのエタノール（沸点７８．３℃）２１１．２６ｇと２−イソプロポキシエタノール（沸点１４２℃）３５．２１ｇとジアセトンアルコール（沸点１６９℃）５．０３ｇを添加し、２５℃で１時間撹拌した。これにより、液中にケイ素アルコキシドの第１加水分解物に加えて、フッ素含有シランの第２加水分解物が生成された液組成物を得た。
<Example 1>
34.66 g of tetraethoxysilane (TEOS) as a silicon alkoxide was added with 34.56 g of ethanol (boiling point 78.3° C.) as an organic solvent, and 29.78 g of ion-exchanged water was added at a temperature of 20° C. in a separable flask at a temperature of 15° C. The first liquid was prepared by stirring for 1 minute. Separately from the first liquid, 0.56 g of ethanol and 0.44 g of nitric acid having a concentration of 60% by mass were put into a beaker and mixed, and the second liquid was prepared by stirring at a temperature of 20° C. for 15 minutes. did. Next, the above-prepared first liquid was kept at a temperature of 60° C. in a water bath, and then the second liquid was added to the first liquid, followed by stirring at 60° C. for 2 hours. Thereby, the first hydrolyzate of the silicon alkoxide was obtained. In the liquid in which the first hydrolyzate of silicon alkoxide was produced, 0.15 g of the fluorine-containing silane represented by the above formula (28), ethanol (boiling point 78.3° C.) 211.26 g as an organic solvent, and 2-isopropoxy. 35.21 g of ethanol (boiling point 142° C.) and 5.03 g of diacetone alcohol (boiling point 169° C.) were added, and the mixture was stirred at 25° C. for 1 hour. As a result, a liquid composition was obtained in which, in addition to the first hydrolyzate of silicon alkoxide, the second hydrolyzate of fluorine-containing silane was produced in the liquid.
＜実施例２＞
表１及び表２に示すように、ケイ素アルコキシドをテトラメトキシシラン（ＴＭＯＳ）の３〜５量体のオリゴマー（三菱化学製商品名MS-51）に変え、有機溶媒をメタノールに変え、触媒をテトライソプロポキシチタン（Ｔｉ(isoＰｒＯ) ４）に変え、フッ素含有シランを式（２７）に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液中にケイ素アルコキシドの第１加水分解物に加えて、フッ素含有シランの第２加水分解物が生成された液組成物を得た。
<Example 2>
As shown in Tables 1 and 2, the silicon alkoxide was replaced with tetramethoxysilane (TMOS) trimer to pentamer oligomer (trade name MS-51 manufactured by Mitsubishi Chemical), the organic solvent was changed to methanol, and the catalyst was changed to tetra Liquid propellant was prepared in the same manner as in Example 1 except that isopropoxy titanium (Ti(isoPrO) 4 ) was used, the fluorine-containing silane was changed to the formula (27), and the amount (g) of each raw material of the liquid composition was changed. A liquid composition was obtained in which, in addition to the first hydrolyzate of silicon alkoxide, the second hydrolyzate of fluorine-containing silane was produced.
＜実施例３＞
表１及び表２に示すように、フッ素含有シランを式（１９）に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Example 3>
As shown in Table 1 and Table 2, a liquid composition was prepared in the same manner as in Example 1 except that the fluorine-containing silane was changed to the formula (19) and the amount (g) of each raw material of the liquid composition was changed. Obtained.
＜実施例４＞
表１及び表２に示すように、触媒を塩酸に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 4>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that the catalyst was changed to hydrochloric acid and the amount (g) of each raw material of the liquid composition was changed.
＜実施例５＞
表１及び表２に示すように、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 5>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that the amount (g) of each raw material of the liquid composition was changed.
＜実施例６＞
表１及び表２に示すように、触媒を８５％リン酸水溶液に変え、第１溶媒を2-エトキシエタノールと２−メトキシエタノールの質量比にて１：１の混合溶媒に、第３溶媒をエタノール８５％、ｎ−プロピルアルコール１０％、２−プロピルアルコール５％の混合溶媒に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 6>
As shown in Table 1 and Table 2, the catalyst was changed to 85% phosphoric acid aqueous solution, the first solvent was a mixed solvent of 1:1 by mass ratio of 2-ethoxyethanol and 2-methoxyethanol, and the third solvent was. Liquid composition in the same manner as in Example 1 except that the mixed solvent of 85% of ethanol, 10% of n-propyl alcohol and 5% of 2-propyl alcohol was changed to change each compounding amount (g) of the raw material of the liquid composition. Got
＜実施例７＞
表１及び表２に示すように、第１溶媒を１−メトキシ−２−プロパノールと１−エトキシ−２−プロパノールの質量比にて１：１の混合溶媒に、第３溶媒をエタノール８５％、ｎ−プロピルアルコール１０％、２−プロピルアルコール５％の混合溶媒に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 7>
As shown in Table 1 and Table 2, the first solvent is a mixed solvent of 1:1 by mass ratio of 1-methoxy-2-propanol and 1-ethoxy-2-propanol, and the third solvent is 85% ethanol, A liquid composition was obtained in the same manner as in Example 1 except that the mixed solvent of 10% of n-propyl alcohol and 5% of 2-propyl alcohol was changed to change each compounding amount (g) of the raw material of the liquid composition.
＜実施例８＞
表１及び表２に示すように、第２溶媒をジエチレングリコールモノメチルエーテルと３−メトキシ−３−メチル−１−ブタノールの質量比にて１：３の混合溶媒に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 8>
As shown in Table 1 and Table 2, the second solvent was changed to a mixed solvent of 1:3 in a mass ratio of diethylene glycol monomethyl ether and 3-methoxy-3-methyl-1-butanol to prepare each of the raw materials of the liquid composition. A liquid composition was obtained in the same manner as in Example 1 except that the compounding amount (g) was changed.
＜実施例９＞
表１及び表２に示すように、第２溶媒をＮ−メチルピロリドン及び３−メトキシ−３−メチル−１−ブタノールの質量比にて１：３の混合溶媒に変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Example 9>
As shown in Table 1 and Table 2, the second solvent was changed to a mixed solvent of 1:3 at a mass ratio of N-methylpyrrolidone and 3-methoxy-3-methyl-1-butanol to prepare a liquid composition raw material. A liquid composition was obtained in the same manner as in Example 1 except that each compounding amount (g) was changed.
＜実施例１０＞
表１及び表２に示すように、組成比を変えた以外、実施例１と同様にして、液組成物を得た。
<Example 10>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that the composition ratio was changed.
＜比較例１＞
表１及び表２に示すように、フッ素含有シラン添加しないで、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative Example 1>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that each compounding amount (g) of the raw material of the liquid composition was changed without adding the fluorine-containing silane.
＜比較例２＞
表１及び表２に示すように、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative example 2>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that the respective compounding amounts (g) of the raw materials of the liquid composition were changed.
＜比較例３＞
表１及び表２に示すように、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative example 3>
As shown in Table 1 and Table 2, a liquid composition was obtained in the same manner as in Example 1 except that the respective compounding amounts (g) of the raw materials of the liquid composition were changed.
＜比較例４＞
表１及び表２に示すように、第１溶媒を添加しないで、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative example 4>
As shown in Tables 1 and 2, a liquid composition was obtained in the same manner as in Example 1 except that the first solvent was not added and the amount (g) of each raw material of the liquid composition was changed.
＜比較例５＞
表１及び表２に示すように、第２溶媒を添加しないで、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative Example 5>
As shown in Tables 1 and 2, a liquid composition was obtained in the same manner as in Example 1 except that the second solvent was not added and the amount (g) of each raw material of the liquid composition was changed.
＜比較例６＞
表１及び表２に示すように、第１溶媒及び第２溶媒を添加しないで、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして、液組成物を得た。
<Comparative example 6>
As shown in Table 1 and Table 2, the liquid composition was prepared in the same manner as in Example 1 except that the first solvent and the second solvent were not added and the respective compounding amounts (g) of the raw materials of the liquid composition were changed. Got
＜比較例７＞
表１及び表２に示すように、第１溶媒を１−エトキシ−２−プロパノールに変え、第２溶媒をＮ−メチルピロリドンに変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Comparative Example 7>
As shown in Table 1 and Table 2, the first solvent was changed to 1-ethoxy-2-propanol, the second solvent was changed to N-methylpyrrolidone, and each compounding amount (g) of the raw material of the liquid composition was changed. A liquid composition was obtained in the same manner as in Example 1 except for the above.
＜比較例８＞
表１及び表２に示すように、第１溶媒を１−エトキシ−２−プロパノールに変え、第２溶媒をＮ−メチルピロリドンに変え、液組成物の原料の各配合量(g)を変えた以外、実施例１と同様にして液組成物を得た。
<Comparative Example 8>
As shown in Table 1 and Table 2, the first solvent was changed to 1-ethoxy-2-propanol, the second solvent was changed to N-methylpyrrolidone, and each compounding amount (g) of the raw material of the liquid composition was changed. A liquid composition was obtained in the same manner as in Example 1 except for the above.
実施例１〜１０及び比較例１〜８の液組成物の原料となるケイ素アルコキシドの第１加水分解物を調製するための第１液及び第２液の種類と配合量を表１に示す。また第１加水分解物を含む液にフッ素含有シランと第１溶媒、第２溶媒及び第３溶媒を添加してフッ素含有シランの第２加水分解物を調製するための各原料の種類と配合量を表２に示す。表２において、フッ素含有シランの種類として、例えば「式（２８）」と記載したものは、「式（２８）に示される化合物」を意味する。更にケイ素アルコキシドの第１加水分解物の質量％及びフッ素含有シランの第２加水分解物の質量％、液組成物１００質量％に対する第１加水分解物と第２加水分解物の合計量の含有割合、この合計量１００質量％に対するに対するフッ素含有シランの含有割合、第１溶媒、第２溶媒及び第３溶媒の質量比、及び液組成物中の水の含有割合を表３に示す。なお、第３溶媒は、ケイ素アルコキシドの加水分解によって生じる溶媒も含む。また表３の水は液組成物に対する質量％である。表３に示される液組成物に対するケイ素アルコキシドの第１加水分解物の質量％はケイ素アルコキシドの質量から加水分解により分解するアルコキシドの質量の差を求め、この差を全溶液量で割ることにより算出され、液組成物に対するフッ素含有シランの第２加水分解物の質量％も同様にして算出される。液組成物に対する第１及び第２加水分解物の合計量の質量％は上記で算出された第１加水分解物の質量と第２加水分解物の合計量の質量を、全溶液量で割ることにより算出される。また第１及び第２加水分解物の合計量に対するフッ素含有シランの第２加水分解物の質量％は第２加水分解物の質量を第１及び第２加水分解物の合計量の質量で割ることにより算出される。更に加水分解によって生じる溶媒と、後から添加する溶媒を合計した数値を用いて、第１溶媒と第２溶媒と第３溶媒の質量比は算出される。更に液組成物に対する水の質量％は加水分解時に添加した水の量を全溶液量で割ることにより算出される。 Table 1 shows the types and blending amounts of the first liquid and the second liquid for preparing the first hydrolyzate of silicon alkoxide, which is a raw material for the liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 8. Further, the type and blending amount of each raw material for preparing the second hydrolyzate of the fluorine-containing silane by adding the fluorine-containing silane and the first solvent, the second solvent and the third solvent to the liquid containing the first hydrolyzate. Is shown in Table 2. In Table 2, as the type of the fluorine-containing silane, for example, one described as "formula (28)" means "a compound represented by formula (28)". Further, the content ratio of the total amount of the first hydrolyzate and the second hydrolyzate with respect to 100% by mass of the first hydrolyzate of silicon alkoxide and the second hydrolyzate of fluorine-containing silane. Table 3 shows the content ratio of the fluorine-containing silane, the mass ratio of the first solvent, the second solvent and the third solvent, and the content ratio of water in the liquid composition with respect to the total amount of 100 mass %. The third solvent also includes a solvent generated by hydrolysis of silicon alkoxide. Further, water in Table 3 is% by mass based on the liquid composition. The mass% of the first hydrolyzate of silicon alkoxide with respect to the liquid composition shown in Table 3 is calculated by obtaining the difference in mass of alkoxide decomposed by hydrolysis from the mass of silicon alkoxide, and dividing this difference by the total amount of solution. Then, the mass% of the second hydrolyzate of the fluorine-containing silane with respect to the liquid composition is calculated in the same manner. The mass% of the total amount of the first and second hydrolyzates with respect to the liquid composition is obtained by dividing the mass of the first hydrolyzate and the mass of the second hydrolyzate calculated above by the total amount of the solution. Is calculated by Further, the mass% of the second hydrolyzate of the fluorine-containing silane with respect to the total amount of the first and second hydrolyzates is obtained by dividing the mass of the second hydrolyzate by the mass of the total amount of the first and second hydrolysates. Is calculated by Further, the mass ratio of the first solvent, the second solvent, and the third solvent is calculated by using the numerical value obtained by summing the solvent generated by hydrolysis and the solvent added later. Further, the mass% of water relative to the liquid composition is calculated by dividing the amount of water added during hydrolysis by the total amount of solution.
＜比較試験及び評価＞
実施例１〜１０及び比較例１〜８で得られた液組成物を、バーコーター（安田精機製作所製、型番No.３）を用いて、厚さ２ｍｍ、たて１５０ｍｍ、よこ７５ｍｍのＳＵＳ基材上にそれぞれ乾燥後の厚さが０．５〜１μｍとなるように塗布し、１８種類の塗膜を形成した。ここで、先ずバーコーターによる塗布時の成膜性を評価した。続いてすべての塗膜を室温にて、３時間乾燥して１８種類の防汚性と離型性が付与された膜を得た。これらの膜について、膜表面の撥水性、撥油性、膜の耐水性、膜の強度、膜の基材への密着性及び膜付き基材からの離型性を評価した。これらの結果を表４に示す。
<Comparison test and evaluation>
The liquid compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 8 were SUS-based with a thickness of 2 mm, a vertical length of 150 mm, and a horizontal length of 75 mm by using a bar coater (manufactured by Yasuda Seiki Seisakusho, model No. 3). Each material was applied so that the thickness after drying would be 0.5 to 1 μm, and 18 types of coating films were formed. Here, first, the film forming property at the time of coating with a bar coater was evaluated. Subsequently, all the coating films were dried at room temperature for 3 hours to obtain 18 types of films having stain resistance and releasability. These films were evaluated for water repellency, oil repellency of the film, water resistance of the film, strength of the film, adhesion of the film to the substrate, and releasability from the film-coated substrate. The results are shown in Table 4.
(1) 成膜性
成膜性は、膜を目視にて評価した。膜全体に弾き、筋等の発生がなく、液組成物を均一に塗布できたものは「良好」とし、膜の一部に僅かに弾き、筋等が生じたものは「可」とし、膜全体に弾き、筋等が生じたものは「不良」とした。
(1) Film-forming property The film-forming property was evaluated by visually observing the film. If the liquid composition could be applied uniformly without flickering or streaks on the whole film, it was evaluated as "good", and if the liquid composition was slightly repelled on a part of the film and streaks were generated, it was evaluated as "OK". A piece that was flipped and had streaks, etc., was rated as "bad".
(2) 膜表面の撥水性（接触角）
協和界面科学製ドロップマスターDM-700を用いて、シリンジに２２℃±１℃のイオン交換水を準備し、シリンジの針の先端から２μＬの液滴を飛び出した状態にする。次いで評価するＳＵＳ基材上の防汚性膜をこの液滴に近づけて防汚性膜に液滴を付着させる。この付着した水の接触角を測定した。静止状態で水が膜表面に触れた１秒後の接触角をθ／２法により解析した値を水の接触角とし、膜表面の撥水性を評価した。
(2) Water repellency of film surface (contact angle)
Using a Dropmaster DM-700 manufactured by Kyowa Interface Science, prepare ion-exchanged water at 22° C.±1° C. in a syringe, and make a state in which 2 μL droplets are ejected from the tip of the needle of the syringe. Then, the antifouling film on the SUS substrate to be evaluated is brought close to this droplet to attach the droplet to the antifouling film. The contact angle of this attached water was measured. The water-repellent property of the film surface was evaluated by setting the value obtained by analyzing the contact angle 1 second after the water was in contact with the film surface in a static state by the θ/2 method as the water contact angle.
(3) 膜表面の撥油性（接触角）
協和界面科学製ドロップマスターDM-700を用いて、シリンジに２２℃±１℃のｎ−ヘキサデカン（以下、油という。）を準備し、シリンジの針の先端から２μＬの液滴を飛び出した状態にする。次いで評価するＳＵＳ基材上の防汚性膜をこの液滴に近づけて防汚性膜に液滴を付着させる。この付着した油の接触角を測定した。静止状態で油が膜表面に触れた１秒後の接触角をθ／２法により解析した値を油の接触角とし、膜表面の撥油性を評価した。
(3) Oil repellency of film surface (contact angle)
Kyowa Interface Science Drop Master DM-700 was used to prepare n-hexadecane (hereinafter referred to as oil) at 22°C ± 1°C in a syringe, and 2 μL of droplet was ejected from the tip of the syringe needle. To do. Then, the antifouling film on the SUS substrate to be evaluated is brought close to this droplet to attach the droplet to the antifouling film. The contact angle of this adhered oil was measured. The oil repellency of the film surface was evaluated using the value obtained by analyzing the contact angle 1 second after the oil was in contact with the film surface in a static state by the θ/2 method as the oil contact angle.
(4) 膜の耐水性
評価する防汚性膜をＳＵＳ基材とともに５〜１５℃の水道水が５００ｍＬ／分の速度で流れている水中に、水平状態で２４時間置き、室温にて乾燥した後、水と油の接触角を測定し、浸漬前の接触角と１５度未満の差である場合を「良好」とし、１５度以上異なる場合は、「不良」とし、膜の耐水性を評価した。
(4) Water resistance of the film The antifouling film to be evaluated was placed in water in which tap water of 5 to 15°C was flowing at a rate of 500 mL/min together with the SUS substrate for 24 hours in a horizontal state, and dried at room temperature. After that, the contact angle between water and oil is measured, and when the difference between the contact angle before immersion and the contact angle is less than 15 degrees is “good”, and when the difference is 15 degrees or more, it is “poor” and the water resistance of the film is evaluated. did.
(5) 膜の強度
水を含ませたスポンジで、膜を２０回擦り、膜を目視にて評価した。膜に全く剥離が生じていない場合を「良好」とし、膜の一部に僅かに剥離が生じている場合を「可」とし、膜の大部分に剥離が生じている場合を「不良」とした。
(5) Strength of Membrane The membrane was rubbed 20 times with a sponge containing water, and the membrane was visually evaluated. If the film does not peel at all, it is defined as “good”, if a part of the film peels slightly, it is defined as “OK”, and if most of the film peels, it is defined as “poor”. did.
(6) 膜の基材への密着性及び膜付き基材からの離型性
７５ｍｍ×１５０ｍｍ×厚さ２ｍｍのＳＵＳ３０４基材上に塗膜を形成した。塗膜の上に、セロファンテープを貼り付けた後、テープを剥がしたときに、塗膜がテープ側に全く付かなかった場合を「密着良好」とし、塗膜の一部が僅かにテープ側に付いたが、最終的にテープ側に貼り付かなかった場合を「密着可」とし、塗膜の大部分がテープ側に貼り付き、ＳＵＳ基材界面で塗膜が剥がれてしまった場合を「密着不良」とした。
(6) Adhesion of film to substrate and releasability from film-coated substrate A coating film was formed on a SUS304 substrate having a size of 75 mm×150 mm×thickness of 2 mm. After the cellophane tape was pasted on the coating film, when the tape was peeled off and the coating film did not stick to the tape side at all, it was defined as “adhesion was good”, and a part of the coating film slightly adhered to the tape side. If it was attached, but it was not attached to the tape side finally, it is set as “adhesion is possible”, and most of the coating film is attached to the tape side, and if the coating film is peeled off at the interface of the SUS substrate, “adhesion is possible”. Bad”.
膜の基材への密着性を確認するために用いたＳＵＳ３０４基材と同一の基材に膜を形成した。膜の上に、コニシ製エポキシ樹脂とガラスクロスを積層し、８時間乾燥させＦＲＰ層を形成した。形成したＦＲＰ層をＳＵＳ３０４基材から剥がしたときに、ＦＲＰ層のみが膜から剥離したものは、膜の基材への密着性と膜からの離型性が「良好」であるとした。ＦＲＰ層が膜とともにＳＵＳ基材から剥離したものは密着性が不十分であるが、離型性は「可」とした。ＦＲＰ層がＳＵＳ基材上の膜から全く剥離しなかったものは、離型性は「不良」であるが、膜の基材への密着性は「密着良好」とした。 A film was formed on the same substrate as the SUS304 substrate used to confirm the adhesion of the film to the substrate. On the film, an epoxy resin made by Konishi and glass cloth were laminated and dried for 8 hours to form an FRP layer. When the formed FRP layer was peeled from the SUS304 substrate, only the FRP layer was peeled from the film, and the adhesion of the film to the substrate and the releasability from the film were “good”. The one in which the FRP layer was peeled from the SUS substrate together with the film had insufficient adhesion, but the releasability was set to "OK". When the FRP layer was not peeled off from the film on the SUS substrate at all, the releasability was “poor”, but the film adhesion to the substrate was “good adhesion”.
表４から明らかなように、比較例１の液組成物では、フッ素を含有していないため、成膜性に優れるが、水及びヘキサデカンの接触角から明らかなように、撥水撥油性の機能が発現していなかった。そのため、離型性試験にてもＦＲＰ層の剥離ができなかった。比較例２の液組成物では、第１及び第２加水分解物を合計した配合量が少なすぎるため、水及びヘキサデカンの接触角も悪く、膜が薄すぎるため膜強度も不足していた。 As is clear from Table 4, the liquid composition of Comparative Example 1 does not contain fluorine and thus is excellent in film-forming property, but as is clear from the contact angle of water and hexadecane, the function of water and oil repellency. Was not expressed. Therefore, the FRP layer could not be peeled off even in the releasability test. In the liquid composition of Comparative Example 2, since the total amount of the first and second hydrolyzates was too small, the contact angle between water and hexadecane was poor, and the film was too thin, resulting in insufficient film strength.
また比較例３の液組成物では、第１及び第２加水分解物を合計した配合量が多すぎるため、粘度も高く、均一に成膜することができなかった。そのため、スポンジで擦る試験にて、一部塗膜が剥離した。また、離型性試験でも剥離する箇所としない箇所がまだらに存在する結果となっていた。比較例４の液組成物では第２溶媒が配合されていなかっため、塗膜の急激な乾燥を防止できなかった。また比較例５の液組成物では第１溶媒が配合されていなかったため、乾燥速度の調整が難しかった。また比較例６の液組成物では第１溶媒も第２溶媒も配合されていなかったため、更に乾燥速度の調整を行うことができなかった。 Further, in the liquid composition of Comparative Example 3, the total amount of the first and second hydrolyzates added was too large, so that the viscosity was high and a uniform film could not be formed. Therefore, in the test of rubbing with a sponge, a part of the coating film peeled off. Also, in the releasability test, there were spots where there was peeling and spots where there was no peeling. In the liquid composition of Comparative Example 4, the second solvent was not blended, and therefore the rapid drying of the coating film could not be prevented. Further, since the liquid composition of Comparative Example 5 did not contain the first solvent, it was difficult to adjust the drying rate. Further, in the liquid composition of Comparative Example 6, neither the first solvent nor the second solvent was blended, so that the drying rate could not be further adjusted.
また比較例７の液組成物では、第１溶媒が多過ぎ、第３溶媒が少な過ぎるため、乾燥速度の調整を行うことができなかった。結果として比較例４〜７の液組成物では、成膜時に筋、水玉等が発生し、表面の荒れた状態となった。そのため、膜強度試験にてスポンジで擦ると、一部の塗膜が剥離した。また離型性試験でも離型する箇所としない箇所が生じていた。更に比較例８の液組成物では、高沸点の第２溶媒が多過ぎるため、塗布状態において基材への弾きも見られ、室温２４時間の乾燥条件でも膜が乾燥しなかった。そのため、接触角、離型性試験は実施できなかった。 Further, in the liquid composition of Comparative Example 7, the amount of the first solvent was too much and the amount of the third solvent was too little, so that the drying rate could not be adjusted. As a result, with the liquid compositions of Comparative Examples 4 to 7, streaks, polka dots and the like were generated during film formation, and the surface became rough. Therefore, when the film was rubbed with a sponge in the film strength test, a part of the coating film was peeled off. In the releasability test, some parts were released and some were not. Furthermore, in the liquid composition of Comparative Example 8, the amount of the second solvent having a high boiling point was too large, so that the liquid was repelled by the substrate in the coated state, and the film was not dried even under the drying condition of room temperature for 24 hours. Therefore, the contact angle and releasability test could not be carried out.
これに対して、表４から明らかなように、実施例１〜９の液組成物では、成膜性、塗膜の撥水撥油性、耐水性、膜の強度において、良好な結果であり、膜付き基材からの離型性も良好であった。また実施例１０の液組成物では、全加水分解物に対してフッ素含有シランの含有量が多めであったため、撥水撥油性及び膜の基材への密着性は優れていたが、成膜性、膜の強度及び離型性はいずれも「可」であり、膜付き基材からの離型性試験では「密着可」であった。 On the other hand, as is clear from Table 4, the liquid compositions of Examples 1 to 9 have good results in film-forming properties, water and oil repellency of coating films, water resistance, and film strength. The releasability from the film-coated substrate was also good. Further, in the liquid composition of Example 10, the content of the fluorine-containing silane was large relative to the total hydrolyzate, so that the water and oil repellency and the adhesion of the film to the substrate were excellent, but the film formation The film, the strength of the film, and the releasability were all “good”, and the releasability test from the film-coated substrate was “adhesive”.
本発明の膜形成用液組成物は、機械油を使用する工場、油が飛散する厨房、油蒸気が立ちこめるレンジフード、換気扇、冷蔵庫扉等において、油汚れを防止する分野に用いられる。またプレス成形法、ＦＲＰ成形法等により樹脂成形体又はセラミック成形体を作る場合に、成形体を金型等から容易に離型させる分野に用いられる。 The film-forming liquid composition of the present invention is used in the field of preventing oil stains in a factory using mechanical oil, a kitchen in which oil is scattered, a range hood in which oil vapor is trapped, a ventilation fan, a refrigerator door, and the like. It is also used in the field of easily releasing a molded product from a mold or the like when a resin molded product or a ceramic molded product is produced by a press molding method, an FRP molding method or the like.
Claims (4)
前記第１加水分解物と前記第２加水分解物が合計して前記液組成物１００質量％に対して０．１〜１０．０質量％含まれ、
前記所定の溶媒が、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒と、沸点が１２０℃未満の第３溶媒と、水とを混合した混合溶媒であり、
前記第１溶媒、前記第２溶媒及び前記第３溶媒の質量比が、第１溶媒：第２溶媒：第３溶媒＝９〜１５：１〜３：８２〜９０である
ことを特徴とする膜形成用液組成物。
The first hydrolyzate and the second hydrolyzate are contained in a total amount of 0.1 to 10.0 mass% with respect to 100 mass% of the liquid composition,
The predetermined solvent is a mixture of a first solvent having a boiling point of 120° C. or more and less than 160° C., a second solvent having a boiling point of 160° C. or more and 220° C. or less, a third solvent having a boiling point of less than 120° C., and water. Mixed solvent,
The mass ratio of the first solvent, the second solvent, and the third solvent is first solvent:second solvent:third solvent=9 to 15:1 to 3:82 to 90. Forming liquid composition.
前記有機溶媒が、沸点が１２０℃以上１６０℃未満の第１溶媒と、沸点が１６０℃以上２２０℃以下の第２溶媒と、沸点が１２０℃未満の第３溶媒とからなり、The organic solvent comprises a first solvent having a boiling point of 120° C. or more and less than 160° C., a second solvent having a boiling point of 160° C. or more and 220° C. or less, and a third solvent having a boiling point of less than 120° C.,
前記ケイ素アルコキシドの第１加水分解物が、前記ケイ素アルコキシドと前記第３溶媒と水とを混合して調製された第１液と、前記第３溶媒と有機酸、無機酸又はチタン化合物からなる触媒とを混合して調製された第２液とを混合することにより、調製され、A catalyst comprising the first hydrolyzate of the silicon alkoxide, the first liquid prepared by mixing the silicon alkoxide, the third solvent and water, and the third solvent and an organic acid, an inorganic acid or a titanium compound. Is prepared by mixing the second liquid prepared by mixing and
前記第１加水分解物と前記第２加水分解物の合計量１００質量％に対して前記第２加水分解物が０．１〜１０．０質量％含まれ、0.1 to 10.0 mass% of the second hydrolyzate is contained with respect to a total amount of 100 mass% of the first hydrolyzate and the second hydrolyzate,
前記第１溶媒、前記第２溶媒及び前記第３溶媒の質量比が、第１溶媒：第２溶媒：第３溶媒＝９〜１５：１〜３：８２〜９０であるThe mass ratio of the first solvent, the second solvent and the third solvent is first solvent:second solvent:third solvent=9 to 15:1 to 3:82 to 90.
ことを特徴とする膜形成用液組成物の製造方法。A method for producing a film forming liquid composition, comprising:
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