JP6652407B2 - Liquid composition for forming antifouling film and method for forming antifouling film using this liquid composition - Google Patents
Liquid composition for forming antifouling film and method for forming antifouling film using this liquid composition Download PDFInfo
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- JP6652407B2 JP6652407B2 JP2016042330A JP2016042330A JP6652407B2 JP 6652407 B2 JP6652407 B2 JP 6652407B2 JP 2016042330 A JP2016042330 A JP 2016042330A JP 2016042330 A JP2016042330 A JP 2016042330A JP 6652407 B2 JP6652407 B2 JP 6652407B2
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- acrylic acid
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- 239000000203 mixture Substances 0.000 title claims description 84
- 239000007788 liquid Substances 0.000 title claims description 81
- 230000003373 anti-fouling effect Effects 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 124
- 239000000178 monomer Substances 0.000 claims description 104
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 73
- 239000003505 polymerization initiator Substances 0.000 claims description 73
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 72
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000003513 alkali Substances 0.000 claims description 50
- 239000002904 solvent Substances 0.000 claims description 37
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- -1 acryl Chemical group 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 229940048053 acrylate Drugs 0.000 description 115
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 87
- 239000000243 solution Substances 0.000 description 52
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 38
- 239000003921 oil Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 25
- 229920002799 BoPET Polymers 0.000 description 7
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229940117986 sulfobetaine Drugs 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 2
- VHJHZYSXJKREEE-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropyl prop-2-enoate Chemical compound FC(F)C(F)(F)COC(=O)C=C VHJHZYSXJKREEE-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- ICCCRCJXHNMZPJ-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) 2,2-dimethyl-3-prop-2-enoyloxypropanoate Chemical compound C=CC(=O)OCC(C)(C)COC(=O)C(C)(C)COC(=O)C=C ICCCRCJXHNMZPJ-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- HIBIBNJUUBAHQK-UHFFFAOYSA-N [1,1-bis(2-methylprop-2-enoyloxy)-2-phosphonooxyethyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(COP(O)(O)=O)(OC(=O)C(C)=C)OC(=O)C(C)=C HIBIBNJUUBAHQK-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- SYWIXHZXHQDFOO-UHFFFAOYSA-N methyl n-phenyliminocarbamate Chemical class COC(=O)N=NC1=CC=CC=C1 SYWIXHZXHQDFOO-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、親水性及び撥油性を有する防汚性膜を形成するための液組成物及びこの液組成物を用いて防汚性膜を形成する方法に関するものである。 The present invention relates to a liquid composition for forming an antifouling film having hydrophilicity and oil repellency, and a method for forming an antifouling film using the liquid composition.
基材に汚れが付着するのを防止する方法として、基材表面を撥水化して汚れをはじきやすくする方法がある。また基材に付着した汚れを容易に洗い流す方法として、基材表面を親水化して水と一緒に汚れを流してしまう方法がある。中でも疎水性成分を多く含む汚れに対しては塗膜の表面をできるだけ親水性にした方がよいという提案がなされている（例えば、非特許文献１参照。）。 As a method of preventing dirt from adhering to the substrate, there is a method of making the surface of the substrate water-repellent to easily repel dirt. In addition, as a method of easily washing off the dirt attached to the base material, there is a method of making the surface of the base material hydrophilic so that the dirt is flushed with water. In particular, it has been proposed that the surface of a coating film should be made as hydrophilic as possible for stains containing a large amount of hydrophobic components (for example, see Non-Patent Document 1).
一方、一般的な樹脂組成物を使用した塗料の塗布表面や成型体表面は、水の接触角が比較的大きく水をはじく性質はあるが油の接触角が小さく油になじむ性質を持っており、防汚に十分な撥液性はなく、親水性でもなく、汚れにくい表面とはなっていない。塗膜を親水化する方法については種々研究されており、例えば光触媒性酸化物を含む防汚性コーティング組成物を使って塗膜を形成する方法などが挙げられる（例えば、特許文献１参照。）。別の塗膜を親水化する方法として光触媒性コーティング液にシリケート系の化合物を添加した浴室部材用コーティング組成物を塗布して塗膜を親水化する方法が知られている（例えば、特許文献２参照）。 On the other hand, the surface of a coating or molded article using a general resin composition has a relatively large water contact angle and has the property of repelling water, but has a small oil contact angle and has the property of being compatible with oil. It does not have sufficient liquid repellency for antifouling, is not hydrophilic, and does not have a stain-resistant surface. Various studies have been made on a method for hydrophilizing a coating film, and for example, a method of forming a coating film using an antifouling coating composition containing a photocatalytic oxide, and the like (for example, see Patent Document 1). . As a method for hydrophilizing another coating film, there is known a method for applying a coating composition for bathroom members obtained by adding a silicate-based compound to a photocatalytic coating solution to hydrophilize the coating film (for example, Patent Document 2). reference).
しかしながら、特許文献１及び特許文献２に示される防汚性のコーティング組成物を用いて塗膜を親水化し、水を使用して汚れを落とした場合、この塗膜には親油性の性質が残存するため、塗膜は親水親油性となって、油などの疎水性の汚れが付着した場合、塗膜に油がなじみ、十分な防汚効果が得られないことがあった。 However, when the coating film is hydrophilized by using the antifouling coating composition disclosed in Patent Documents 1 and 2, and the stain is removed using water, the lipophilic property remains in the coating film. Therefore, the coating film becomes hydrophilic and lipophilic, and when hydrophobic dirt such as oil adheres, the coating film may be adapted to the oil and a sufficient antifouling effect may not be obtained.
本発明の目的は、塗膜を形成した場合に、塗膜表面が親水撥油性になって、塗膜に防汚機能を付与することができ、また水に接触し続けても膜が膨潤剥離しない防汚性膜形成用液組成物を提供することにある。また本発明の別の目的は、この液組成物を用いて防汚性膜を形成する方法を提供することにある。 An object of the present invention is that when a coating film is formed, the surface of the coating film becomes hydrophilic and oil-repellent, and can impart an antifouling function to the coating film, and the film swells and peels even when it is kept in contact with water. It is an object of the present invention to provide a liquid composition for forming an antifouling film, which is not used. Another object of the present invention is to provide a method for forming an antifouling film using the liquid composition.
本発明の第１の観点は、アクリル酸、アルカリを含む水溶液、３個以上のビニル基をそれぞれ有する多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマー、重合開始剤及び溶媒を含有し、前記アクリル酸１００質量部に対して前記アルカリを５〜２３質量部含み、前記多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマー１００質量部に対して前記アクリル酸を５〜４０質量部含み、前記アクリル酸と前記多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマーを合計した全アクリル１００質量部に対して前記重合開始剤を１〜１０質量部含み、かつ前記水溶液中の水１００質量部に対して前記アクリル酸と前記アルカリで形成されるアクリル酸塩を８〜６０質量部含む含む防汚性膜形成用液組成物である。 According to a first aspect of the present invention, there is provided an acrylic acid, an aqueous solution containing an alkali, a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer each having at least three vinyl groups, a polymerization initiator and a solvent. 5 to 23 parts by mass of the alkali is contained with respect to 100 parts by mass, and 5 to 40 parts by mass of the acrylic acid is contained with respect to 100 parts by mass of the polyfunctional acrylate monomer and / or the polyfunctional acrylate oligomer. The polyacrylic acid monomer and / or the polyacrylic acid oligomer includes 1 to 10 parts by mass of the polymerization initiator based on 100 parts by mass of the total acryl, and the acrylic acid and 100 parts by mass of water in the aqueous solution. For forming an antifouling film containing 8 to 60 parts by mass of the acrylate formed by the alkali It is a composition.
本発明の第２の観点は、前記液組成物１００質量部中に、両性型含窒素フッ素系化合物、リン酸含有アクリレートモノマー又はフッ素含有アクリレートモノマーの少なくとも１種を３質量部以下更に含むことを特徴とする。 A second aspect of the present invention is that 100 parts by mass of the liquid composition further contains at least one kind of an amphoteric nitrogen-containing fluorine-based compound, a phosphoric acid-containing acrylate monomer or a fluorine-containing acrylate monomer in an amount of 3 parts by mass or less. Features.
本発明の第３の観点は、第１又は第２の観点の液組成物を基材表面に塗布して塗膜を形成し、前記塗膜を乾燥した後、前記塗膜に紫外線を照射するか前記塗膜を加熱することにより、防汚性膜を形成する方法である。 A third aspect of the present invention is to apply a liquid composition according to the first or second aspect to a substrate surface to form a coating film, and after irradiating the coating film with ultraviolet light after drying the coating film. Or a method of forming an antifouling film by heating the coating film.
本発明の第１の観点の防汚性膜形成用液組成物は、アクリル酸に対するアルカリの質量割合、多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマーに対するアクリル酸の質量割合、全アクリルに対する重合開始剤の質量割合、及びアクリル酸とアルカリで形成されるアクリル酸塩に対する水溶液中の水の質量割合をそれぞれ所定の範囲に制御して構成される。この液組成物を基材上に塗布した後、上記モノマー及び／又はオリゴマーを重合して塗膜を硬化させることにより、親水性を有する一方、水と接触して塗膜が水を含んでも膜が膨潤せず、基材表面から膜が剥離しない。また水を含んだ塗膜は撥油性を生じる。 The liquid composition for forming an antifouling film according to the first aspect of the present invention comprises: a mass ratio of alkali to acrylic acid; a mass ratio of acrylic acid to a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer; The mass ratio of the agent and the mass ratio of water in the aqueous solution with respect to the acrylate formed by acrylic acid and alkali are each controlled in a predetermined range. After the liquid composition is applied on a substrate, the monomer and / or oligomer is polymerized to cure the coating film, so that the coating film has hydrophilicity, while being in contact with water and containing water. Does not swell and the film does not peel off from the substrate surface. Further, a coating film containing water produces oil repellency.
本発明の第２の観点の防汚性膜形成用液組成物は、液組成物中に、両性型含窒素フッ素系化合物を３質量部以下更に含むことにより、この両性型含窒素フッ素系化合物が塗膜の乾燥時にその低い表面張力により、塗膜の表層部に析出し、より一層塗膜の親水撥油性を高める。また液組成物中に、リン酸含有アクリレートモノマー又はフッ素含有アクリレートモノマー少なくとも１種を３質量部以下更に含むことにより、リン酸含有アクリレートモノマーは、親水性を更に付与し、フッ素含有アクリレートモノマーは更に撥油性を付与する。 The liquid composition for forming an antifouling film according to the second aspect of the present invention further comprises an amphoteric nitrogen-containing fluorine-based compound in an amount of 3 parts by mass or less in the liquid composition. Is deposited on the surface layer of the coating film due to its low surface tension when the coating film is dried, and further increases the hydrophilic oil repellency of the coating film. Further, in the liquid composition, by further containing at least one kind of phosphoric acid-containing acrylate monomer or fluorine-containing acrylate monomer in an amount of 3 parts by mass or less, the phosphoric acid-containing acrylate monomer further imparts hydrophilicity, and the fluorine-containing acrylate monomer further comprises Gives oil repellency.
本発明の第３の観点の防汚性膜を形成する方法は、塗膜に紫外線を照射するか又は塗膜を加熱することにより、上記モノマー及び／又はオリゴマーを重合して塗膜を硬化させ、塗膜に防汚機能を付与することができる。 The method for forming an antifouling film according to the third aspect of the present invention comprises irradiating the coating film with ultraviolet rays or heating the coating film to polymerize the monomer and / or oligomer and cure the coating film. In addition, an antifouling function can be imparted to the coating film.
次に本発明を実施するための形態を説明する。 Next, an embodiment for carrying out the present invention will be described.
〔防汚性膜形成用液組成物〕
本実施の形態の防汚性膜形成用液組成物は、アクリル酸、アルカリを含む水溶液、３以上のビニル基をそれぞれ有する多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマー、重合開始剤及び溶媒を混合して調製される。アクリル酸としては、アクリル酸、メタクリル酸等の不飽和カルボン酸が挙げられる。特にアクリル酸が好ましい。アルカリを含む水溶液としては、水酸化ナトリウム水溶液、水酸化カリウム水溶液、アンモニア水溶液等が挙げられる。この液組成物は、多官能アクリレートモノマーと多官能アクリレートオリゴマーのいずれか一方又は双方を含む。これらのモノマー又はオリゴマーは３個以上のビニル基を有する。ビニル基が１個又は２個のものは立体構造を取りにくいため、ｎ−ヘキサデカンの転落性が発現せず、塗膜にしたときに親油性に劣る。多官能アクリレートモノマーとしては、ペンタエリスリトールトリアクリレート（ビニル基：３個）、ペンタエリスリトールテトラアクリレート（ビニル基：４個）、トリペンタエリスリトールトリアクリレート（ビニル基：３個）、トリメチロールプロパントリメタクリレート（ビニル基：３個）、ジペンタエリスリトールペンタアクリレート（ビニル基：５個）、ジペンタエリスリトールヘキサアクリレート（ビニル基：６個）等が挙げられ、多官能アクリレートオリゴマーとしては、ウレタンアクリレートオリゴマー、エポキシアクリレートオリゴマー等が挙げられる。
(Liquid composition for forming an antifouling film)
The liquid composition for forming an antifouling film according to the present embodiment comprises an aqueous solution containing acrylic acid and an alkali, a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer each having at least three vinyl groups, a polymerization initiator and a solvent. It is prepared by mixing. Acrylic acid includes unsaturated carboxylic acids such as acrylic acid and methacrylic acid. Particularly, acrylic acid is preferred. Examples of the aqueous solution containing an alkali include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonia solution. The liquid composition contains one or both of a polyfunctional acrylate monomer and a polyfunctional acrylate oligomer. These monomers or oligomers have three or more vinyl groups. Those having one or two vinyl groups do not easily form a three-dimensional structure, so that n-hexadecane does not exhibit falling properties and is poor in lipophilicity when formed into a coating film. Examples of the polyfunctional acrylate monomer include pentaerythritol triacrylate (vinyl group: 3), pentaerythritol tetraacrylate (vinyl group: 4), tripentaerythritol triacrylate (vinyl group: 3), trimethylolpropane trimethacrylate ( Vinyl group: 3), dipentaerythritol pentaacrylate (vinyl group: 5), dipentaerythritol hexaacrylate (vinyl group: 6), and the like. Polyfunctional acrylate oligomers include urethane acrylate oligomer and epoxy acrylate Oligomers and the like.
重合開始剤は、上記モノマー及び／又はオリゴマーを重合を開始させるためのものであって、この重合開始剤としては、加熱若しくは紫外線照射によりラジカルを発生してモノマーの重合を開始させるものであれば特に制限はない。熱重合開始剤としては、例えば、アゾビスイソブチロニトリル等のアゾニトリル化合物、アゾエステル化合物、アゾアミド化合物、ｔｅｒｔ−ブチルヒドロペルオキシド、過酸化ベンゾイル、ペルオキソ二硫酸アンモニウム等の有機過酸化物が挙げられる。光重合開始剤としては、例えば、アセトフェノン系化合物、ベンゾイン系化合物等を挙げることができる。上記重合開始剤により上記モノマー及び／又はオリゴマーを重合させると、得られる塗膜は良好な被膜性を有し、また塗膜の基材への接着性に優れる。また塗膜を水に接触させ続けても膜が膨潤せず、基材から剥離しにくくなる。溶媒は、上記モノマー及び／又はオリゴマーを溶解しかつ水溶性であれば特に制限はない。具体的には、エタノール、アセトン、エチレングリコールモノエチルエーテル等が挙げられる。 The polymerization initiator is for initiating the polymerization of the above monomer and / or oligomer. As the polymerization initiator, any one can be used as long as it generates a radical by heating or irradiation with ultraviolet light to initiate polymerization of the monomer. There is no particular limitation. Examples of the thermal polymerization initiator include azonitrile compounds such as azobisisobutyronitrile, azoester compounds, azoamide compounds, and organic peroxides such as tert-butyl hydroperoxide, benzoyl peroxide, and ammonium peroxodisulfate. Examples of the photopolymerization initiator include an acetophenone-based compound and a benzoin-based compound. When the above-mentioned monomer and / or oligomer is polymerized by the above-mentioned polymerization initiator, the resulting coating film has good film properties and excellent adhesion of the coating film to the substrate. Further, even if the coating film is kept in contact with water, the film does not swell and it is difficult to peel off the film from the substrate. The solvent is not particularly limited as long as it dissolves the monomer and / or oligomer and is water-soluble. Specific examples include ethanol, acetone, and ethylene glycol monoethyl ether.
本実施の形態の防汚性膜形成用液組成物は、両性型含窒素フッ素系化合物、リン酸含有アクリレートモノマー又はフッ素含有アクリレートモノマーの少なくとも１種を更に含んでもよい。両性型含窒素フッ素系化合物は、下記式（１）で示される化合物である。 The antifouling film-forming liquid composition of the present embodiment may further include at least one of an amphoteric nitrogen-containing fluorine-based compound, a phosphoric acid-containing acrylate monomer, and a fluorine-containing acrylate monomer. The amphoteric nitrogen-containing fluorine-based compound is a compound represented by the following formula (1).
上記式（１）中、Ｒｆ１、Ｒｆ２は、それぞれ同一又は互いに異なる、炭素数１〜６であって直鎖状又は分岐状のペルフルオロアルキル基である。また、Ｒｆ３は、炭素数１〜６であって、直鎖状又は分岐状のペルフルオロアルキレン基である。 In the above formula (1), Rf 1 and Rf 2 are the same or different, each having 1 to 6 carbon atoms and being a linear or branched perfluoroalkyl group. Rf 3 is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
また上記式（１）中、Ｒは、２価の有機基である連結基である。前記Ｒは、直鎖状又は分岐状の有機基であってもよい。また、前記Ｒは、分子鎖中にエーテル結合、エステル結合、アミド結合及びウレタン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し、含まなくてもよい。 In the above formula (1), R is a linking group that is a divalent organic group. R may be a linear or branched organic group. R may or may not include one or more bonds selected from an ether bond, an ester bond, an amide bond, and a urethane bond in the molecular chain.
また上記式（１）中、Ｘは、カルボベタイン型、スルホベタイン型、アミンオキシド型及びホスホベタイン型のうち、いずれかの末端を有する両性型の親水性賦与基である、本実施の形態の含窒素フッ素系化合物は両性型であるため、親水性付与基Ｘは、末端に、カルボベタイン型の「−Ｎ＋Ｒ８Ｒ９（ＣＨ２）ｎＣＯ２ −」、スルホベタイン型の「−Ｎ＋Ｒ８Ｒ９（ＣＨ２）ｎＳＯ３ −」、アミンオキシド型の「−Ｎ＋Ｒ８Ｒ９Ｏ−」又はホスホベタイン型の「−ＯＰＯ３ −（ＣＨ２）ｎＮ＋Ｒ８Ｒ９Ｒ１０」（ｎは１〜５の整数、Ｒ８及びＲ９は水素原子又は炭素数１〜１０のアルキル基、Ｒ１０は水素原子又は炭素数１〜１０のアルキル基又は炭素数１〜１０のアルキレン基）を有する。 In the above formula (1), X is an amphoteric type hydrophilicity-imparting group having any one of a carbobetaine type, a sulfobetaine type, an amine oxide type and a phosphobetaine type. Since the nitrogen-containing fluorine-based compound is of the amphoteric type, the hydrophilicity-imparting group X has a carbobetaine-type “—N + R 8 R 9 (CH 2 ) n CO 2 − ” and a sulfobetaine “-” n + R 8 R 9 (CH 2) n SO 3 - ", of the amine oxide type" -N + R 8 R 9 O - "or phosphobetaine type" -OPO 3 - (CH 2) n n + R 8 R 9 R 10 ”(n is an integer of 1 to 5, R 8 and R 9 are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms or 1 carbon atom. To 10 alkylene groups).
上記式（１）で表される両性型含窒素フッ素系化合物としては、次の式（２）で表されるカルボベタイン型化合物、式（３）〜（５）で表されるスルホベタイン型化合物が例示される。 Examples of the amphoteric nitrogen-containing fluorine-based compound represented by the above formula (1) include a carbobetaine-type compound represented by the following formula (2) and a sulfobetaine-type compound represented by the following formulas (3) to (5) Is exemplified.
・式（２）で表されるカルボベタイン型化合物 ・ Carbobetaine type compound represented by formula (2)
・式（３）で表されるスルホベタイン型化合物 ・ Sulfobetaine type compound represented by formula (3)
・式（４）で表されるスルホベタイン型化合物 ・ Sulfobetaine type compound represented by formula (4)
・式（５）で表されるスルホベタイン型化合物 ・ Sulfobetaine type compound represented by formula (5)
またリン酸含有アクリレートモノマーとしては、トリスアクリロイルオキシエチルフォスフェート、トリスメタアクリロイルオキシエチルフォスフェート、２−アクリロイルオキシエチルアシッドフォスフェート等が挙げられ、フッ素含有アクリレートモノマーとしては、２，２，２−トリフルオロエチルアクリレート、２，２，３，３−テトラフルオロプロピルアクリレート、１Ｈ，１Ｈ，５Ｈ−オクタフルオロプロペンチルアクリレート等が挙げられる。また、下記式（６）〜（１８）に記載されているフッ素含有アクリレートも挙げられる。 Examples of the phosphoric acid-containing acrylate monomer include trisacryloyloxyethyl phosphate, trismethacryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, and the like, and fluorine-containing acrylate monomers include 2,2,2- Examples include trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropropentyl acrylate, and the like. Further, fluorine-containing acrylates represented by the following formulas (6) to (18) are also included.
本実施の形態の防汚性膜形成用液組成物におけるアルカリの質量割合は、アクリル酸１００質量部に対して、５〜２３質量部、好ましくは５〜１６質量部である。アルカリの質量割合が下限値未満であると、親水性を発現するアクリル酸塩が過少となり、塗膜に親水性が発現しない。アルカリの質量割合が上限値を超えると、塗膜が水に接触したときに、吸水量が過剰となることで塗膜が膨潤し、膜の強度を保持することができない。 The mass ratio of alkali in the antifouling film-forming liquid composition of the present embodiment is 5 to 23 parts by mass, preferably 5 to 16 parts by mass with respect to 100 parts by mass of acrylic acid. If the mass ratio of the alkali is less than the lower limit, the amount of the acrylate that exhibits hydrophilicity is too small, and the hydrophilicity is not exhibited in the coating film. When the mass ratio of the alkali exceeds the upper limit, when the coating comes into contact with water, the coating absorbs an excessive amount of water and swells, so that the strength of the coating cannot be maintained.
本実施の形態の防汚性膜形成用液組成物におけるアクリル酸の質量割合は、多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマー１００質量部に対して、５〜４０質量部、好ましくは５〜２５質量部である。多官能アクリレートモノマーのみに、アルカリを添加した膜は、親水性が全く発現せず、アクリル酸塩を付与することで、親水性が発現する。そのため、アクリル酸の質量割合が下限値未満であると、塗膜中のアクリル酸塩の基が過少となり、塗膜に親水性が発現しない。アクリル酸の質量割合が上限値を超えると、塗膜が水に接触したときに吸水量が過剰となることで塗膜が膨潤し、膜の強度を保持することができない。 The mass ratio of acrylic acid in the antifouling film-forming liquid composition of the present embodiment is 5 to 40 parts by mass, preferably 5 to 40 parts by mass, based on 100 parts by mass of the polyfunctional acrylate monomer and / or the polyfunctional acrylate oligomer. 25 parts by mass. A film obtained by adding an alkali to only a polyfunctional acrylate monomer does not exhibit any hydrophilicity, but exhibits hydrophilicity by adding an acrylate. Therefore, if the mass ratio of acrylic acid is less than the lower limit, the number of acrylate groups in the coating film is too small, and the coating film does not exhibit hydrophilicity. When the mass ratio of acrylic acid exceeds the upper limit, the coating film swells due to an excessive amount of water absorption when the coating film comes into contact with water, and the strength of the film cannot be maintained.
本実施の形態の防汚性膜形成用液組成物における重合開始剤の質量割合は、アクリル酸と多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマーを合計した全アクリル１００質量部に対して、１〜１０質量部、好ましくは３〜８質量部である。重合開始剤の質量割合が下限値未満であると、ビニル基の架橋が不十分となり塗膜に親水性が発現せず、塗膜が水に接触したときに膨潤し、膜の強度を保持することができない。重合開始剤の質量割合が上限値を超えると、重合開始剤が組成物中に溶解しにくくなること、成膜過程にて、塗膜にひび割れが発生する等不具合が生じる。 The mass ratio of the polymerization initiator in the antifouling film-forming liquid composition of the present embodiment is 1 to 100 parts by mass of total acrylic obtained by adding acrylic acid and a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer. 10 to 10 parts by mass, preferably 3 to 8 parts by mass. When the mass ratio of the polymerization initiator is less than the lower limit, the crosslinking of the vinyl group is insufficient and the coating film does not exhibit hydrophilicity, swells when the coating film comes into contact with water, and maintains the strength of the film. I can't. If the mass ratio of the polymerization initiator exceeds the upper limit, problems such as the difficulty of dissolving the polymerization initiator in the composition and the occurrence of cracks in the coating film during the film formation process occur.
本実施の形態の防汚性膜形成用液組成物におけるアルカリを含む水溶液中の水１００質量部に対してアクリル酸とアルカリで形成されるアクリル酸塩（アクリル酸ナトリウム等）の質量割合は、８〜６０質量部、好ましくは８〜４０質量部である。アクリル酸塩の質量割合が上限値を超えると、水が少ないため、アクリル酸塩が溶解できず、得られた液組成物中にフロック（白だま）が発生し、塗料化することができない。アクリル酸塩の質量割合が下限値未満であると、理由は定かではないが、塗膜の親水性及びｎ−ヘキサデカンの転落性が劣る他、多官能アクリレートモノマー、重合開始剤が組成物中に溶解しない不具合が生じる。 The mass ratio of an acrylate (such as sodium acrylate) formed with acrylic acid and alkali to 100 parts by mass of water in an aqueous solution containing alkali in the antifouling film-forming liquid composition of the present embodiment is as follows: It is 8 to 60 parts by mass, preferably 8 to 40 parts by mass. If the mass ratio of the acrylate exceeds the upper limit, the acrylate cannot be dissolved because of a small amount of water, and flocs (white balls) are generated in the obtained liquid composition, so that it cannot be formed into a paint. When the mass ratio of the acrylate is less than the lower limit, the reason is not clear, but the hydrophilicity of the coating film and the falling property of n-hexadecane are poor, and a polyfunctional acrylate monomer and a polymerization initiator are contained in the composition. Failure to dissolve occurs.
本実施の形態の防汚性膜形成用液組成物中の両性型含窒素フッ素系化合物の含有量は３質量部以下である。両性型含窒素フッ素系化合物を含むことにより、防汚性がより向上する。３質量部を超えると、得られた液組成物の安定性及び成膜性が悪化し易い。 The content of the amphoteric nitrogen-containing fluorine-based compound in the antifouling film-forming liquid composition of the present embodiment is 3 parts by mass or less. By containing the amphoteric nitrogen-containing fluorine-based compound, the antifouling property is further improved. If the amount exceeds 3 parts by mass, the stability and film formability of the obtained liquid composition are likely to deteriorate.
本実施の形態の防汚性膜形成用液組成物中のリン酸含有アクリレートモノマー又フッ素含有アクリレートモノマー（以下、「その他のモノマー」という。）の含有量は３質量部以下である。その他のモノマーを含むことにより、リン酸含有アクリレートモノマーは、親水性を更に付与し、フッ素含有アクリレートモノマーは更に撥油性がより向上する。３質量部を超えると、組成物の安定性、成膜性の不具合を生じ易い。 The content of the phosphoric acid-containing acrylate monomer or the fluorine-containing acrylate monomer (hereinafter, referred to as “other monomers”) in the antifouling film-forming liquid composition of the present embodiment is 3 parts by mass or less. By including other monomers, the phosphoric acid-containing acrylate monomer further imparts hydrophilicity, and the fluorine-containing acrylate monomer further improves oil repellency. If the amount exceeds 3 parts by mass, the stability of the composition and the problem of film forming property are likely to occur.
〔防汚性膜の形成方法〕
本実施の形態の防汚性膜は、例えば、基材であるガラス上、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、２５〜１３０℃の温度で乾燥させ、重合開始剤が熱重合性重合開始剤であれば、２５〜１３０℃の温度で１〜６０分間加熱することにより、また重合開始剤が光重合性重合開始剤であれば、１００〜１０００ｍJ／ｃｍ２の強度で紫外線を照射することにより、形成される。
(Method of forming antifouling film)
The antifouling film of the present embodiment is obtained by, for example, applying the above-mentioned liquid composition to a substrate glass or a polyester film such as polyethylene terephthalate (PET), polybutylene terephthalate or polyethylene naphthalate by a screen printing method After coating by a bar coating method, a die coating method, a doctor blade, a spinning method, and the like, drying is performed at a temperature of 25 to 130 ° C., and when the polymerization initiator is a thermopolymerizable polymerization initiator, a temperature of 25 to 130 ° C. It is formed by heating for 1 to 60 minutes and, if the polymerization initiator is a photopolymerizable polymerization initiator, by irradiating ultraviolet rays with an intensity of 100 to 1000 mJ / cm 2 .
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＞
アクリル酸０．２００ｇと、ビニル基を３個有する多官能アクリレートモノマーであるペンタエリスリトールトリアクリレート（大阪有機化学工業製ビスコート♯３００）１．６５６ｇと、溶媒であるエタノール６．０００ｇと、光重合開始剤のアルキルフェノン系重合開始剤（チバジャパン製イルガキュア９０７）０．１１１ｇを秤量し、十分に混合した後、この混合液にアルカリ水溶液として１２％水酸化ナトリウム水溶液０．０９３ｇを更に添加混合して液組成物を調製した。
<Example 1>
0.200 g of acrylic acid, 1.656 g of pentaerythritol triacrylate (Biscoat # 300, manufactured by Osaka Organic Chemical Industry), a polyfunctional acrylate monomer having three vinyl groups, and 6.000 g of ethanol, a solvent, start photopolymerization. 0.111 g of an alkylphenone-based polymerization initiator (Irgacure 907 manufactured by Ciba Japan) was weighed and thoroughly mixed, and then 0.093 g of a 12% aqueous sodium hydroxide solution as an aqueous alkali solution was further added to and mixed with the mixed solution. A liquid composition was prepared.
＜実施例２＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 2>
A liquid composition was prepared in the same manner as in Example 1 using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, except that 0.185 g of a 12% aqueous sodium hydroxide solution was weighed. Prepared.
＜実施例３＞
１２％水酸化ナトリウム水溶液を０．３７０ｇ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 3>
A liquid composition was prepared in the same manner as in Example 1 using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, except that 0.370 g of a 12% aqueous sodium hydroxide solution was weighed. Prepared.
＜実施例４＞
アクリル酸を０．１００ｇ、多官能アクリレートモノマーを２．０７０ｇ、重合開始剤を０．１３０ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 4>
0.100 g of acrylic acid, 2.070 g of polyfunctional acrylate monomer, and 0.130 g of polymerization initiator, respectively, except that the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1 were used. A liquid composition was prepared in the same manner as in Example 1.
＜実施例５＞
アクリル酸を０．３００ｇ、多官能アクリレートモノマーを１．５５２ｇ、１２％水酸化ナトリウム水溶液を０．２７８ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 5>
The same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution and polymerization initiator as in Example 1 except that 0.300 g of acrylic acid, 1.552 g of polyfunctional acrylate monomer, and 0.278 g of 12% aqueous sodium hydroxide solution were weighed respectively. A liquid composition was prepared in the same manner as in Example 1 using a solvent.
＜実施例６＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．０１９ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 6>
Using the same acrylic acid, polyfunctional acrylate monomer, alkaline aqueous solution, polymerization initiator and solvent as in Example 1, except that 0.185 g of a 12% aqueous sodium hydroxide solution and 0.019 g of a polymerization initiator were weighed, respectively. A liquid composition was prepared in the same manner as in Example 1.
＜実施例７＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１８６ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 7>
Using the same acrylic acid, polyfunctional acrylate monomer, alkaline aqueous solution, polymerization initiator, and solvent as in Example 1, except that 0.185 g of a 12% aqueous sodium hydroxide solution and 0.186 g of a polymerization initiator were weighed, respectively, A liquid composition was prepared in the same manner as in Example 1.
＜実施例８＞
アルカリ水溶液として１６．８％水酸化カリウム水溶液を選定し、このアルカリ水溶液を０．１８５ｇ秤量し、実施例１の液組成物に更に上記式（４）で表されるスルホベタイン型化合物を０．０８２ｇ添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 8>
A 16.8% aqueous potassium hydroxide solution was selected as the aqueous alkali solution, 0.185 g of the aqueous alkali solution was weighed, and the sulfobetaine compound represented by the above formula (4) was added to the liquid composition of Example 1 in an amount of 0.1%. 082 g was added and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例９＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ秤量し、実施例１の液組成物に更に上記式（３）で表されるスルホベタイン型化合物を０．００８ｇ添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 9>
0.185 g of a 12% aqueous sodium hydroxide solution was weighed, and 0.008 g of the sulfobetaine compound represented by the above formula (3) was further added to the liquid composition of Example 1 and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１０＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ秤量し、実施例１の液組成物に更に上記式（５）で表されるスルホベタイン型化合物０．００８ｇ添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 10>
0.185 g of a 12% aqueous sodium hydroxide solution was weighed, and 0.008 g of a sulfobetaine compound represented by the above formula (5) was further added to the liquid composition of Example 1 and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１１＞
アクリル酸０．２００ｇと、ビニル基を３個有する多官能アクリレートモノマーであるトリペンタエリスリトールトリアクリレート（大阪有機化学工業製ビスコート♯８０２）１．６５６ｇと、溶媒であるエタノール６．０００ｇと、光重合開始剤のアルキルフェノン系重合開始剤（チバジャパン製イルガキュア９０７）０．１１１ｇを秤量し、十分に混合した後、この混合液にアルカリ水溶液として１２％水酸化ナトリウム水溶液０．１８５ｇを更に添加混合して液組成物を調製し、この液組成物に更に上記式（２）で表されるカルボベタイン型化合物０．００８ｇを添加混合した。
<Example 11>
0.200 g of acrylic acid, 1.656 g of tripentaerythritol triacrylate (Biscoat # 802, manufactured by Osaka Organic Chemical Industry), a polyfunctional acrylate monomer having three vinyl groups, 6.000 g of ethanol as a solvent, and photopolymerization After weighing out 0.111 g of an alkylphenone-based polymerization initiator (Irgacure 907 manufactured by Ciba Japan) as an initiator and mixing well, 0.185 g of a 12% aqueous sodium hydroxide solution as an aqueous alkali solution was further added to the mixed solution, followed by mixing. A liquid composition was prepared, and 0.008 g of a carbobetaine type compound represented by the above formula (2) was further added to and mixed with the liquid composition.
＜実施例１２＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１２２ｇそれぞれ秤量し、実施例１の液組成物に更にリン酸含有アクリレートモノマーであるトリスアクリロイルオキシエチルフォスフェート０．１８６ｇを添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 12>
0.185 g of a 12% aqueous sodium hydroxide solution and 0.122 g of a polymerization initiator were weighed, and 0.186 g of trisacryloyloxyethyl phosphate, which is a phosphoric acid-containing acrylate monomer, was further added to the liquid composition of Example 1 and mixed. did. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１３＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１２２ｇそれぞれ秤量し、実施例１の液組成物に更にリン酸含有アクリレートモノマーであるトリスメタアクリロイルオキシエチルフォスフェート０．１８６ｇを添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 13>
0.185 g of a 12% aqueous sodium hydroxide solution and 0.122 g of a polymerization initiator were weighed, and 0.186 g of a phosphoric acid-containing acrylate monomer, tris-methacryloyloxyethyl phosphate, was further added to the liquid composition of Example 1. Mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１４＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１２６ｇそれぞれ秤量し、実施例１の液組成物に更にフッ素含有アクリレートモノマーである２，２，２−トリフルオロエチルアクリレート０．２５０ｇを添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 14>
0.185 g of a 12% aqueous sodium hydroxide solution and 0.126 g of a polymerization initiator were respectively weighed, and 0.250 g of a fluorine-containing acrylate monomer, 2,2,2-trifluoroethyl acrylate, was further added to the liquid composition of Example 1. Was added and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１５＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１１７ｇそれぞれ秤量し、実施例１の液組成物に更にフッ素含有アクリレートモノマーである２，２，３，３−テトラフルオロプロピルアクリレート０．０９３ｇを添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 15>
0.185 g of a 12% aqueous sodium hydroxide solution and 0.117 g of a polymerization initiator were weighed, and the liquid composition of Example 1 was further added with 2,2,3,3-tetrafluoropropyl acrylate, a fluorine-containing acrylate monomer. 0.093 g was added and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１６＞
１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１１７ｇそれぞれ秤量し、実施例１の液組成物に更にフッ素含有アクリレートモノマーである１Ｈ，１Ｈ，５Ｈ−オクタフルオロプロペンチルアクリレート０．０９３ｇと式（３）で表されるスルホベタイン型化合物を０．００８ｇをそれぞれ添加混合した。それ以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 16>
0.185 g of a 12% aqueous sodium hydroxide solution and 0.117 g of a polymerization initiator were weighed, and the liquid composition of Example 1 was further added with a fluorine-containing acrylate monomer, 1H, 1H, 5H-octafluoropropentyl acrylate. 093 g and 0.008 g of the sulfobetaine type compound represented by the formula (3) were added and mixed. Otherwise, using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１７＞
多官能アクリレートモノマーとして多官能アクリル酸エステル（第一工業製薬製ＭＦ−００１）を選定し、アクリル酸を０．１００ｇ、上記多官能アクリレートモノマーを１．０００ｇと３官能アクリレートモノマーのビスコート♯３００を０．８５０ｇと重合開始剤を０．１１７ｇそれぞれ秤量した。それ以外、実施例１と同じアクリル酸、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 17>
A polyfunctional acrylate ester (MF-001 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was selected as the polyfunctional acrylate monomer, and 0.100 g of acrylic acid, 1.000 g of the polyfunctional acrylate monomer, and biscoat # 300 of a trifunctional acrylate monomer were used. 0.850 g and 0.117 g of the polymerization initiator were weighed respectively. Otherwise, using the same acrylic acid, alkali aqueous solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１８＞
多官能アクリレートモノマーの代わりに多官能アクリレートオリゴマーを用いた。このオリゴマーとしてウレタンアクリレートオリゴマー（第一工業製薬製ＧＸ−８８０１Ａ）を選定した。多官能アクリレートオリゴマーを１．６６０ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１１２ｇそれぞれ秤量した。それ以外、実施例１と同じアクリル酸、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 18>
A polyfunctional acrylate oligomer was used instead of the polyfunctional acrylate monomer. As this oligomer, a urethane acrylate oligomer (GX-8801A manufactured by Daiichi Kogyo Seiyaku) was selected. 1.660 g of a polyfunctional acrylate oligomer, 0.185 g of a 12% aqueous sodium hydroxide solution, and 0.112 g of a polymerization initiator were weighed. Otherwise, using the same acrylic acid, alkali aqueous solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例１９＞
多官能アクリレートモノマーの代わりに多官能アクリレートオリゴマーを用いた。このオリゴマーとしてウレタンアクリレートオリゴマー（荒川化学工業製ビームセット５７７）を選定した。この多官能アクリレートオリゴマーを１．４５０ｇ、アクリル酸を０．５８０ｇ、１２％水酸化ナトリウム水溶液を０．５３７ｇ、重合開始剤を０．１２２ｇそれぞれ秤量した。それ以外、実施例１と同じアクリル酸、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 19>
A polyfunctional acrylate oligomer was used instead of the polyfunctional acrylate monomer. A urethane acrylate oligomer (Arakawa Chemical Industries beam set 577) was selected as this oligomer. 1.450 g of this polyfunctional acrylate oligomer, 0.580 g of acrylic acid, 0.537 g of a 12% aqueous sodium hydroxide solution, and 0.122 g of a polymerization initiator were weighed. Otherwise, using the same acrylic acid, alkali aqueous solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例２０＞
多官能アクリレートモノマーの代わりに多官能アクリレートオリゴマーを用いた。このオリゴマーとしてウレタンアクリレートオリゴマー（日本合成化学製紫光７０００Ｂ）を選定した。この多官能アクリレートオリゴマーを１．６５６ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１１２ｇそれぞれ秤量した。それ以外、実施例１と同じアクリル酸、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 20>
A polyfunctional acrylate oligomer was used instead of the polyfunctional acrylate monomer. As this oligomer, a urethane acrylate oligomer (Shinko 7000B manufactured by Nippon Synthetic Chemical Co., Ltd.) was selected. 1.656 g of this polyfunctional acrylate oligomer, 0.185 g of a 12% aqueous sodium hydroxide solution, and 0.112 g of a polymerization initiator were weighed. Otherwise, using the same acrylic acid, alkali aqueous solution, polymerization initiator, and solvent as in Example 1, a liquid composition was prepared in the same manner as in Example 1.
＜実施例２１＞
アクリル酸を０．５００ｇ、多官能アクリレートモノマーを４．１００ｇ、２０％水酸化ナトリウム水溶液を０．２７８ｇ、重合開始剤を０．２７６ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 21>
The same acrylic acid and polyfunctional acrylate as in Example 1 except that 0.500 g of acrylic acid, 4.100 g of polyfunctional acrylate monomer, 0.278 g of 20% aqueous sodium hydroxide solution, and 0.276 g of polymerization initiator were weighed respectively. A liquid composition was prepared in the same manner as in Example 1 using the monomer, the polymerization initiator, and the solvent.
＜実施例２２＞
アクリル酸を０．５００ｇ、多官能アクリレートモノマーを４．１００ｇ、３．４％水酸化ナトリウム水溶液を０．４６３ｇ、重合開始剤を０．２７６ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 22>
0.500 g of acrylic acid, 4.100 g of a polyfunctional acrylate monomer, 0.463 g of a 3.4% aqueous sodium hydroxide solution, and 0.276 g of a polymerization initiator, respectively, except that the same acrylic acid and polyacrylic acid as in Example 1 were weighed. Using a functional acrylate monomer, a polymerization initiator, and a solvent, a liquid composition was prepared in the same manner as in Example 1.
＜実施例２３＞
重合開始剤として熱重合開始剤であるペルオキソ二硫酸アンモニウムを用いた。この重合開始剤０．１１１ｇを秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Example 23>
As a polymerization initiator, ammonium peroxodisulfate, which is a thermal polymerization initiator, was used. A liquid composition was prepared in the same manner as in Example 1, except that 0.111 g of the polymerization initiator was weighed, and using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, and solvent as in Example 1.
＜比較例１＞
１２％水酸化ナトリウム水溶液を０．０４６ｇ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 1>
A liquid composition was prepared in the same manner as in Example 1 using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, except that 0.046 g of a 12% aqueous sodium hydroxide solution was weighed. Prepared.
＜比較例２＞
１２％水酸化ナトリウム水溶液を０．４６３ｇ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 2>
A liquid composition was prepared in the same manner as in Example 1 using the same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, polymerization initiator, and solvent as in Example 1, except that 0.463 g of a 12% aqueous sodium hydroxide solution was weighed. Prepared.
＜比較例３＞
アクリル酸を０．０５０ｇ、多官能アクリレートモノマーを２．０７０ｇ、１２％水酸化ナトリウム水溶液を０．０４６ｇ、重合開始剤を０．１２７ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 3>
The same acrylic acid and polyfunctional acrylate as in Example 1 except that 0.050 g of acrylic acid, 2.070 g of polyfunctional acrylate monomer, 0.046 g of 12% aqueous sodium hydroxide solution, and 0.127 g of polymerization initiator were weighed respectively. A liquid composition was prepared in the same manner as in Example 1 using the monomer, the aqueous alkali solution, the polymerization initiator, and the solvent.
＜比較例４＞
多官能アクリレートモノマーを０．４６０ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．０４０ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 4>
The same acrylic acid, polyfunctional acrylate monomer, alkali aqueous solution, and polymerization start as in Example 1 except that 0.460 g of the polyfunctional acrylate monomer, 0.185 g of the 12% aqueous sodium hydroxide solution, and 0.040 g of the polymerization initiator were respectively weighed. A liquid composition was prepared in the same manner as in Example 1 using the agent and the solvent.
＜比較例５＞
多官能アクリレートモノマーを１．６０６ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．００９ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 5>
The same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, and polymerization start as in Example 1 except that 1.606 g of a polyfunctional acrylate monomer, 0.185 g of a 12% aqueous sodium hydroxide solution, and 0.009 g of a polymerization initiator were weighed respectively. A liquid composition was prepared in the same manner as in Example 1 using the agent and the solvent.
＜比較例６＞
多官能アクリレートモノマーを１．６０６ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．２２３ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 6>
The same acrylic acid, polyfunctional acrylate monomer, aqueous alkali solution, and polymerization start as in Example 1 except that 1.606 g of the polyfunctional acrylate monomer, 0.185 g of the 12% aqueous sodium hydroxide solution, and 0.223 g of the polymerization initiator were respectively weighed. A liquid composition was prepared in the same manner as in Example 1 using the agent and the solvent.
＜比較例７＞
多官能アクリレートモノマーとしてビニル基を２個有するヒドロキシビバリン酸ネオペンチルグリコールジアクリレート（第一工業製薬製ニューフロンティアＨＰＮ）を選定した。この多官能アクリレートモノマーを１．５７６ｇ、１２％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．１０７ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、アルカリ水溶液、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 7>
As the polyfunctional acrylate monomer, neopentyl glycol diacrylate hydroxybivalate having two vinyl groups (New Frontier HPN manufactured by Daiichi Kogyo Seiyaku) was selected. The same acrylic acid, alkali aqueous solution, polymerization initiator, and solvent as in Example 1 were used except that 1.576 g of this polyfunctional acrylate monomer, 0.185 g of a 12% aqueous sodium hydroxide solution, and 0.107 g of a polymerization initiator were respectively weighed. A liquid composition was prepared in the same manner as in Example 1.
＜比較例８＞
アクリル酸を０．５００ｇ、多官能アクリレートモノマーを４．１００ｇ、３０％水酸化ナトリウム水溶液を０．１８５ｇ、重合開始剤を０．２７６ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 8>
The same acrylic acid and polyfunctional acrylate as in Example 1 except that 0.500 g of acrylic acid, 4.100 g of polyfunctional acrylate monomer, 0.185 g of 30% aqueous sodium hydroxide solution and 0.276 g of polymerization initiator were weighed respectively. A liquid composition was prepared in the same manner as in Example 1 using the monomer, the polymerization initiator, and the solvent.
＜比較例９＞
アクリル酸を０．５００ｇ、多官能アクリレートモノマーを４．１００ｇ、２．５％水酸化ナトリウム水溶液を２．２２０ｇ、重合開始剤を０．２７６ｇそれぞれ秤量した以外、実施例１と同じアクリル酸、多官能アクリレートモノマー、重合開始剤、溶媒を用いて、実施例１と同様にして液組成物を調製した。
<Comparative Example 9>
0.500 g of acrylic acid, 4.100 g of a polyfunctional acrylate monomer, 2.220 g of a 2.5% aqueous sodium hydroxide solution, and 0.276 g of a polymerization initiator, respectively, except that the same acrylic acid and polyacrylic acid as in Example 1 were weighed. A liquid composition was prepared in the same manner as in Example 1 using a functional acrylate monomer, a polymerization initiator, and a solvent.
実施例１〜２３及び比較例１〜９の液組成物における、アクリル酸、多官能アクリレートモノマー又は多官能アクリレートオリゴマー、アルカリの種類及び各秤量値を表１に、また重合開始剤、溶媒、その他のモノマー、両性型含窒素フッ素系化合物の種類及び各秤量値を表２にそれぞれ示す。なお、表１中、ビニル基を３個有する、実施例１の多官能アクリレートモノマーは「３官能モノマー１」とし、実施例１１の多官能アクリレートモノマーは「３官能モノマー２」としてそれぞれ示している。また実施例１８〜２０の多官能アクリレートオリゴマーは「多官能オリゴマー１」、「多官能オリゴマー２」、「多官能オリゴマー３」として示し、比較例７のビニル基を２個有する多官能アクリレートモノマーは「２官能モノマー」として示している。また表２中、両性型含窒素フッ素系化合物の種類として、例えば「式（２）」と記載したものは、「式（２）に示される化合物」を意味する。 In the liquid compositions of Examples 1 to 23 and Comparative Examples 1 to 9, acrylic acid, polyfunctional acrylate monomer or polyfunctional acrylate oligomer, types of alkali and respective weighed values are shown in Table 1, and a polymerization initiator, a solvent, and others Table 2 shows the types of monomers, amphoteric nitrogen-containing fluorine-based compounds, and their weighed values. In Table 1, the polyfunctional acrylate monomer of Example 1 having three vinyl groups is referred to as "trifunctional monomer 1", and the polyfunctional acrylate monomer of Example 11 is referred to as "trifunctional monomer 2". . The polyfunctional acrylate oligomers of Examples 18 to 20 are referred to as “polyfunctional oligomer 1”, “polyfunctional oligomer 2”, and “polyfunctional oligomer 3”, and the polyfunctional acrylate monomer having two vinyl groups of Comparative Example 7 is It is shown as "bifunctional monomer". In Table 2, as a kind of the amphoteric nitrogen-containing fluorine-based compound, for example, a compound described as “formula (2)” means “a compound represented by formula (2)”.
また実施例１〜２３及び比較例１〜９の液組成物における、アクリル酸に対するアルカリの割合、多官能アクリレートモノマー・多官能アクリレートオリゴマーに対するアクリル酸の割合、アクリル酸と多官能アクリレートモノマー・多官能アクリレートオリゴマーを合計した全アクリルに対する重合開始剤の割合、アルカリ水溶液中の水に対するアクリル酸塩の割合、液組成物中のその他のモノマー及び両性型含窒素フッ素系化合物の各割合を表３に示す。上記「その他のモノマー」とは、リン酸含有アクリレートモノマー又はフッ素含有アクリレートモノマーをいう。 Further, in the liquid compositions of Examples 1 to 23 and Comparative Examples 1 to 9, the ratio of alkali to acrylic acid, the ratio of acrylic acid to polyfunctional acrylate monomer / polyfunctional acrylate oligomer, acrylic acid and polyfunctional acrylate monomer / polyfunctional Table 3 shows the ratio of the polymerization initiator to the total acryl obtained by adding the acrylate oligomer, the ratio of the acrylate to the water in the aqueous alkali solution, and the ratio of each of the other monomers and the amphoteric nitrogen-containing fluorine-based compound in the liquid composition. . The "other monomer" refers to a phosphoric acid-containing acrylate monomer or a fluorine-containing acrylate monomer.
＜比較試験及び評価＞
実施例１〜２３及び比較例１〜９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.8）を用いて、厚さ６０μｍ、たて２９７ｍｍ、よこ２１０ｍｍのポリエチレンテレフタレート（ＰＥＴ）のフィルム基材（東レ社製ルミラー100A60）上にそれぞれ乾燥後の厚さが１〜３μｍとなるように塗布し、塗膜を形成した。実施例１〜２２及び比較例１〜９の液組成物から形成された塗膜については、７０℃の大気雰囲気中にて３０秒間乾燥し、更に、この乾燥した塗膜に紫外線を照射量４８０ｍＪ／ｃｍ２にて照射し、３１種類の防汚性膜を得た。一方、実施例２３で得られた液組成物から形成された塗膜については、１００℃の大気雰囲気中にて３０分間乾燥して１種類の防汚性膜を得た。これらの防汚性膜について、膜表面の水濡れ性（親水性）、撥油性、ヘキサデカンの転落性及び膜の耐水性を評価した。これらの結果を表３に示す。なお、表３における割合は分母を１００として算出し、算出値の小数点以下を四捨五入した値である。また比較例８の液組成物は、フロックが発生し、塗料化できなかったため、水とｎ−ヘキサデカンの各接触角、ヘキサデカンの転落性及び膜の耐水性は測定できなかった。
<Comparison test and evaluation>
Using a bar coater (manufactured by Yasuda Seiki Seisakusho, Model No. 8), the liquid compositions obtained in Examples 1 to 23 and Comparative Examples 1 to 9 were polyethylene terephthalate having a thickness of 60 μm, a length of 297 mm, and a width of 210 mm. The film was applied on a (PET) film base material (Lumirror 100A60 manufactured by Toray Industries, Inc.) so that the thickness after drying became 1 to 3 μm to form a coating film. The coating films formed from the liquid compositions of Examples 1 to 22 and Comparative Examples 1 to 9 were dried in an air atmosphere at 70 ° C. for 30 seconds, and the dried coating films were irradiated with ultraviolet rays at 480 mJ. / Cm 2 to obtain 31 types of antifouling films. On the other hand, the coating film formed from the liquid composition obtained in Example 23 was dried in an air atmosphere at 100 ° C. for 30 minutes to obtain one kind of antifouling film. With respect to these antifouling films, water wettability (hydrophilicity), oil repellency, hexadecane falling off property and water resistance of the film surface were evaluated. Table 3 shows the results. The ratio in Table 3 is a value calculated by setting the denominator to 100 and rounding off the calculated value to the decimal point. In addition, the liquid composition of Comparative Example 8 generated flocs and could not be formed into a coating, so that the respective contact angles of water and n-hexadecane, the falling property of hexadecane, and the water resistance of the film could not be measured.
(1) 膜表面の水濡れ性（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ＰＥＴフィルム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、膜表面の水濡れ性（親水性）を評価した。
(1) Water wettability of the film surface (contact angle)
Using a drop master DM-700 manufactured by Kyowa Interface Science, ion-exchanged water of 22 ° C. ± 1 ° C. is prepared in the syringe, and a 2 μL droplet is ejected from the tip of the needle of the syringe. Next, the antifouling film on the PET film to be evaluated is brought close to the droplet, and the droplet is attached to the antifouling film. The contact angle of the attached water was measured. The value obtained by analyzing the contact angle one second after the water touched the film surface in the stationary state by the θ / 2 method was defined as the water contact angle, and the water wettability (hydrophilicity) of the film surface was evaluated.
(2) 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ＰＥＴフィルム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。
(2) Oil repellency of the film surface (contact angle)
Using a drop master DM-700 manufactured by Kyowa Interface Science, prepare n-hexadecane (hereinafter referred to as oil) at 22 ° C. ± 1 ° C. in a syringe, and drop 2 μL of droplet from the tip of the needle of the syringe. I do. Next, the antifouling film on the PET film to be evaluated is brought close to the droplet, and the droplet is attached to the antifouling film. The contact angle of the attached oil was measured. The value obtained by analyzing the contact angle one second after the oil touched the film surface in the stationary state by the θ / 2 method was defined as the oil contact angle, and the oil repellency of the film surface was evaluated.
(3) ヘキサデカンの転落性
上記(2)の膜表面の撥油性試験時に用いたシリンジの針の先端からｎ−ヘキサデカンの２μＬの液滴を水平状態に置かれたＰＥＴフィルム上に落下させた後、このＰＥＴフィルムを７０度傾斜させ、ｎ−ヘキサデカンが流れ落ちるか否か、即ちヘキサデカンの転落性を評価した。更に、転落した試料に関しては、転落角を測定した。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５μＬの液滴を飛び出した状態にする。次いで評価するＰＥＴフィルム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。次に、試料をのせた台を傾けて、油が転落を開始する角度を測定した。
(3) Falling property of hexadecane After dropping 2 μL of n-hexadecane droplet from the tip of the needle of the syringe used in the oil repellency test on the film surface in the above (2) onto a PET film placed horizontally. The PET film was inclined at 70 degrees, and whether or not n-hexadecane flowed off, that is, the falling property of hexadecane was evaluated. Further, the falling angle of the fallen sample was measured. Using a drop master DM-700 manufactured by Kyowa Interface Science, prepare n-hexadecane (hereinafter referred to as oil) at 22 ° C. ± 1 ° C. in a syringe, and drop a 5 μL droplet from the tip of the syringe needle. I do. Next, the antifouling film on the PET film to be evaluated is brought close to the droplet, and the droplet is attached to the antifouling film. Next, the base on which the sample was placed was tilted, and the angle at which the oil started to fall was measured.
(4) 膜の耐水性
評価する防汚性膜をＰＥＴフィルムとともに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、目視にて、防汚性膜がＰＥＴフィルムから剥離するか否か、即ち膜の耐水性を評価した。
(4) Water resistance of the membrane The antifouling membrane to be evaluated is placed in a horizontal state at a flow rate of 500 mL / min of tap water at 5 to 15 ° C together with the PET film for 24 hours in a horizontal state, and the stain resistance is visually observed. Whether or not the water-resistant film was peeled from the PET film, that is, the water resistance of the film was evaluated.
表３から明らかなように、比較例１では、アクリル酸に対するアルカリが３質量部であったため、耐水試験で膜は膨潤剥離しなかったが、膜表面の水濡れ性及び撥油性に劣り、ヘキサデカンの液滴は転落しなかった。比較例２では、アクリル酸に対するアルカリが２８質量部であったため、膜表面の水濡れ性及び撥油性は良好であり、ヘキサデカンの液滴は転落したが、耐水試験で膜は膨潤剥離した。比較例３では、全アクリルに対するアクリル酸の割合が２質量部であったため、耐水試験で膜は膨潤剥離しなかったが、膜表面の水濡れ性及び撥油性に劣り、ヘキサデカンの液滴は転落しなかった。比較例４では、全アクリルに対するアクリル酸の割合が４３質量部であったため、膜表面の水濡れ性が良好であったが、撥油性に劣り、ヘキサデカンの液滴は転落せず、耐水試験で膜は膨潤剥離した。 As is clear from Table 3, in Comparative Example 1, the film did not swell and peel in the water resistance test because the alkali to acrylic acid was 3 parts by mass, but the film surface was poor in water wettability and oil repellency, and hexadecane Did not fall. In Comparative Example 2, since the alkali with respect to acrylic acid was 28 parts by mass, water wettability and oil repellency of the film surface were good, and hexadecane droplets fell, but the film swelled and peeled off in the water resistance test. In Comparative Example 3, since the ratio of acrylic acid to all acryl was 2 parts by mass, the film did not swell and peel in the water resistance test, but the water wettability and oil repellency of the film surface were poor, and hexadecane droplets fell. Did not. In Comparative Example 4, the ratio of acrylic acid to the total acryl was 43 parts by mass, so that the water wettability on the film surface was good, but the oil repellency was poor, and the droplets of hexadecane did not fall down, and the water resistance test was performed. The film swelled and peeled.
また比較例５では、光重合開始剤の割合が全アクリルに対して０．５質量部であったため、耐水試験で膜は膨潤剥離しなかったが、膜表面の水濡れ性及び撥油性に劣り、ヘキサデカンの液滴は転落しなかった。比較例６では、光重合開始剤の割合が全アクリルに対して１２質量部であったため、成膜後の膜にひび割れが発生していた。ただし、膜表面の水濡れ性及び撥油性は良好であった。比較例７では、ビニル基が２個のアクリレートであったため、膜表面の水濡れ性が良好であったが、撥油性に劣り、ヘキサデカンの液滴は転落せず、耐水試験で膜は膨潤剥離した。比較例８では、水に対するアクリル酸ナトリウムの割合が１０１質量部であったため、得られた液組成物はフロック（白だま）が発生し、塗料化することができなかった。比較例９では、水に対するアクリル酸ナトリウムの割合が６質量部であったため、耐水試験で膜は膨潤剥離しなかったが、膜表面の水濡れ性及び撥油性に劣り、ヘキサデカンの液滴は転落しなかった。 In Comparative Example 5, since the ratio of the photopolymerization initiator was 0.5 parts by mass with respect to the total acryl, the film did not swell and peel in the water resistance test, but was poor in water wettability and oil repellency of the film surface. The hexadecane droplet did not fall. In Comparative Example 6, since the ratio of the photopolymerization initiator was 12 parts by mass with respect to the total acryl, cracks were generated in the formed film. However, the water wettability and oil repellency of the film surface were good. In Comparative Example 7, since the vinyl group was two acrylates, the water wettability of the film surface was good, but the oil repellency was poor, and hexadecane droplets did not fall down, and the film swelled and peeled off in the water resistance test. did. In Comparative Example 8, since the ratio of sodium acrylate to water was 101 parts by mass, the obtained liquid composition generated flocs (white balls) and could not be formed into a paint. In Comparative Example 9, since the ratio of sodium acrylate to water was 6 parts by mass, the film did not swell and peel in the water resistance test, but the film surface was poor in water wettability and oil repellency, and hexadecane droplets fell. Did not.
これに対して、表３から明らかなように、実施例１〜２３では、アクリル酸に対してアルカリが５〜２３質量部の範囲に含まれ、多官能アクリレートモノマー・多官能アクリレートオリゴマーに対してアクリル酸が５〜４０質量部の範囲に含まれ、全アクリルに対して重合開始剤が１〜１０質量部の範囲に含まれ、かつ水に対してアクリル酸塩が８〜６０質量部の範囲に含まれていたため、膜表面の水濡れ性及び撥油性は良好であり、ヘキサデカンの液滴は転落せずに、耐水試験で膜は膨潤剥離しなかった。 On the other hand, as is clear from Table 3, in Examples 1 to 23, the alkali is contained in the range of 5 to 23 parts by mass with respect to acrylic acid, and the alkali is contained in the polyfunctional acrylate monomer / polyfunctional acrylate oligomer. Acrylic acid is contained in the range of 5 to 40 parts by mass, the polymerization initiator is contained in the range of 1 to 10 parts by mass based on the total acryl, and the acrylate is in the range of 8 to 60 parts by mass with respect to water. , The water wettability and oil repellency of the film surface were good, hexadecane droplets did not fall, and the film did not swell and peel in the water resistance test.
本発明の防汚性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等において、油汚れを防止する分野に用いられる。 The liquid composition for forming an antifouling film of the present invention is used in the field of preventing oil stains in factories that use machine oil, kitchens where oil is scattered, range hoods where oil vapor is trapped, and the like.
Claims (3)
前記アクリル酸１００質量部に対して前記アルカリを５〜２３質量部含み、
前記多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマー１００質量部に対して前記アクリル酸を５〜４０質量部含み、
前記アクリル酸と前記多官能アクリレートモノマー及び／又は多官能アクリレートオリゴマーを合計した全アクリル１００質量部に対して前記重合開始剤を１〜１０質量部含み、かつ
前記水溶液中の水１００質量部に対して前記アクリル酸と前記アルカリで形成されるアクリル酸塩を８〜６０質量部含む
ことを特徴とする防汚性膜形成用液組成物。 Acrylic acid, an aqueous solution containing an alkali, a polyfunctional acrylate monomer and / or a polyfunctional acrylate oligomer each having at least three vinyl groups, a polymerization initiator and a solvent,
Contains 5 to 23 parts by mass of the alkali with respect to 100 parts by mass of the acrylic acid,
The polyfunctional acrylate monomer and / or 5 to 40 parts by mass of the acrylic acid is contained with respect to 100 parts by mass of the polyfunctional acrylate oligomer,
The acrylic acid and the polyfunctional acrylate monomer and / or polyfunctional acrylate oligomer containing 1 to 10 parts by mass of the polymerization initiator based on 100 parts by mass of the total acryl, and 100 parts by mass of water in the aqueous solution A liquid composition for forming an antifouling film, comprising 8 to 60 parts by mass of an acrylate formed by the acrylic acid and the alkali.
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