JP5013779B2 - Water-soluble wetting agent composition - Google Patents
Water-soluble wetting agent composition Download PDFInfo
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- JP5013779B2 JP5013779B2 JP2006235275A JP2006235275A JP5013779B2 JP 5013779 B2 JP5013779 B2 JP 5013779B2 JP 2006235275 A JP2006235275 A JP 2006235275A JP 2006235275 A JP2006235275 A JP 2006235275A JP 5013779 B2 JP5013779 B2 JP 5013779B2
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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Description
本発明は、濡れの作用を増大する水溶性湿潤剤に関する。より詳細には、分岐鎖を有するフッ素系界面活性剤と、炭化水素系界面活性剤との相乗的作用により、濡れの作用を増大する水溶性湿潤剤に関する。 The present invention relates to a water-soluble wetting agent that increases the action of wetting. More specifically, the present invention relates to a water-soluble wetting agent that increases the wetting action by a synergistic action of a branched fluorine-containing surfactant and a hydrocarbon surfactant.
表面張力が高い水及び一定の水溶液は、樹脂や金属に対して濡れ難い。一方、各種コーティングや表面処理、洗浄等を行う場合、対象とする基板に対して十分に濡れることが必須条件である。 Water with a high surface tension and a certain aqueous solution are difficult to wet with resin and metal. On the other hand, when various coatings, surface treatments, cleaning, and the like are performed, it is an essential condition that the substrate is sufficiently wetted.
これらのことから、各種コーティング液、表面処理液や洗浄液等に、濡れ性を向上させる目的で界面活性剤を添加することがある。しかしながら、各種コーティング液や表面処理液等の塗工液に関しては、十分な湿潤性が得られない場合もある。 For these reasons, a surfactant may be added to various coating liquids, surface treatment liquids, cleaning liquids and the like for the purpose of improving wettability. However, sufficient wettability may not be obtained with respect to coating liquids such as various coating liquids and surface treatment liquids.
濡れ性を向上させるために、直鎖型フッ素系界面活性剤と炭化水素系界面活性剤とを併用した水溶液の組成物が知られている（特許文献１）。しかしながら、本組成物ではまだ十分な湿潤性が得られないという問題があり、さらに湿潤効果に改善の余地があった。
本発明は、濡れの作用を増大する水溶性湿潤剤組成物を提供することを目的とする。 It is an object of the present invention to provide a water-soluble wetting agent composition that increases the action of wetting.
本発明者は、上記課題を解決すべく鋭意検討を行った結果、分岐鎖を有するフッ素系界面活性剤と、炭化水素系界面活性剤とを併用することにより、湿潤性が相乗的に向上することを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to solve the above problems, the present inventor synergistically improves wettability by using a fluorine-containing surfactant having a branched chain and a hydrocarbon-based surfactant in combination. I found out. The present invention has been completed based on such findings.
即ち、本発明は、以下に掲げる態様の発明を提供する。 That is, this invention provides the invention of the aspect hung up below.
項１．分岐鎖を有するフッ素系界面活性剤、及び炭化水素系界面活性剤を含有することを特徴とする水溶性湿潤剤組成物。 Item 1. A water-soluble wetting agent composition comprising a fluorine-containing surfactant having a branched chain and a hydrocarbon-based surfactant.
項２．フッ素系界面活性剤の分岐鎖がパーフルオロアルケニル基であることを特徴とする項１記載の水溶性湿潤剤組成物。 Item 2. Item 2. The water-soluble wetting agent composition according to Item 1, wherein the branched chain of the fluorosurfactant is a perfluoroalkenyl group.
項３．フッ素系界面活性剤の分岐鎖が、下記式（１）または（２）で表されるパーフルオロアルケニル基であることを特徴とする項１または２に記載の水溶性湿潤剤組成物。 Item 3. Item 3. The water-soluble wetting agent composition according to Item 1 or 2, wherein the branched chain of the fluorosurfactant is a perfluoroalkenyl group represented by the following formula (1) or (2).
項４．分岐鎖を有するフッ素系界面活性剤の添加量が０．００１〜９５重量％かつ炭化水素系界面活性剤の添加量が０．００１〜８０重量％である項１〜３のいずれか一項に記載の水溶性湿潤剤組成物。 Item 4. The addition amount of the fluorine-containing surfactant having a branched chain is 0.001 to 95% by weight, and the addition amount of the hydrocarbon surfactant is 0.001 to 80% by weight. The water-soluble wetting agent composition described.
項５．分岐鎖を有するフッ素系界面活性剤と炭化水素系界面活性剤との重量比が９５：５〜２０：８０であることを特徴とする項１〜４のいずれか一項に記載の水溶性湿潤剤組成物。
項６．項１〜５のいずれか一項に記載の水溶性湿潤剤組成物を含む塗工液組成物。 Item 6. The coating liquid composition containing the water-soluble wetting agent composition as described in any one of claim | item 1 -5.
項７．分岐鎖を有するフッ素系界面活性剤の含有量が０．００１〜１重量％かつ炭化水素系界面活性剤の含有量が０．００１〜１重量％である項６に記載の塗工液組成物。 Item 7. Item 7. The coating liquid composition according to Item 6, wherein the content of the fluorine-containing surfactant having a branched chain is 0.001 to 1% by weight and the content of the hydrocarbon surfactant is 0.001 to 1% by weight. .
項８．項６または７に記載の塗工液組成物を用いて基板をコーティングすることを特徴とする塗工液のコーティング方法。 Item 8. Item 8. A coating solution coating method comprising coating a substrate using the coating solution composition according to Item 6 or 7.
項９．基板が、樹脂、金属またはガラスからなることを特徴とする、項８に記載の方法。 Item 9. Item 9. The method according to Item 8, wherein the substrate is made of resin, metal, or glass.
項１０．樹脂が、（メタ）アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリスチレン樹脂またはフッ素樹脂であることを特徴とする、項９に記載の方法。
項１１．金属が、鉄、ステンレス、アルミニウムまたはアルミニウム合金であることを特徴とする、項９に記載の方法。
Item 11.
本発明に係る水溶性湿潤剤組成物は、相乗的な濡れの作用を増大する効果を発揮することにより、より低濃度で十分な濡れの作用を増大する効果が得られる。これによって、各種基板に対して高い湿潤性を発揮するコーティング液や表面処理液等の塗工液を得ることができる。 The water-soluble wetting agent composition according to the present invention exhibits an effect of increasing the synergistic wetting action, thereby obtaining an effect of increasing the sufficient wetting action at a lower concentration. As a result, coating liquids such as coating liquids and surface treatment liquids that exhibit high wettability with respect to various substrates can be obtained.
本発明の方法を用いることによって、基板に対して満遍なく均一なコーティングをすることができる。また、比較的高価なフッ素系界面活性剤の使用量を減らしながらも高い濡れ性を示す塗工液を得ることができる。 By using the method of the present invention, it is possible to uniformly coat the substrate. In addition, it is possible to obtain a coating liquid exhibiting high wettability while reducing the amount of the relatively expensive fluorine-based surfactant used.
本発明の水溶性湿潤剤組成物は、分岐鎖を有するフッ素系界面活性剤と、炭化水素系界面活性剤とを含有してなる。 The water-soluble wetting agent composition of the present invention comprises a fluorinated surfactant having a branched chain and a hydrocarbon surfactant.
本発明において、フッ素系界面活性剤の分岐鎖は、特に限定されないが、パーフルオロアルケニル基であることが好ましく、更に好ましくは式（１）または（２）で示される。 In the present invention, the branched chain of the fluorosurfactant is not particularly limited, but is preferably a perfluoroalkenyl group, and more preferably represented by the formula (1) or (2).
また、分岐鎖を有するフッ素系界面活性剤としては、陰イオン性、非イオン性、陽イオン性または両性のフッ素系界面活性剤が挙げられるが、陰イオン性または非イオン性のフッ素系界面活性剤が好ましい。 In addition, examples of the fluorine-containing surfactant having a branched chain include anionic, nonionic, cationic or amphoteric fluorine-based surfactants, and anionic or nonionic fluorine-based surfactants. Agents are preferred.
塗工液の有効成分は、陰イオン性である場合が多いので、分岐鎖を有するフッ素系界面活性剤も陰イオン性または非イオン性のものを用いることによって、界面活性剤と陰イオンとの相互作用による凝集等を生じさせることなく、それぞれを塗工液中に安定して溶解、分散させておくことができる。 Since the active ingredient of the coating liquid is often anionic, the use of anionic or nonionic fluorinated surfactants having a branched chain allows the surfactant and anion to be used. Each can be stably dissolved and dispersed in the coating liquid without causing aggregation or the like due to interaction.
具体的には、分岐鎖を有する陰イオン性フッ素系界面活性剤として、パーフルオロアルケニルオキシベンゼンスルホン酸ナトリウム（株式会社ネオス製；フタージェント１００、以降ＦＴ−１００と略す。株式会社ネオス製：フタージェント１１０、以降ＦＴ−１１０と略す）、パーフルオロアルケニルオキシベンジルホスホン酸（株式会社ネオス製；フタージェント１４０Ａ、以降ＦＴ−１４０Ａと略す）、パーフルオロアルケニルオキシフェニルスルホニル−Ｎ−メチルカルボン酸ナトリウム（株式会社ネオス製；フタージェント１５０、以降ＦＴ−１５０と略す）が挙げられる。 Specifically, as an anionic fluorosurfactant having a branched chain, sodium perfluoroalkenyloxybenzenesulfonate (manufactured by Neos Co., Ltd .; Footent 100, hereinafter abbreviated as FT-100. Made by Neos Co., Ltd .: Footer) Gento 110, hereinafter abbreviated as FT-110), perfluoroalkenyloxybenzylphosphonic acid (manufactured by Neos Co., Ltd .; aftergent 140A, hereinafter abbreviated as FT-140A), sodium perfluoroalkenyloxyphenylsulfonyl-N-methylcarboxylate ( Manufactured by Neos Co., Ltd .; aftergent 150, hereinafter abbreviated as FT-150).
ＦＴ−１００、ＦＴ−１４０Ａ、ＦＴ−１５０のパーフルオロアルケニル基は、式（１）の構造である。ＦＴ−１１０のパーフルオロアルケニル基は、式（２）の構造である。 The perfluoroalkenyl group of FT-100, FT-140A, and FT-150 has the structure of formula (1). The perfluoroalkenyl group of FT-110 has the structure of formula (2).
また、分岐鎖を有する非イオン性フッ素系界面活性剤として、α−ペルフルオロノネニルオキシ−ω−メチルポリエチレンオキシド（株式会社ネオス製：フタージェント２５０、以降ＦＴ−２５０と略す。株式会社ネオス製：ＦＴＸ−２１２ＭＨ）が挙げられる。 Further, as a nonionic fluorine-based surfactant having a branched chain, α-perfluorononenyloxy-ω-methylpolyethylene oxide (manufactured by Neos Co., Ltd .: Footent 250, hereinafter abbreviated as FT-250. Made by Neos Co., Ltd .: FTX-212MH).
ＦＴ−２５０、ＦＴＸ−２１２ＭＨのパーフルオロアルケニル基は、式（１）の構造である。 The perfluoroalkenyl group of FT-250 and FTX-212MH has the structure of formula (1).
また、分岐鎖を有する陽イオン性フッ素系界面活性剤として、ヨウ化フルオロアルキルトリメチルアンモニウム（株式会社ネオス製；フタージェント３００、以降ＦＴ−３００と略す。）、臭化フルオロアルキルトリアルキルアンモニウム（株式会社ネオス製；フタージェント３２０、以降ＦＴ−３２０と略す。）等が挙げられる。 Further, as a cationic fluorine-based surfactant having a branched chain, fluoroalkyltrimethylammonium iodide (manufactured by Neos Co., Ltd .; Footent 300, hereinafter abbreviated as FT-300), fluoroalkyltrialkylammonium bromide (stock) Manufactured by company Neos; footage 320, hereinafter abbreviated as FT-320).
ＦＴ−３００、ＦＴ３２０のパーフルオロアルケニル基は、式（１）の構造である。 The perfluoroalkenyl group of FT-300 and FT320 has the structure of formula (1).
また、分岐鎖を有する両イオン性フッ素系界面活性剤として、フルオロアルキルベタイン(株式会社ネオス製；フタージェント４００Ｓ、以降ＦＴ−４００Ｓと略す。)等が挙げられる。 Examples of the zwitterionic fluorosurfactant having a branched chain include fluoroalkylbetaines (manufactured by Neos Co., Ltd .; Footent 400S, hereinafter abbreviated as FT-400S).
ＦＴ−４００Ｓのパーフルオロアルケニル基は、式（１）の構造である。 The perfluoroalkenyl group of FT-400S has the structure of formula (1).
炭化水素系界面活性剤としては、陰イオン性、非イオン性、陽イオン性または両性の炭化水素系界面活性剤が挙げられるが、陰イオン性、非イオン性または両性の炭化水素系界面活性剤が好ましく、特に陰イオン性または非イオン性の炭化水素系界面活性剤が好ましい。 Hydrocarbon surfactants include anionic, nonionic, cationic or amphoteric hydrocarbon surfactants, but anionic, nonionic or amphoteric hydrocarbon surfactants. In particular, anionic or nonionic hydrocarbon surfactants are preferred.
塗工液の有効成分は、陰イオン性である場合が多いので、炭化水素系界面活性剤も陰イオン性または非イオン性のものを用いることによって、界面活性剤と陰イオンとの相互作用による凝集等を生じさせることなく、それぞれを塗工液中に安定して溶解、分散させておくことができる。 Since the active ingredient of the coating liquid is often anionic, by using an anionic or nonionic hydrocarbon surfactant, the interaction between the surfactant and the anion is effective. Each can be stably dissolved and dispersed in the coating solution without causing aggregation or the like.
具体的には、陰イオン性炭化水素系界面活性剤としては、脂肪酸塩（例えば、オレイン酸ナトリウム等）、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩（例えば、Ａｅｒｏｓｏｌ ＯＴ等）、カルボキシル化ポリオキシエチレンアルキルエーテル及びその塩（例えば、日光ケミカルズ社製ＮＩＫＫＯＬ ＥＣＴ−７等）、ポリオキシエチレンアルキルエーテル硫酸塩［例えば、日光ケミカルズ社製ＮＩＫＫＯＬ ＳＢＬ−２Ｎ−２７（以降ＳＢＬ−２Ｎ−２７と略す）、ＮＩＫＫＯＬ ＳＢＬ−４Ｎ等］、ナフタリンスルホン酸ホルマリン縮合物の塩［例えば、花王社製デモールＲＮ（以降デモールＲＮと略す）等］、アルキルスルホネート、アルキルエーテルカルボン酸塩、アルキル硫酸エステル塩、アルファオレフィンスルホネート、アルキルリン酸エステル塩、リン酸アルキルポリオキシエチレン塩等が挙げられる。 Specifically, examples of the anionic hydrocarbon surfactant include fatty acid salts (for example, sodium oleate), alkylbenzene sulfonates, alkylsulfosuccinates (for example, Aerosol OT), carboxylated polyoxyethylene, and the like. Alkyl ethers and salts thereof (for example, NIKKOL ECT-7 manufactured by Nikko Chemicals), polyoxyethylene alkyl ether sulfates (for example, NIKKOL SBL-2N-27 manufactured by Nikko Chemicals (hereinafter abbreviated as SBL-2N-27), NIKKOL SBL-4N, etc.], salts of naphthalenesulfonic acid formalin condensates [eg, DEMO RN manufactured by Kao Corporation (hereinafter abbreviated as DEMO RN), etc.], alkyl sulfonate, alkyl ether carboxylate, alkyl sulfate ester salt, alpha olefin sulfate Sulfonates, alkyl phosphates, alkyl phosphate polyoxyethylene salts, and the like.
非イオン性炭化水素系界面活性剤としては、ポリオキシエチレンアルキルエーテル［例えば、第一工業製薬社製ノイゲンＳＤ−６０（以降ＳＤ−６０と略す）、第一工業製薬社製ノイゲンＸＬ−５０（以降ＸＬ−５０と略す）、第一工業製薬社製ノイゲンＴＤＳ−５０（以降ＴＤＳ−５０と略す）、第一工業製薬社製ノイゲンＴＤＳ−８０（以降ＴＤＳ−８０と略す）、三洋化成工業社製サンノニックＳＳ−５０（以降ＳＳ−５０と略す）等］、ポリオキシエチレンアルキルフェニルエーテル、アルキルピロリドン（例えば、和光純薬工業社製試薬１−オクチル−２−ピロリドン等）、アルキルグルコシド（例えば、花王社製マイドール１０、花王社製マイドール１２等）、ソルビタン脂肪酸エステル［例えば、花王社製レオドールＳＰ−Ｌ１０（以降ＳＰ−Ｌ１０と略す）等］、モノ及びジエタノールアミン脂肪酸アミド［例えば、竹本油脂社製パイオニンＤ−９５１−Ｐ（以降Ｄ−９５１−Ｐと略す）等］、アルキルアミンのポリオキシエチレン付加物［例えば、日本油脂社製ナイミーンＬ−２０７（以降、Ｌ−２０７と略す）等］、エトキシレート化テトラメチルドデシンジオール［例えば、日信化学工業社製ダイノールＤＹＮＯＬ６０４（以降ＤＹＮＯＬ６０４と略す）等］、テトラメチルデシンジオール［例えば、日信化学工業社製サーフィノールＳＵＲＦＹＮＯＬ１０４ＰＡ（以降１０４ＰＡと略す）等］、グリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル、ポリオキシエチレンポリオキシプロピレングリコール、ポリエチレングリコール脂肪酸エステル、脂肪酸ポリオキシエチレンソルビタン等が挙げられる。
Examples of the nonionic hydrocarbon surfactant include polyoxyethylene alkyl ethers [for example, Neugen SD-60 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (hereinafter abbreviated as SD-60), Neugen XL-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Hereinafter referred to as XL-50), Neugen TDS-50 (hereinafter referred to as TDS-50) manufactured by Daiichi Kogyo Seiyaku, Neugen TDS-80 (hereinafter referred to as TDS-80) manufactured by Daiichi Kogyo Seiyaku, Sanyo Chemical Industries Sannonic SS-50 (hereinafter abbreviated as SS-50), etc.], polyoxyethylene alkylphenyl ether, alkylpyrrolidone (eg, reagent 1-octyl-2-pyrrolidone, etc., manufactured by Wako Pure Chemical Industries, Ltd.), alkyl glucoside (eg,
陽イオン性炭化水素系界面活性剤としては、アルキルアミン塩（例えば、花王社製アセタミン２４、アセタミン８６）、塩化アルキルトリメチルアンモニウム（例えば、ライオン社製アーカードＣ−５０）、塩化ジアルキルジメチルアンモニウム（例えば、ライオン社製；アーカード２Ｃ−７５）、ＥＯ付加型アンモニウムクロライド（例えば、ライオン社製；エソカードＣ／２５）等が挙げられる。 Examples of the cationic hydrocarbon-based surfactant include alkylamine salts (for example, Acetamine 24 and Acetamine 86 manufactured by Kao Corporation), alkyltrimethylammonium chloride (for example, Archard C-50 manufactured by Lion Corporation), dialkyldimethylammonium chloride (for example, , Lion Corporation; Arcard 2C-75), EO addition type ammonium chloride (for example, Lion Corporation; Esocard C / 25) and the like.
両性炭化水素系界面活性剤としては、アルキルベタイン［例えば、第一工業製薬社製アモーゲンＫ等］、脂肪酸アミドプロピルベタイン、２−アルキル−１−（−２−ヒドロキシエチル）イミダゾリニウム−１−アセテート、アルキルジアミノエチルグリシン、ジアルキルジアミノエチルグリシン、アルキルアミンオキシド等が挙げられる。 Examples of amphoteric hydrocarbon surfactants include alkylbetaines [for example, Amogen K manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], fatty acid amidopropylbetaines, 2-alkyl-1-(-2-hydroxyethyl) imidazolinium-1- Examples include acetate, alkyldiaminoethylglycine, dialkyldiaminoethylglycine, alkylamine oxide, and the like.
炭化水素系界面活性剤としては、非イオン性、陰イオン性または両性の中から選択される任意の炭化水素系界面活性剤が用いることができ、分岐鎖を有するフッ素系界面活性剤に対して、炭化水素系界面活性剤を２種以上併用してもよい。 As the hydrocarbon-based surfactant, any hydrocarbon-based surfactant selected from nonionic, anionic or amphoteric can be used. For the fluorine-based surfactant having a branched chain, Two or more hydrocarbon surfactants may be used in combination.
本発明の水溶性湿潤剤組成物において、分岐鎖を有するフッ素系界面活性剤：炭化水素系界面活性剤の配合割合は、重量部で９５：５〜２０：８０であり、好ましくは９０：１０〜４０：６０である。尚、分岐鎖を有するフッ素系界面活性剤：炭化水素系界面活性剤の配合割合が、前記９５：５〜２０：８０の範囲外であると、濡れの作用を増大する相乗効果は得られない。 In the water-soluble wetting agent composition of the present invention, the blending ratio of the fluorine-containing surfactant: hydrocarbon surfactant having a branched chain is 95: 5 to 20:80 by weight, preferably 90:10. ~ 40: 60. In addition, when the blending ratio of the fluorine-containing surfactant having a branched chain to the hydrocarbon-based surfactant is out of the range of 95: 5 to 20:80, a synergistic effect that increases the wetting action cannot be obtained. .
本発明の水溶性湿潤剤組成物における各々の界面活性剤の添加量は、分岐鎖を有するフッ素系界面活性剤の添加量が０．００１〜９５重量％かつ炭化水素系界面活性剤の添加量が０．００１〜８０重量％であり、好ましくは分岐鎖を有するフッ素系界面活性剤の添加量が０．００５〜９０重量％かつ炭化水素系界面活性剤の添加量が０．００５〜６０重量％である。両者の界面活性剤の一般的な配合割合が、下限値より少なければ湿潤剤としての効果が発揮できず、上限値より多いと、コストが高くなり経済的に好ましくない。 The addition amount of each surfactant in the water-soluble wetting agent composition of the present invention is such that the addition amount of the fluorine-containing surfactant having a branched chain is 0.001 to 95% by weight and the addition amount of the hydrocarbon-based surfactant. Is 0.001 to 80% by weight, preferably 0.005 to 90% by weight of the fluorine-containing surfactant having a branched chain and 0.005 to 60% by weight of the hydrocarbon-based surfactant. %. If the general blending ratio of both surfactants is less than the lower limit value, the effect as a wetting agent cannot be exhibited, and if it is more than the upper limit value, the cost increases, which is not economically preferable.
本発明の水溶性湿潤剤組成物は、分岐鎖を有するフッ素系界面活性剤、炭化水素系界面活性剤及び水の他に、樹脂、染料等の各種有機成分及び塩、顔料等の各種無機成分を濡れ性効果を損なわない範囲で適宜含んでいてもよい。 The water-soluble wetting agent composition of the present invention includes various organic components such as resins and dyes, and various inorganic components such as salts and pigments, in addition to the fluorine-containing surfactant having a branched chain, the hydrocarbon surfactant, and water. As long as the wettability effect is not impaired.
このようにして調製される本発明の水溶性湿潤剤組成物は、通常、工業的に使用される（メタ）アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリスチレン樹脂、フッ素樹脂（テトラフルオロエチレン等）等の樹脂、鉄、ステンレス、アルミニウム、アルミニウム合金等の金属またはガラスからなる基板に対して樹脂膜、塗膜、保護膜等をコーティングする際の用途として広く使用することができる。 The water-soluble wetting agent composition of the present invention thus prepared is usually used in industrial applications (meth) acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, fluorine resin (tetrafluoroethylene, etc.), etc. It can be widely used as an application in coating a resin film, a coating film, a protective film or the like on a substrate made of a metal such as resin, iron, stainless steel, aluminum, aluminum alloy or glass.
塗工液
本発明は、上記本発明の水溶性湿潤剤組成物を含む塗工液組成物を提供する。
Coating liquid The present invention provides a coating liquid composition comprising the water-soluble wetting agent composition of the present invention.
１つの実施形態において、本発明の塗工液組成物は原料の塗工液に本発明の水溶性湿潤剤組成物を混合することによって得られる。 In one embodiment, the coating liquid composition of the present invention is obtained by mixing the water-soluble wetting agent composition of the present invention with a raw material coating liquid.
ここで、塗工液としては、例えば、樹脂コーティング液、塗料、インク、表面処理液等が挙げられるが、これらに限定されない。 Here, examples of the coating liquid include, but are not limited to, a resin coating liquid, a paint, an ink, and a surface treatment liquid.
本発明の塗工液組成物において、通常、分岐鎖を有するフッ素系界面活性剤の含有量が０．００１〜１重量％かつ炭化水素系界面活性剤の含有量が０．００１〜１重量％であり、好ましくは、分岐鎖を有するフッ素系界面活性剤の含有量が０.００２５〜０.５重量％かつ炭化水素系界面活性剤の含有量が０.００２５〜０.５重量％であり、より好ましくは、分岐鎖を有するフッ素系界面活性剤の含有量が０.００５〜０.４３８重量％かつ炭化水素系界面活性剤の含有量が０.００５〜０.２５重量％である。 In the coating liquid composition of the present invention, the content of the fluorine-containing surfactant having a branched chain is usually 0.001 to 1% by weight and the content of the hydrocarbon surfactant is 0.001 to 1% by weight. Preferably, the content of the fluorine-containing surfactant having a branched chain is 0.0025 to 0.5% by weight and the content of the hydrocarbon surfactant is 0.0025 to 0.5% by weight. More preferably, the content of the fluorine-containing surfactant having a branched chain is 0.005 to 0.438% by weight and the content of the hydrocarbon surfactant is 0.005 to 0.25% by weight.
また、本発明の水溶性湿潤剤組成物をそのまま表面処理剤等の塗工液組成物として用いることもできる。 Further, the water-soluble wetting agent composition of the present invention can be used as it is as a coating liquid composition such as a surface treatment agent.
また、本発明の塗工液組成物には、塗工液と本発明の水溶性湿潤剤組成物との混合により得られる塗工液組成物と同様の成分を有するものであれば、水溶性湿潤剤組成物を調製することなく塗工液に上記フッ素系界面活性剤及び炭化水素系界面活性剤を直接添加してなるものも含まれる。 Further, the coating liquid composition of the present invention is water-soluble so long as it has the same components as the coating liquid composition obtained by mixing the coating liquid and the water-soluble wetting agent composition of the present invention. Also included are those obtained by directly adding the fluorinated surfactant and hydrocarbon surfactant to the coating liquid without preparing a wetting agent composition.
本発明の塗工液組成物は、各種基板に対して高い湿潤性を発揮するという効果を奏する。
したがって、本発明の塗工液組成物を用いることによって、基板に対して満遍なく均一なコーティングをすることができる。また、比較的高価なフッ素系界面活性剤の使用量を減らしながらも高い濡れ性を示す塗工液を得ることができる。
The coating liquid composition of the present invention has an effect of exhibiting high wettability with respect to various substrates.
Therefore, a uniform coating can be uniformly applied to the substrate by using the coating liquid composition of the present invention. In addition, it is possible to obtain a coating liquid exhibiting high wettability while reducing the amount of the relatively expensive fluorine-based surfactant used.
コーティング方法
本発明は、上記の本発明の塗工液組成物を用いて基板をコーティングする工程を含むことを特徴とする塗工液のコーティング方法を提供する。
Coating Method The present invention provides a coating liquid coating method characterized by including a step of coating a substrate with the above-described coating liquid composition of the present invention.
次に、上記添加工程により得られた湿潤剤含有塗工液で基板をコーティングする。 Next, the substrate is coated with the wetting agent-containing coating solution obtained by the addition step.
本発明の方法が対象とする基板は、特に限定されないが、例えば、樹脂、金属、ガラス等からなる基板が挙げられる。 Although the board | substrate which the method of this invention makes object is not specifically limited, For example, the board | substrate which consists of resin, a metal, glass etc. is mentioned.
樹脂としては、（メタ）アクリル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリスチレン樹脂、フッ素樹脂等が挙げられる。 Examples of the resin include (meth) acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, and fluororesin.
金属としては、鉄、ステンレス、アルミニウム、これらの金属の合金（アルミニウム合金等）等が挙げられる。 Examples of the metal include iron, stainless steel, aluminum, alloys of these metals (such as aluminum alloys), and the like.
本発明の方法を用いることによって、基板に対して樹脂膜、塗膜、保護膜等を満遍なく均一にコーティングすることができる。 By using the method of the present invention, it is possible to uniformly and uniformly coat a substrate with a resin film, a coating film, a protective film and the like.
以下、実施例に基づいて本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.
表１に、実施例及び比較例の水溶液におけるフッ素系界面活性剤及び炭化水素系界面活性剤の添加量を示した。 Table 1 shows the addition amounts of the fluorine-based surfactant and the hydrocarbon-based surfactant in the aqueous solutions of Examples and Comparative Examples.
＜湿潤性評価試験＞
上記実施例及び比較例の水溶液を用いて、各種基板を対象として接触角を２５℃にて測定した。協和界面科学社製 ＤｒｏｐＭａｓｔｅｒ７００を用いて、滴下５秒後の液滴の接触角を測定した。
<Wetting test>
Using the aqueous solutions of the above Examples and Comparative Examples, the contact angle was measured at 25 ° C. for various substrates. Using a DropMaster 700 manufactured by Kyowa Interface Science Co., Ltd., the contact angle of the droplet after 5 seconds of dropping was measured.
比較例として、飽和直鎖型フッ素系界面活性剤デュポン社ＺＯＮＹＬ ＦＳＯ（ＦＳＯと略す）と炭化水素系界面活性剤を組み合わせた例を示した。ＺＯＮＹＬ ＦＳＯと組み合わせた炭化水素系界面活性剤は、表１に示す通りである。
ＺＯＮＹＬ ＦＳＯの構造は、式（３）で示される。
CF３−(CF２CF２)ｎ−CH２CH２−O(CH２CH２O)ｘ−H （３）
As a comparative example, an example was shown in which a saturated linear fluorosurfactant DuPont ZONYL FSO (abbreviated as FSO) and a hydrocarbon surfactant were combined. The hydrocarbon surfactants combined with ZONYL FSO are as shown in Table 1.
The structure of ZONYL FSO is represented by the formula (3).
CF 3 - (CF 2 CF 2 ) n -CH 2 CH 2 -O (CH 2 CH 2 O) x -H (3)
［実施例１］
水中に添加した界面活性剤の合計が０．５重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液のアクリル板に対する接触角を測定した結果を表２、表３及び図１に示した。
[Example 1]
Table 2 and Table 2 show the results of measuring the contact angle of an aqueous solution combining a fluorosurfactant and a hydrocarbon surfactant so that the total amount of surfactant added in water is 0.5% by weight with respect to the acrylic plate. 3 and FIG.
上記の表２から明らかなように、分岐鎖を有するフッ素系界面活性剤を用いた試料（試料Ｎｏ．１−１、７−１、８−１、９−１、及び１２−１）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれの界面活性剤を単独で添加するよりもアクリル板に対する接触角値が小さくなった。一方、直鎖型フッ素系界面活性剤を用いた試料（試料Ａ−１、Ｂ−１、Ｃ−１及びＤ）においてはフッ素系界面活性剤と炭化水素系界面活性剤を併用しても、それぞれの界面活性剤を単独で添加した場合と比較して、界面活性剤の併用による濡れ性の向上は見られなかった。また、直鎖型フッ素系界面活性剤を用いた試料の接触角値は、分岐鎖を有するフッ素系界面活性剤を用いた試料の値に比べ大きな値であった。 As apparent from Table 2 above, in the samples (sample Nos. 1-1, 7-1, 8-1, 9-1, and 12-1) using the fluorine-based surfactant having a branched chain, By using a fluorine-based surfactant and a hydrocarbon-based surfactant in combination, the contact angle value with respect to the acrylic plate was smaller than when each surfactant was added alone. On the other hand, in samples (samples A-1, B-1, C-1 and D) using a linear fluorine-based surfactant, even if a fluorine-based surfactant and a hydrocarbon-based surfactant are used in combination, Compared with the case where each surfactant was added alone, no improvement in wettability was observed due to the combined use of the surfactant. Further, the contact angle value of the sample using the linear fluorosurfactant was larger than the value of the sample using the fluorosurfactant having a branched chain.
また、表３に示されるように、分岐鎖を有するフッ素系界面活性剤と炭化水素系界面活性剤とを組み合わせた試料において、フッ素系界面活性剤：炭化水素系界面活性剤の使用割合が重量部で０．２５：０．２５である試料よりも、フッ素系界面活性剤の割合の高い試料のほうが、接触角が小さくなる。 Further, as shown in Table 3, in a sample in which a fluorine-containing surfactant having a branched chain and a hydrocarbon-based surfactant are combined, the use ratio of fluorine-based surfactant: hydrocarbon-based surfactant is weight. The contact angle is smaller in the sample having a higher ratio of the fluorosurfactant than in the sample having a ratio of 0.25: 0.25.
また、試料Ｎｏ．４−３としてＦＴ−１００を０．４３８重量％、ＳＤ−６０を０．０６２重量％含む試料を用いて上記と同様に湿潤性評価試験をしたところ、接触角は８度であった。このことから、フッ素系界面活性剤：炭化水素系界面活性剤の使用割合が重量部で０．４３８：０．０６２〜０．３７５：０．１２５の範囲にある試料の接触角が最も小さくなることが分かる（図１）。 Sample No. When a wettability evaluation test was performed in the same manner as described above using a sample containing 0.438 wt% of FT-100 and 0.062 wt% of SD-60 as 4-3, the contact angle was 8 degrees. From this, the contact angle of the sample in which the use ratio of the fluorosurfactant: hydrocarbon surfactant is in the range of 0.438: 0.062 to 0.375: 0.125 by weight is the smallest. (Fig. 1).
［実施例２］
水中に添加した界面活性剤の合計が０．１重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液の、アクリル板に対する接触角を測定した結果を表４に示した。
[Example 2]
Table 4 shows the results of measuring the contact angle of the aqueous solution in which the fluorine-based surfactant and the hydrocarbon-based surfactant are combined so that the total amount of the surfactants added in water is 0.1% by weight with respect to the acrylic plate. Indicated.
界面活性剤添加量の合計を０．１重量％とした場合にも、フッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれ単独で添加した場合に比べアクリル板に対する接触角値が小さくなった。 Even when the total amount of surfactant added is 0.1% by weight, the contact angle with respect to the acrylic plate can be increased by using both a fluorine-based surfactant and a hydrocarbon-based surfactant, compared with the case where each is added alone. The value became smaller.
［実施例３］
水中に添加した界面活性剤の合計が０．０１重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液の、アクリル板に対する接触角を測定した結果を表５に示した。
[Example 3]
Table 5 shows the results of measuring the contact angle of the aqueous solution combining the fluorine-based surfactant and the hydrocarbon-based surfactant so that the total amount of the surfactant added in water is 0.01% by weight with respect to the acrylic plate. Indicated.
界面活性剤添加量の合計を０．０１重量％とした場合にも、分岐鎖を有するフッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれ単独で添加した場合に比べアクリル板に対する接触角値が小さくなった。一方、直鎖型フッ素系界面活性剤を用いた試料（試料Ｅ及びＦ）においてはフッ素系界面活性剤と炭化水素系界面活性剤を併用しても、それぞれの界面活性剤を単独で添加した場合と比較して、界面活性剤の併用による濡れ性の向上は見られなかった。 Even when the total amount of surfactants added is 0.01% by weight, a combination of a fluorine-containing surfactant having a branched chain and a hydrocarbon-based surfactant can be used in comparison with the case where each is added alone. The contact angle value for the plate was reduced. On the other hand, in the samples (samples E and F) using the linear fluorosurfactant, each surfactant was added alone even if the fluorosurfactant and the hydrocarbon surfactant were used in combination. Compared with the case, the wettability improvement by combined use of surfactant was not seen.
［実施例４］
水中に添加した界面活性剤の合計が０．５重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液の、アルミ板に対する接触角を測定した結果を表６に示した。
[Example 4]
Table 6 shows the results of measuring the contact angle of an aqueous solution in which a fluorosurfactant and a hydrocarbon surfactant are combined so that the total amount of surfactants added in water is 0.5% by weight. Indicated.
分岐鎖を有するフッ素系界面活性剤を用いた試料（試料Ｎｏ．１−１、２、３−１、７−１、８−１、１０、１１、１２−１、１３及び１４）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれの界面活性剤を単独で添加するよりもアルミ板に対する接触角が小さくなった。一方、直鎖型フッ素系界面活性剤を用いた試料（試料Ａ−１、Ｂ−１、Ｃ−１及びＤ）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用しても、それぞれの界面活性剤を単独で添加した場合と比較して、界面活性剤の併用による濡れ性の向上は見られなかった。 In the sample (sample No. 1-1, 2, 3-1, 7-1, 8-1, 10, 11, 12-1, 13 and 14) using the fluorine-based surfactant having a branched chain, By using a fluorine-based surfactant and a hydrocarbon-based surfactant in combination, the contact angle with respect to the aluminum plate was smaller than when each surfactant was added alone. On the other hand, in samples (samples A-1, B-1, C-1 and D) using a linear fluorine-based surfactant, the fluorine-based surfactant and the hydrocarbon-based surfactant may be used in combination. As compared with the case where each surfactant was added alone, no improvement in wettability was observed due to the combined use of the surfactant.
［実施例５］
水中に添加した界面活性剤の合計が０．５重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液の、テトラフルオロエチレン板に対する接触角を測定した結果を表７、８に示した。
[Example 5]
The results of measuring the contact angle of an aqueous solution combining a fluorosurfactant and a hydrocarbon surfactant so that the total amount of surfactant added in water is 0.5% by weight with respect to the tetrafluoroethylene plate are shown. 7 and 8.
上記の表７及び８において、分岐鎖を有するフッ素系界面活性剤を用いた試料（試料Ｎｏ．２、８−１、１−２、３−２、４−２、５、６、７−２、８−２、９−２、及び１２−２）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれの界面活性剤を単独で添加するよりもテトラフルオロエチレン板に対する接触角が小さくなった。一方、直鎖型フッ素系界面活性剤を用いた試料（試料Ａ−１、Ａ−２、Ｂ−１、Ｂ−２、Ｃ−１、Ｃ−２、及びＤ）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用しても、それぞれの界面活性剤を単独で添加した場合に比べ大きな接触角値を示し、界面活性剤の併用による濡れ性の向上は見られなかった。 In Tables 7 and 8 above, samples (sample Nos. 2, 8-1, 1-2, 3-2, 4-2, 5, 6, 7-2) using a fluorine-containing surfactant having a branched chain are used. 8-2, 9-2, and 12-2), by using a fluorosurfactant and a hydrocarbon surfactant in combination, tetrafluoroethylene rather than adding each surfactant alone. The contact angle to the plate was reduced. On the other hand, in samples (samples A-1, A-2, B-1, B-2, C-1, C-2, and D) using a linear type fluorine surfactant, the fluorine surfactant is used. Even when the surfactant and the hydrocarbon-based surfactant were used in combination, the contact angle value was larger than when each surfactant was added alone, and no improvement in wettability was observed due to the combined use of the surfactant.
［実施例６］
水中に添加した界面活性剤の合計が０．０１重量％となるようにフッ素系界面活性剤と炭化水素系界面活性剤を組み合わせた水溶液の、テトラフルオロエチレン板に対する接触角を測定した結果を表９に示した。
[Example 6]
The results of measuring the contact angle of an aqueous solution combining a fluorosurfactant and a hydrocarbon surfactant so that the total amount of surfactant added in water is 0.01% by weight with respect to the tetrafluoroethylene plate are shown. 9 shows.
界面活性剤の総添加量を０．０１重量％とした場合にも、分岐鎖を有するフッ素系界面活性剤を用いた試料（試料Ｎｏ．１７及び１８）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用することで、それぞれの界面活性剤を単独で添加するよりもテトラフルオロエチレン板に対する接触角が小さくなった。一方、直鎖型フッ素系界面活性剤を用いた試料（試料Ｅ及びＦ）においては、フッ素系界面活性剤と炭化水素系界面活性剤を併用しても、界面活性剤を単独で添加した場合と比較して、界面活性剤の併用による濡れ性の向上は見られなかった。 Even when the total addition amount of the surfactant is 0.01% by weight, in the samples using the fluorine-containing surfactant having a branched chain (sample Nos. 17 and 18), the fluorine-containing surfactant and the carbonization are performed. By using a hydrogen-based surfactant in combination, the contact angle with respect to the tetrafluoroethylene plate was smaller than when each surfactant was added alone. On the other hand, in samples (samples E and F) using a linear fluorosurfactant, even when a fluorosurfactant and a hydrocarbon surfactant are used in combination, the surfactant is added alone Compared with, no improvement in wettability was observed with the combined use of the surfactant.
本発明によれば、各種基板に対して高い湿潤性を発揮する水溶性組成物を得ることができる。 According to the present invention, a water-soluble composition that exhibits high wettability with respect to various substrates can be obtained.
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