JP2020139046A - Surface treatment agent and method for producing the same, and surface-treated base material and surface treatment method - Google Patents

Surface treatment agent and method for producing the same, and surface-treated base material and surface treatment method Download PDF

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JP2020139046A
JP2020139046A JP2019035419A JP2019035419A JP2020139046A JP 2020139046 A JP2020139046 A JP 2020139046A JP 2019035419 A JP2019035419 A JP 2019035419A JP 2019035419 A JP2019035419 A JP 2019035419A JP 2020139046 A JP2020139046 A JP 2020139046A
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surface treatment
treatment agent
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copolymer
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JP7236635B2 (en
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雄太 青海
Yuta Aomi
雄太 青海
英夫 澤田
Hideo Sawada
英夫 澤田
健一 土澤
Kenichi Tsuchizawa
健一 土澤
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Nitto Boseki Co Ltd
Hirosaki University NUC
Fujikura Composites Inc
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Nitto Boseki Co Ltd
Hirosaki University NUC
Fujikura Composites Inc
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Abstract

To provide a surface treatment agent that can impart excellent hydrophilicity and oil repellency and a method for producing the same, a surface-treated base material that can express excellent hydrophilicity and oil repellency, and a surface treatment method that can impart excellent hydrophilicity and oil repellency to the surface of a base material to be treated.SOLUTION: A surface treatment agent contains a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allyl amine and an amide compound or a carboxylic acid, and a solvent. In formula (1), R1 is a group containing a fluoroalkyl group, R2 is an alkyl group or alkoxyalkyl group, R3 and R4 independently represent a hydrogen atom or a monovalent organic group, x is an integer of 1-100, y is an integer of 0-100.SELECTED DRAWING: None

Description

本発明は、表面処理剤及びその製造方法、並びに表面処理基材及び当該表面処理剤を用いた表面処理方法に関する。 The present invention relates to a surface treatment agent and a method for producing the same, and a surface treatment base material and a surface treatment method using the surface treatment agent.

産業用機械部品等の生産には、多種、多量の油が使用されており、製造工程における部品洗浄や製品洗浄の工程等で排出される含油排水の量も多くなっている。このような含油排水から油と水とを分離する油水分離技術として、例えば、比重分離等の静置分離技術、遠心分離技術、吸着分離技術等が知られている。 A large amount of oil is used in the production of industrial machine parts and the like, and the amount of oil-containing wastewater discharged in the parts cleaning process and the product cleaning process in the manufacturing process is also large. As an oil-water separation technique for separating oil and water from such oil-containing wastewater, for example, a static separation technique such as specific gravity separation, a centrifugal separation technique, an adsorption separation technique, and the like are known.

これらの分離技術のうち、静置分離技術は多大な時間を要するという問題があり、遠心分離技術は大掛かりな装置を必要とするという問題があり、吸着分離技術は大量の含油排水の処理に不向きであるという問題がある。そこで、従来、所定のフッ素化合物と無機化合物とがナノコンポジット化された複合材料であって、親水・撥油性を有するフッ素含有ナノコンポジット粒子をろ紙や不織布に担持させた油水分離膜が提案されている（特許文献１参照）。 Of these separation technologies, the static separation technology has the problem of requiring a large amount of time, the centrifugal separation technology has the problem of requiring a large-scale device, and the adsorption separation technology is not suitable for treating a large amount of oil-containing wastewater. There is a problem that it is. Therefore, conventionally, an oil-water separation membrane in which a predetermined fluorine compound and an inorganic compound are nanocomposited and fluorine-containing nanocomposite particles having hydrophilicity and oil repellency are supported on a filter paper or a non-woven fabric has been proposed. (See Patent Document 1).

物品表面に付着した油汚れを防止する方法として、物品表面を、撥油性を有する表面処理剤で処理して、物品表面に防汚膜を形成する方法が知られている。撥油性を有する表面処理剤としては、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリクロロトリフルオロエチレン等のフッ素樹脂等が広く用いられている。しかしながら、フッ素樹脂は高い撥水性を有するため、物品表面に付着した油汚れを水洗浄により洗い流すことが困難である。そのため、油汚れを防止するための撥油性と、付着した油汚れを水洗浄するための親水性とを有する表面処理剤の提案が望まれている。 As a method for preventing oil stains adhering to the surface of an article, a method of treating the surface of the article with an oil-repellent surface treatment agent to form an antifouling film on the surface of the article is known. As the surface treatment agent having oil repellency, fluororesins such as polytetrafluoroethylene (PTFE) and polychlorotrifluoroethylene are widely used. However, since fluororesin has high water repellency, it is difficult to wash away oil stains adhering to the surface of an article by washing with water. Therefore, it is desired to propose a surface treatment agent having oil repellency for preventing oil stains and hydrophilicity for washing adhering oil stains with water.

従来、表面処理剤に含まれる親水性及び撥油性を有する樹脂組成物として、炭素数１〜１８のペルフルオロアルキル（メタ）アクリル酸エステルと親水基含有モノマーとを構成成分に含む共重合体が知られている（特許文献２参照）。 Conventionally, as a resin composition having hydrophilicity and oil repellency contained in a surface treatment agent, a copolymer containing a perfluoroalkyl (meth) acrylic acid ester having 1 to 18 carbon atoms and a hydrophilic group-containing monomer as constituent components has been known. (See Patent Document 2).

特開２０１５−１８７２２０号公報JP-A-2015-187220 特開２００８−２９７４８２号公報Japanese Unexamined Patent Publication No. 2008-297482

上記特許文献１に記載されている油水分離技術や上記特許文献２に記載されている防汚膜を形成するための表面処理剤等の技術分野においては、優れた親水性及び撥油性を有する材料が必須であり、当該親水性及び撥油性をさらに向上させてなる材料の提案に対する要望が高まっている。 Materials having excellent hydrophilicity and oil repellency in technical fields such as the oil-water separation technique described in Patent Document 1 and the surface treatment agent for forming an antifouling film described in Patent Document 2. Is essential, and there is an increasing demand for proposals for materials that further improve the hydrophilicity and oil repellency.

上記課題に鑑みて、本発明は、優れた親水性及び撥油性を付与可能な表面処理剤及びその製造方法、優れた親水性及び撥油性を発現可能な表面処理基材、並びに被処理基材の表面に優れた親水性及び撥油性を付与可能な表面処理方法を提供することを目的とする。 In view of the above problems, the present invention presents a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency and a method for producing the same, a surface treatment substrate capable of exhibiting excellent hydrophilicity and oil repellency, and a substrate to be treated. It is an object of the present invention to provide a surface treatment method capable of imparting excellent hydrophilicity and oil repellency to the surface of the above.

上記課題を解決するために、本発明は、下記式（１）で示されるフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物又はカルボン酸の共重合体と、溶媒とを含有することを特徴とする表面処理剤を提供する。 In order to solve the above problems, the present invention contains a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a carboxylic acid, and a solvent. Provided is a characteristic surface treatment agent.

Figure 2020139046
上記式（１）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表し、ｘは１〜１００の整数であり、ｙは０〜１００の整数である。
Figure 2020139046
In the above formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 are independent hydrogen atoms or monovalent organic groups, respectively. , X is an integer of 1 to 100, and y is an integer of 0 to 100.

前記共重合体は、下記式（２）で示される化学構造を有するものであってもよいし、下記式（３）で示される化学構造を有するものであってもよく、前記フッ素含有化合物と前記共重合体との含有比（質量基準）が、１：１〜２５であればよく、前記溶媒が、炭素数１〜５のアルコール系溶媒であればよい。 The copolymer may have a chemical structure represented by the following formula (2), or may have a chemical structure represented by the following formula (3), and may be used with the fluorine-containing compound. The content ratio (based on mass) with the copolymer may be 1: 1 to 25, and the solvent may be an alcohol solvent having 1 to 5 carbon atoms.

Figure 2020139046
上記式（２）中、Ｒ1’及びＲ2’は各々独立して炭素数１〜４のアルキル基を表し、Ｘ-はハロゲン化物イオン、無機アニオン又は有機アニオンを表す。
Figure 2020139046
In the above formula (2), R 1 'and R 2' represents an alkyl group having 1 to 4 carbon atoms each independently, X - represents a halide ion, an inorganic anion or an organic anion.

Figure 2020139046
上記式（３）中、Ｒ3’及びＲ4’は各々独立して炭素数１〜４のアルキル基を表し、Ｘ-はハロゲン化物イオン、無機アニオン又は有機アニオンを表す。
Figure 2020139046
In the above formula (3), R 3 'and R 4' represents an alkyl group having 1 to 4 carbon atoms each independently, X - represents a halide ion, an inorganic anion or an organic anion.

前記式（１）において、ｙが０であればよく、Ｒ1で表されるフルオロアルキル基を含有する基が、下記式（４）で表される基であればよく、Ｒ2はメチル基であればよく、ｘが１〜１０の整数であればよい。 In the above formula (1), y may be 0, and the group containing the fluoroalkyl group represented by R 1 may be a group represented by the following formula (4), and R 2 is a methyl group. However, x may be an integer of 1 to 10.

Figure 2020139046
上記式（４）中、ｐは０〜２の整数である。
Figure 2020139046
In the above equation (4), p is an integer of 0 to 2.

本発明は、第１面及び当該第１面に対向する第２面を有する基部と、前記基部の少なくとも前記第１面に設けられてなる表面処理層とを備え、前記表面処理層は、上記表面処理剤を用いた表面処理が前記基部の前記第１面に施されることにより形成されてなるものであることを特徴とする表面処理基材を提供する。 The present invention includes a base having a first surface and a second surface facing the first surface, and a surface treatment layer provided on at least the first surface of the base, and the surface treatment layer is described above. Provided is a surface treatment base material, which is formed by applying a surface treatment using a surface treatment agent to the first surface of the base portion.

本発明は、下記式（１）で示されるフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物又はカルボン酸の共重合体と、溶媒とを混合することを特徴とする表面処理剤の製造方法を提供する。かかる製造方法において、酸触媒及びアルカリ触媒のいずれをも混合させないのが好ましい。 The present invention is for producing a surface treatment agent, which comprises mixing a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a carboxylic acid, and a solvent. Provide a method. In such a production method, it is preferable not to mix either the acid catalyst or the alkali catalyst.

Figure 2020139046
上記式（１）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表し、ｘは１〜１００の整数であり、ｙは０〜１００の整数である。
Figure 2020139046
In the above formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 are independent hydrogen atoms or monovalent organic groups, respectively. , X is an integer of 1 to 100, and y is an integer of 0 to 100.

本発明は、上記表面処理剤を用いて被処理基材に表面処理を施すことを特徴とする表面処理方法を提供する。 The present invention provides a surface treatment method characterized by subjecting a substrate to be treated with a surface treatment using the above-mentioned surface treatment agent.

本発明によれば、優れた親水性及び撥油性を付与可能な表面処理剤及びその製造方法、優れた親水性及び撥油性を発現可能な表面処理基材、並びに被処理基材の表面に優れた親水性及び撥油性を付与可能な表面処理方法を提供することができる。 According to the present invention, a surface treatment agent capable of imparting excellent hydrophilicity and oil repellency and a method for producing the same, a surface treatment substrate capable of exhibiting excellent hydrophilicity and oil repellency, and a surface treatment substrate are excellent. It is possible to provide a surface treatment method capable of imparting hydrophilicity and oil repellency.

本発明の実施の形態について説明する。
［表面処理剤］
本実施形態に係る表面処理剤は、下記式（１）で示されるフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物又はカルボン酸の共重合体と、溶媒とを含有する。かかる表面処理剤は、上記フッ素含有化合物と上記共重合体との反応生成物をミセル状態で含むものであって、当該ミセル状の反応生成物を製造するときの反応溶液として調製され得る。 Embodiments of the present invention will be described.
[Surface treatment agent]
The surface treatment agent according to the present embodiment contains a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a carboxylic acid, and a solvent. Such a surface treatment agent contains a reaction product of the fluorine-containing compound and the copolymer in a micelle state, and can be prepared as a reaction solution for producing the micelle-like reaction product.

Figure 2020139046
式（１）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表し、ｘは１〜１００の整数であり、ｙは０〜１００の整数である。
Figure 2020139046
In formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 independently represent a hydrogen atom or a monovalent organic group. Represented, x is an integer of 1 to 100, and y is an integer of 0 to 100.

式（１）において、Ｒ1で表されるフルオロアルキル基を含有する基としては、例えば、−ＣＦ3、−Ｃ2Ｆ5、−Ｃ3Ｆ7、−Ｃ6Ｆ13、−Ｃ7Ｆ15等の−ＣqＦ2q+1（ｑ＝１〜１０）で表されるフルオロアルキル基；オキシフルオロアルキレン基等を挙げることができ、これらのうち、下記式（４）で示されるオキシフルオロアルキレン基であるのが好ましい。 In the formula (1), examples of the group containing a fluoroalkyl group represented by R 1 include -CF 3 , -C 2 F 5 , -C 3 F 7 , -C 6 F 13 , and -C 7 F. Fluoroalkyl groups represented by −C q F 2q + 1 (q = 1 to 10) such as 15 ; oxyfluoroalkylene groups and the like can be mentioned, and among these, oxyfluoro represented by the following formula (4). It is preferably an alkylene group.

Figure 2020139046
式（４）中、ｐは０〜２の整数である。
Figure 2020139046
In equation (4), p is an integer from 0 to 2.

式（１）において、Ｒ2で表されるアルキル基としては、例えば、メチル基、エチル基等の炭素数１〜２のアルキル基が挙げられ、Ｒ2で表されるアルコキシアルキル基としては、例えば、メトキシメチル基、メトキシエチル基、エトキシメチル基、エトキシエチル基等の炭素数２〜４のアルコキシアルキル基が挙げられる。これらのうち、Ｒ2で表される基としては、アルキル基が好ましく、メチル基が特に好ましい。 In the formula (1), the alkyl group represented by R 2, for example, include an alkyl group having 1 to 2 carbon atoms such as a methyl group, an ethyl group, as alkoxyalkyl group represented by R 2, For example, an alkoxyalkyl group having 2 to 4 carbon atoms such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group can be mentioned. Of these, as the group represented by R 2 , an alkyl group is preferable, and a methyl group is particularly preferable.

式（１）において、Ｒ3及びＲ4で表される有機基としては、例えば、下記式（ｉ）〜（ｖ）で示される基を挙げることができる。 Examples of the organic group represented by R 3 and R 4 in the formula (1) include the groups represented by the following formulas (i) to (v).

Figure 2020139046
Figure 2020139046

式（１）において、トリアルコキシシリル基又はトリアルコキシアルコキシシリル基（−Ｓｉ(ＯＲ2)3）が結合する中間鎖（−ＣＨ2−ＣＨ−）の数ｘは、１〜１００であり、好ましくは１〜５０、より好ましくは１〜１０、特に好ましくは２〜５である。また、中間鎖（−ＣＨ2−ＣＲ3Ｒ4−）の数ｙは、０〜１００であり、好ましくは０〜５０、より好ましくは０〜１０である。 In the formula (1), the number x of the intermediate chains (-CH 2- CH-) to which the trialkoxysilyl group or the trialkoxyalkoxysilyl group (-Si (OR 2 ) 3 ) is bonded is preferably 1 to 100. Is 1 to 50, more preferably 1 to 10, and particularly preferably 2 to 5. Moreover, medium chain (-CH 2 -CR 3 R 4 - ) number y of 0 to 100, preferably 0 to 50, more preferably 0-10.

上記フッ素含有化合物として好適な化合物としては、下記式（５）〜（９）で示される化合物を例示することができる。特に、上記フッ素含有化合物が式（５）又は式（８）で示される化合物（式（１）においてｙ＝０である化合物）であると、１分子中に占められるフッ素原子の割合が大きいことで、本実施形態における反応生成物を生成する反応を効率的に進行させることができる。 As a suitable compound as the fluorine-containing compound, compounds represented by the following formulas (5) to (9) can be exemplified. In particular, when the fluorine-containing compound is a compound represented by the formula (5) or the formula (8) (a compound in which y = 0 in the formula (1)), the proportion of fluorine atoms in one molecule is large. Therefore, the reaction for producing the reaction product in the present embodiment can be efficiently advanced.

Figure 2020139046
式（５）中、ｘ’は２又は３である。
Figure 2020139046
In formula (5), x'is 2 or 3.

Figure 2020139046
Figure 2020139046

Figure 2020139046
式（６）及び式（７）中、Ｒ5は、−ＣＦ(ＣＦ3)ＯＣＦ2ＣＦ(ＣＦ3)ＯＣ3Ｆ7で表される基である。式（６）中、ｘａは１〜１００の整数である。式（７）中、ｘｂは１〜１００の整数であり、ｙｂは１〜５００の整数である。
Figure 2020139046
In formulas (6) and (7), R 5 is a group represented by −CF (CF 3 ) OCF 2 CF (CF 3 ) OC 3 F 7 . In equation (6), xa is an integer from 1 to 100. In equation (7), xb is an integer of 1 to 100 and yb is an integer of 1 to 500.

Figure 2020139046
式（８）中、ｘｃは１〜１０の整数であり、ｙｃは０〜１００の整数である。
Figure 2020139046
In equation (8), xc is an integer of 1 to 10, and yc is an integer of 0 to 100.

Figure 2020139046
式（９）中、ｘｄは１〜１０の整数であり、ｙｄは０〜１００の整数である。
Figure 2020139046
In equation (9), xd is an integer of 1 to 10, and yd is an integer of 0 to 100.

上記式（１）で示されるフッ素含有化合物は、下記式（Ｉａ）で示されるフッ素含有過酸化物の存在下に、下記式（Ｉｂ）で示される単量体と、下記式（Ｉｃ）で示される単量体とを重合させることにより得られる。なお、この反応生成物（フッ素含有化合物）中には、フルオロアルキル基を含有する基（Ｒ1）が片末端のみに導入されているオリゴマーが任意の割合で含まれていてもよい。 The fluorine-containing compound represented by the above formula (1) has a monomer represented by the following formula (Ib) and a monomer represented by the following formula (Ic) in the presence of the fluorine-containing peroxide represented by the following formula (Ia). It is obtained by polymerizing with the indicated monomer. The reaction product (fluorine-containing compound) may contain an oligomer in which a group (R 1 ) containing a fluoroalkyl group is introduced only at one end in an arbitrary ratio.

Figure 2020139046
式（Ｉａ）〜（Ｉｃ）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表す。
Figure 2020139046
In formulas (Ia) to (Ic), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 are independently hydrogen atoms or monovalents, respectively. Represents an organic group of.

本実施形態に係る表面処理剤は、アリルアミンの４級アンモニウム塩とアミド化合物との共重合体、又はアリルアミンの４級アンモニウム塩とカルボン酸との共重合体を含む。これらの共重合体の構成成分であるアリルアミンの４級アンモニウム塩としては、例えば、ジアリルジアルキルアンモニウムクロリド、ジアリルジアルキルアンモニウムアルキルサルフェイト、ジアリルジアルキルアンモニウムヒドロキシド、ジアリルジアルキルアンモニウムフルオリド等が挙げられる。ジアリルジアルキルアンモニウムクロリドとしては、例えば、ジアリルジメチルアンモニウムクロリド、ジアリルエチルメチルアンモニウムクロリド、ジアリルジエチルアンモニウムクロリド等が挙げられる。ジアリルアルキルアンモニウムアルキルサルフェイトとしては、例えば、ジアリルジメチルアンモニウムメチルサルフェイト、ジアリルエチルメチルアンモニウムメチルサルフェイト、ジアリルジエチルアンモニウムメチルサルフェイト、ジアリルジメチルアンモニウムエチルサルフェイト、ジアリルエチルメチルアンモニウムエチルサルフェイト、ジアリルジエチルアンモニウムエチルサルフェイト等が挙げられる。ジアリルジアルキルアンモニウムヒドロキシドとしては、例えば、ジアリルジメチルアンモニウムヒロドキシド、ジアリルエチルメチルアンモニウムヒドロキシド、ジアリルジエチルアンモニウムヒドロキシド等が挙げられる。ジアリルジアルキルアンモニウムフルオリドとしては、ジアリルジメチルアンモニウムフルオリド、ジアリルエチルメチルアンモニウムフルオリド、ジアリルジエチルアンモニウムフルオリド等が挙げられる。 The surface treatment agent according to the present embodiment contains a copolymer of a quaternary ammonium salt of allylamine and an amide compound, or a copolymer of a quaternary ammonium salt of allylamine and a carboxylic acid. Examples of the quaternary ammonium salt of allylamine, which is a constituent component of these copolymers, include diallyldialkylammonium chloride, diallyldialkylammoniumalkylsulfate, diallyldialkylammonium hydroxide, diallyldialkylammonium fluoride and the like. Examples of the diallyldialkylammonium chloride include diallyldimethylammonium chloride, diallylethylmethylammonium chloride, diallyldiethylammonium chloride and the like. Examples of the diallylalkylammoniumalkylsulfate include diallyldimethylammonium methyl sulfate, diallylethylmethylammonium methylsulfate, diallyldiethylammonium methylsulfate, diallyldimethylammonium ethylsulfate, diallylethylmethylammonium ethylsulfate, and diallyldiethyl. Ammonium ethyl sulfate and the like can be mentioned. Examples of the diallyldialkylammonium hydroxide include diallyldimethylammonium hydroxide, diallylethylmethylammonium hydroxide, diallyldiethylammonium hydroxide and the like. Examples of the diallyldialkylammonium fluoride include diallyldimethylammonium fluoride, diallylethylmethylammonium fluoride, diallyldiethylammonium fluoride and the like.

上記共重合体の構成成分であるアミド化合物としては、例えば、アクリルアミド、アルキルアクリルアミド、ジアルキルアクリルアミド、アミノアルキルアクリルアミド、ヒドロキシアルキルアクリルアミド等が挙げられ、カルボン酸としては、例えば、アクリル酸、メタクリル酸等のモノカルボン酸；マレイン酸、フマル酸等のジカルボン酸等が挙げられる。 Examples of the amide compound which is a constituent component of the copolymer include acrylamide, alkylacrylamide, dialkylacrylamide, aminoalkylacrylamide, hydroxyalkylacrylamide and the like, and examples of the carboxylic acid include acrylic acid and methacrylic acid. Monocarboxylic acid; examples thereof include dicarboxylic acids such as maleic acid and fumaric acid.

上記共重合体としては、例えば、下記式（２）又は下記式（３）で示される化学構造を有するもの等が挙げられ、ＰＡＳ−Ｊ−４１、ＰＡＳ−Ｊ−８１、ＰＡＳ−Ｊ−８１Ｌ、ＰＡＳ−２３５１、ＰＡＳ−２４５１等の市販品（いずれも製品名，ニットーボーメディカル社製）を用いてもよい。 Examples of the copolymer include those having a chemical structure represented by the following formula (2) or the following formula (3), PAS-J-41, PAS-J-81, PAS-J-81L. , PAS-2351, PAS-2451 and the like (all product names, manufactured by Nittobo Medical Co., Ltd.) may be used.

Figure 2020139046
式（２）中、Ｒ1’及びＲ2’は各々独立して炭素数１〜４のアルキル基を表し、Ｘ-はハロゲン化物イオン、無機アニオン又は有機アニオンを表す。
Figure 2020139046
Wherein (2), R 1 'and R 2' represents an alkyl group having 1 to 4 carbon atoms each independently, X - represents a halide ion, an inorganic anion or an organic anion.

Figure 2020139046
式（３）中、Ｒ3’及びＲ4’は各々独立して炭素数１〜４のアルキル基を表し、Ｘ-はハロゲン化物イオン、無機アニオン又は有機アニオンを表す。
Figure 2020139046
Wherein (3), R 3 'and R 4' represents an alkyl group having 1 to 4 carbon atoms each independently, X - represents a halide ion, an inorganic anion or an organic anion.

式（２）及び式（３）において、Ｒ１’、Ｒ２’、Ｒ３’及びＲ４’で表されるアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基等の炭素数１〜４のアルキル基が挙げられる。式（２）及び式（３）において、Ｘ-で表されるハロゲン化物イオンとしては、例えば、フッ化物イオン（Ｆ-）、塩化物イオン（Ｃｌ-）等が挙げられ、無機アニオンとしては、例えば、水酸化物イオン（ＯＨ-）、硫酸水素イオン（ＨＳＯ4 -）、硝酸イオン（ＮＯ3 -）等が挙げられ、有機アニオンとしては、例えば、メチル硫酸イオン（ＣＨ3ＳＯ4 -）等のアルキル硫酸イオン、酢酸イオン（ＣＨ3ＣＯＯ-）等が挙げられる。 In the formulas (2) and (3), examples of the alkyl group represented by R1', R2', R3'and R4' include carbons such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Alkyl groups of numbers 1 to 4 can be mentioned. In the formula (2) and (3), X - as the halide ion represented by, for example, a fluoride ion (F -), chloride ion (Cl -). Examples of the inorganic anion, For example, hydroxide ions (OH -), hydrogen sulfate ion (HSO 4 -), nitrate ion (NO 3 -). Examples of the organic anion, e.g., methylsulfate ion (CH 3 SO 4 -), etc. alkyl sulfate ion, acetate ion (CH 3 COO -) and the like.

式（２）で示される化学構造を有する共重合体としては、例えば、下記式（２−１）で示されるジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体（例えば、ニットーボーメディカル社製のＰＡＳ−Ｊ−４１、ＰＡＳ−Ｊ−８１、ＰＡＳ−Ｊ−８１Ｌ等）等が挙げられ、式（３）で示される化学構造を有する共重合体としては、例えば、下記式（３−１）で示されるジアリルエチルメチルアンモニウムエチルサルフェイト・マレイン酸共重合体（例えば、ニットーボーメディカル社製のＰＡＳ−２４５１等）、下記式（３−２）で示されるジアリルジメチルアンモニウムクロリド・マレイン酸共重合体（例えば、ニットーボーメディカル社製のＰＡＳ−２３５１等）等が挙げられる。 Examples of the copolymer having the chemical structure represented by the formula (2) include the diallyldimethylammonium chloride / acrylamide copolymer represented by the following formula (2-1) (for example, PAS-J- manufactured by Nittobo Medical Co., Ltd.). 41, PAS-J-81, PAS-J-81L, etc.), etc., and examples of the copolymer having a chemical structure represented by the formula (3) include diallyl represented by the following formula (3-1). Ethylmethylammonium ethylsulfate-maleic acid copolymer (for example, PAS-2451 manufactured by Nittobo Medical Co., Ltd.), diallyldimethylammonium chloride-maleic acid copolymer represented by the following formula (3-2) (for example, Nittobo) PAS-2351 manufactured by Medical Co., Ltd., etc.) and the like.

Figure 2020139046
Figure 2020139046

Figure 2020139046
Figure 2020139046

Figure 2020139046
Figure 2020139046

共重合体の重量平均分子量は特に限定されるものではなく、例えば１００００以上であればよいが、式（２）で示される化学構造を有する共重合体の重量平均分子量は１５００００以上であるのが好ましく、１８００００以上であるのが特に好ましい。式（２）で示される化学構造を有する共重合体の重量平均分子量が１５００００以上であることで、所望とする親水性が発現されやすくなる。 The weight average molecular weight of the copolymer is not particularly limited, and may be, for example, 10,000 or more, but the weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is 150,000 or more. It is preferably 180,000 or more, and particularly preferably 180,000 or more. When the weight average molecular weight of the copolymer having the chemical structure represented by the formula (2) is 150,000 or more, the desired hydrophilicity can be easily expressed.

本実施形態に係る表面処理剤に含有される溶媒は、上記フッ素含有化合物と上記共重合体との反応生成物をミセル状態で存在（溶解）させ得るものであればよく、例えば、炭素数１〜５のアルコール系溶媒（メタノール、エタノール、プロパノール、ブタノール等）であればよく、炭素数４以上のアルコール系溶媒が用いられる場合には、ノルマルアルコールであるのが好ましい。かかるアルコール系溶媒は僅かに水を含んでいてもよいが、アルコール濃度が９５容量％以上であればよく、９８容量％以上であるのが好ましい。かかるアルコール系溶媒に水が５容量％を超えて含まれていると、上記フッ素含有化合物と上記共重合体との反応生成物をミセル状態で存在（溶解）させることが困難となるおそれがある。 The solvent contained in the surface treatment agent according to the present embodiment may be any solvent as long as it can allow (dissolve) the reaction product of the fluorine-containing compound and the copolymer in a micelle state. For example, the number of carbon atoms is 1. It may be any alcohol-based solvent of ~ 5 (methanol, ethanol, propanol, butanol, etc.), and when an alcohol-based solvent having 4 or more carbon atoms is used, it is preferably a normal alcohol. Such an alcohol solvent may contain a small amount of water, but the alcohol concentration may be 95% by volume or more, preferably 98% by volume or more. If water is contained in such an alcohol solvent in an amount of more than 5% by volume, it may be difficult to allow (dissolve) the reaction product of the fluorine-containing compound and the copolymer in a micelle state. ..

本実施形態に係る表面処理剤における上記フッ素含有化合物と上記共重合体との含有比（質量基準）は、１：１〜２５であるのが好ましく、１：２〜２０であるのがより好ましく、１：５〜１５であるのが特に好ましい。上記フッ素含有化合物と上記共重合体との含有比（質量基準）が上記範囲内にあることで、より優れた親水性及び撥油性が発現され得る。上記共重合体が式（３）で示される化学構造を有するもの（構成成分としてカルボン酸を含むもの）である場合、上記フッ素含有化合物と上記共重合体との含有比（質量基準）は、１：２以上であるのが好ましく、１：５〜１５であるのが特に好ましい。当該含有比（質量基準）が１：２未満であると、所望とする親水性が発現され難くなるおそれがある。 The content ratio (mass basis) of the fluorine-containing compound and the copolymer in the surface treatment agent according to the present embodiment is preferably 1: 1 to 25, more preferably 1: 2 to 20. , 1: 5 to 15, which is particularly preferable. When the content ratio (mass standard) of the fluorine-containing compound and the copolymer is within the above range, more excellent hydrophilicity and oil repellency can be exhibited. When the copolymer has a chemical structure represented by the formula (3) (contains a carboxylic acid as a constituent component), the content ratio (mass basis) of the fluorine-containing compound and the copolymer is determined. It is preferably 1: 2 or more, and particularly preferably 1: 5 to 15. If the content ratio (mass standard) is less than 1: 2, it may be difficult to develop the desired hydrophilicity.

本実施形態に係る表面処理剤は、酸触媒（例えば、塩酸、酢酸、リン酸等）及び塩基触媒（例えば、アンモニア水、水酸化ナトリウム水溶液、水酸化カリウム水溶液等）のいずれをも含まない反応系（無触媒条件下）で上記フッ素含有化合物と上記共重合体との反応生成物を製造するときの反応溶液であるのが好ましい。上記触媒を含む反応系（酸性条件下又はアルカリ性条件下）で上記反応生成物を製造すると、得られる反応溶液が白濁してしまう。当該反応溶液を被処理基材の表面処理剤として用いると、被処理基材の表面が白濁するおそれがある。そのため、被処理基材が透明材料であって、視認性を必要とする用途に用いられるものである場合、上記触媒を含む反応系で得られる反応用液を表面処理剤として用いると、被処理基材の視認性が劣化してしまうおそれがある。よって、このような場合には、上記触媒を含まない反応系（無触媒条件下）で得られる反応溶液を表面処理剤として用いるのが好ましい。 The surface treatment agent according to the present embodiment is a reaction that does not contain any of an acid catalyst (for example, hydrochloric acid, acetic acid, phosphoric acid, etc.) and a base catalyst (for example, aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc.). It is preferably a reaction solution for producing a reaction product of the fluorine-containing compound and the copolymer under a system (under catalytic conditions). When the reaction product is produced in a reaction system containing the catalyst (acidic or alkaline conditions), the resulting reaction solution becomes cloudy. When the reaction solution is used as a surface treatment agent for the substrate to be treated, the surface of the substrate to be treated may become cloudy. Therefore, when the base material to be treated is a transparent material and is used for applications requiring visibility, the reaction liquid obtained in the reaction system containing the catalyst is used as a surface treatment agent to be treated. The visibility of the base material may deteriorate. Therefore, in such a case, it is preferable to use the reaction solution obtained in the reaction system (under no-catalyst conditions) containing the catalyst as the surface treatment agent.

上述した本実施形態に係る表面処理剤は、後述する実施例からも明らかなように、優れた親水性と撥油性とを有する。ここで、親水性とは、例えば、上記表面処理剤により表面処理が施された基材（ガラス基材等）の表面について接触角計（例えば、協和界面科学社製のＤｒｏｐＭａｓｔｅｒ３００（製品名）等）を用いて水の接触角（ｄｅｇ）を測定したとき、水の接触角が相対的に小さいことを意味する。具体的には、水の接触角が９０°未満、好ましくは３０°以下、より好ましくは０°である。 The surface treatment agent according to the present embodiment described above has excellent hydrophilicity and oil repellency, as is clear from the examples described later. Here, hydrophilicity means, for example, a contact angle meter (for example, DropMaster 300 (product name) manufactured by Kyowa Interface Science Co., Ltd.) on the surface of a base material (glass base material, etc.) surface-treated with the above-mentioned surface treatment agent. ) Is used to measure the contact angle (deg) of water, which means that the contact angle of water is relatively small. Specifically, the contact angle of water is less than 90 °, preferably 30 ° or less, and more preferably 0 °.

また、撥油性とは、例えば、上記表面処理剤により表面処理が施された基材（ガラス基材等）の表面について接触角計（例えば、協和界面科学社製のＤｒｏｐＭａｓｔｅｒ３００（製品名）等）を用いてドデカンの接触角（ｄｅｇ）を測定したとき、ドデカンの接触角が相対的に大きいことを意味する。具体的には、ドデカンの接触角が３５°以上、好ましくは４０°以上、より好ましくは５０°以上である。 The oil repellency means, for example, a contact angle meter (for example, DodecMaster 300 (product name) manufactured by Kyowa Interface Science Co., Ltd.) on the surface of a base material (glass base material, etc.) surface-treated with the above-mentioned surface treatment agent. When the contact angle (deg) of dodecane is measured using, it means that the contact angle of dodecane is relatively large. Specifically, the contact angle of dodecane is 35 ° or more, preferably 40 ° or more, and more preferably 50 ° or more.

本実施形態に係る表面処理剤によれば、ガラス、プラスチック、繊維、建築部材等の被処理基材の表面処理に用いることで、当該被処理基材の表面に防汚膜等の機能性薄膜（表面処理層）を形成することができる。すなわち、本実施形態に係る親水性及び撥油性を付与可能な表面処理剤は、防汚層形成用表面処理剤として利用することができる。 According to the surface treatment agent according to the present embodiment, by using it for the surface treatment of the base material to be treated such as glass, plastic, fiber, and building member, a functional thin film such as an antifouling film is applied to the surface of the base material to be treated. (Surface treatment layer) can be formed. That is, the surface treatment agent capable of imparting hydrophilicity and oil repellency according to the present embodiment can be used as a surface treatment agent for forming an antifouling layer.

［表面処理剤の製造方法］
本実施形態に係る表面処理剤は、例えば、上記フッ素含有化合物と、上記共重合体とを、溶媒中、無触媒条件下で混合させることにより製造され得る。 [Manufacturing method of surface treatment agent]
The surface treatment agent according to the present embodiment can be produced, for example, by mixing the fluorine-containing compound and the copolymer in a solvent under non-catalytic conditions.

上記フッ素含有化合物と上記共重合体との混合比は、例えば、上記フッ素含有化合物１質量部に対し、１〜２５質量部であるのが好ましく、２〜２０質量部であるのがより好ましく、５〜１５質量部であるのが特に好ましい。上記フッ素含有化合物と上記共重合体との混合比が上記範囲内にあることで、得られる表面処理剤において優れた親水性及び撥油性が発現され得る。上記共重合体が式（３）で示される化学構造を有するもの（構成成分としてカルボン酸を含むもの）である場合、上記フッ素含有化合物１質量部に対し、１質量部以上であるのが好ましく、５〜１５質量部であるのが特に好ましい。当該混合比が上記範囲外であると、所望とする親水性が発現され難くなるおそれがある。 The mixing ratio of the fluorine-containing compound and the copolymer is, for example, preferably 1 to 25 parts by mass, more preferably 2 to 20 parts by mass, based on 1 part by mass of the fluorine-containing compound. It is particularly preferably 5 to 15 parts by mass. When the mixing ratio of the fluorine-containing compound and the copolymer is within the above range, excellent hydrophilicity and oil repellency can be exhibited in the obtained surface treatment agent. When the copolymer has a chemical structure represented by the formula (3) (contains a carboxylic acid as a constituent component), it is preferably 1 part by mass or more with respect to 1 part by mass of the fluorine-containing compound. , 5 to 15 parts by mass is particularly preferable. If the mixing ratio is out of the above range, it may be difficult to develop the desired hydrophilicity.

上記溶媒は、上記フッ素含有化合物と上記共重合体との反応生成物をミセル状態で存在させ得るものであればよく、例えば、炭素数１〜５のアルコール系溶媒（メタノール、エタノール、プロパノール、ブタノール等）であればよく、炭素数４以上のアルコール系溶媒が用いられる場合には、ノルマルアルコールであるのが好ましい。かかるアルコール系溶媒は僅かに水を含んでいてもよいが、アルコール濃度が９５容量％以上であればよく、９８容量％以上であるのが好ましい。アルコール系溶媒に水が５容量％を超えて含まれていると、上記フッ素含有化合物と上記共重合体との反応生成物をミセル状態で存在させることが困難となるおそれがある。 The solvent may be any solvent as long as the reaction product of the fluorine-containing compound and the copolymer can be present in a micelle state. For example, an alcohol solvent having 1 to 5 carbon atoms (methanol, ethanol, propanol, butanol) can be used. Etc.), and when an alcohol solvent having 4 or more carbon atoms is used, it is preferably a normal alcohol. Such an alcohol solvent may contain a small amount of water, but the alcohol concentration may be 95% by volume or more, preferably 98% by volume or more. If the alcohol solvent contains more than 5% by volume of water, it may be difficult to allow the reaction product of the fluorine-containing compound and the copolymer to exist in a micelle state.

［表面処理方法］
本実施形態における表面処理方法は、本実施形態に係る表面処理剤を被処理基材の表面に塗布する工程を含む。表面処理剤を被処理基材の表面に塗布する方法としては、特に限定されるものではなく、例えば、刷毛、ローラー、スプレー等を用いて塗布する方法や、表面処理剤に被処理基材を浸漬させる方法等が挙げられる。 [Surface treatment method]
The surface treatment method in the present embodiment includes a step of applying the surface treatment agent according to the present embodiment to the surface of the base material to be treated. The method of applying the surface treatment agent to the surface of the base material to be treated is not particularly limited, and for example, a method of applying the surface treatment agent using a brush, a roller, a spray, or the like, or a method of applying the surface treatment agent to the surface treatment base material is applied. Examples thereof include a method of immersing.

本実施形態において、表面処理剤を被処理基材の表面に塗布することで形成された塗膜を加熱することで、溶媒を除去してもよい。加熱方法としては、オーブンによる加熱、熱プレスによる加熱等が挙げられるが、特に制限されるものではない。加熱条件としては、例えば、１００〜１８０℃で１０〜６０分程度、好ましくは１００〜１３０℃で１０〜３０分程度である。 In the present embodiment, the solvent may be removed by heating the coating film formed by applying the surface treatment agent to the surface of the substrate to be treated. Examples of the heating method include heating by an oven and heating by a hot press, but the heating method is not particularly limited. The heating conditions are, for example, about 10 to 60 minutes at 100 to 180 ° C., preferably about 10 to 30 minutes at 100 to 130 ° C.

上述したように、本実施形態に係る表面処理剤を用いた表面処理方法を実施することで、被処理基材の表面（被処理面）に表面処理層が形成されてなる表面処理基材を作製することができる。かかる表面処理基材において、表面処理層は、基部としての被処理基材の表面（第１面）に少なくとも形成されていればよいが、裏面（第２面）に形成されていてもよい。このようにして作製された表面処理基材においては、その表面処理層が優れた親水性及び撥油性を発現することができる。 As described above, by implementing the surface treatment method using the surface treatment agent according to the present embodiment, a surface treatment base material in which a surface treatment layer is formed on the surface (surface to be treated) of the base material to be treated can be obtained. Can be made. In such a surface-treated base material, the surface-treated layer may be formed at least on the front surface (first surface) of the base material to be treated as a base, but may be formed on the back surface (second surface). In the surface-treated base material produced in this manner, the surface-treated layer can exhibit excellent hydrophilicity and oil repellency.

以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属するすべての設計変更や均等物をも含む趣旨である。 The embodiments described above have been described for facilitating the understanding of the present invention, and have not been described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

以下、試験例等を挙げて本発明をさらに詳細に説明するが、本発明は下記の試験例等に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to test examples and the like, but the present invention is not limited to the following test examples and the like.

［試料１］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、上記式（２−１）で示されるジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体（ＰＡＳ−Ｊ−４１，ニットーボーメディカル社製，重量平均分子量：１００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 1]
20 mg of the fluorine-containing compound represented by the above formula (5) and a diallyldimethylammonium chloride / acrylamide copolymer represented by the above formula (2-1) (PAS-J-41, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight: 10000) ) 100 mg was added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.

［試料２］
ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体の添加量を３００ｍｇに変更した以外は、試料１と同様にして表面処理剤を調製した。 [Sample 2]
A surface treatment agent was prepared in the same manner as in Sample 1 except that the amount of the diallyldimethylammonium chloride / acrylamide copolymer added was changed to 300 mg.

［試料３］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、上記式（２−１）で示されるジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体（ＰＡＳ−Ｊ−８１，ニットーボーメディカル社製，重量平均分子量：１８００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 3]
20 mg of the fluorine-containing compound represented by the above formula (5) and a diallyldimethylammonium chloride / acrylamide copolymer represented by the above formula (2-1) (PAS-J-81, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight: 10000 ) 100 mg was added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.

［試料４］
ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体の添加量を３００ｍｇに変更した以外は、試料３と同様にして表面処理剤を調製した。 [Sample 4]
A surface treatment agent was prepared in the same manner as in Sample 3 except that the amount of the diallyldimethylammonium chloride / acrylamide copolymer added was changed to 300 mg.

［試料５］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、上記式（２−１）で示されるジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体（ＰＡＳ−Ｊ−８１Ｌ，ニットーボーメディカル社製，重量平均分子量：１００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 5]
20 mg of the fluorine-containing compound represented by the above formula (5) and a diallyldimethylammonium chloride / acrylamide copolymer represented by the above formula (2-1) (PAS-J-81L, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight: 10000 ) 100 mg was added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.

［試料６］
ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体の添加量を３００ｍｇに変更した以外は、試料５と同様にして表面処理剤を調製した。 [Sample 6]
A surface treatment agent was prepared in the same manner as in Sample 5, except that the amount of the diallyldimethylammonium chloride / acrylamide copolymer added was changed to 300 mg.

［試料７］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、上記式（３−１）で示されるジアリルエチルメチルアンモニウムエチルサルフェイト・マレイン酸共重合体（ＰＡＳ−２４５１，ニットーボーメディカル社製，重量平均分子量：３００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 7]
20 mg of a fluorine-containing compound represented by the above formula (5) and a diallylethylmethylammonium ethylsulfate-maleic acid copolymer represented by the above formula (3-1) (PAS-2451, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight) : 30000) 100 mg was added to methanol as a solvent, and the mixture was stirred at room temperature for 3 hours to prepare a surface treatment agent.

［試料８］
ジアリルエチルメチルアンモニウムエチルサルフェイト・マレイン酸共重合体の添加量を３００ｍｇに変更した以外は、試料７と同様にして表面処理剤を調製した。 [Sample 8]
A surface treatment agent was prepared in the same manner as in Sample 7, except that the amount of the diallylethylmethylammonium ethylsulfate / maleic acid copolymer added was changed to 300 mg.

［試料９］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、上記式（３−２）で示されるジアリルジメチルアンモニウムクロリド・マレイン酸共重合体（ＰＡＳ−２３５１，ニットーボーメディカル社製，重量平均分子量：２５０００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 9]
20 mg of a fluorine-containing compound represented by the above formula (5) and a diallyldimethylammonium chloride-maleic acid copolymer represented by the above formula (3-2) (PAS-2351, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight: 25000) A surface treatment agent was prepared by adding 100 mg to methanol as a solvent and stirring at room temperature for 3 hours.

［試料１０］
ジアリルジメチルアンモニウムクロリド・マレイン酸共重合体の添加量を３００ｍｇに変更した以外は、試料９と同様にして表面処理剤を調製した。 [Sample 10]
A surface treatment agent was prepared in the same manner as in Sample 9, except that the amount of the diallyldimethylammonium chloride-maleic acid copolymer added was changed to 300 mg.

［試料１１］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、下記式（１０）で示される３−クロロ−２−ヒドロキシプロピル化ジアリルアミン塩酸塩・ジアリルジメチルアンモニウムクロリド共重合体（ＰＡＳ−８８０，ニットーボーメディカル社製，重量平均分子量：４００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 11]
20 mg of a fluorine-containing compound represented by the above formula (5) and a 3-chloro-2-hydroxypropylated diallylamine hydrochloride / diallyldimethylammonium chloride copolymer represented by the following formula (10) (PAS-880, Nittobo Medical Co., Ltd.) A surface treatment agent was prepared by adding 100 mg (weight average molecular weight: 40,000) to methanol as a solvent and stirring at room temperature for 3 hours.

Figure 2020139046
Figure 2020139046

［試料１２］
３−クロロ−２−ヒドロキシプロピル化ジアリルアミン塩酸塩・ジアリルジメチルアンモニウムクロリド共重合体の添加量を３００ｍｇに変更した以外は、試料１１と同様にして表面処理剤を調製した。 [Sample 12]
A surface treatment agent was prepared in the same manner as in Sample 11 except that the amount of the 3-chloro-2-hydroxypropylated diallylamine hydrochloride / diallyldimethylammonium chloride copolymer was changed to 300 mg.

［試料１３］
上記式（５）で示されるフッ素含有化合物２０ｍｇと、下記式（１１）で示されるジアリルアミン塩酸塩・アクリルアミド共重合体（ＰＡＳ−２１４１ＣＬ，ニットーボーメディカル社製，重量平均分子量：１００００）１００ｍｇとを、溶媒としてのメタノールに添加し、室温で３時間攪拌することで、表面処理剤を調製した。 [Sample 13]
20 mg of the fluorine-containing compound represented by the above formula (5) and 100 mg of a diallylamine hydrochloride / acrylamide copolymer (PAS-2141CL, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight: 10000) represented by the following formula (11) were added. A surface treatment agent was prepared by adding to methanol as a solvent and stirring at room temperature for 3 hours.

Figure 2020139046
Figure 2020139046

［試料１４］
ジアリルアミン塩酸塩・アクリルアミド共重合体の添加量を３００ｍｇに変更した以外は、試料１１と同様にして表面処理剤を調製した。 [Sample 14]
A surface treatment agent was prepared in the same manner as in Sample 11 except that the amount of the diallylamine hydrochloride / acrylamide copolymer added was changed to 300 mg.

［試料１５］
塩基性触媒としてのアンモニア水１ｍＬをさらに添加した以外は、試料３と同様にして表面処理剤を調製した。 [Sample 15]
A surface treatment agent was prepared in the same manner as in Sample 3, except that 1 mL of aqueous ammonia as a basic catalyst was further added.

［試料１６］
塩基性触媒としてのアンモニア水１ｍＬをさらに添加した以外は、試料４と同様にして表面処理剤を調製した。 [Sample 16]
A surface treatment agent was prepared in the same manner as in Sample 4, except that 1 mL of aqueous ammonia as a basic catalyst was further added.

［試料１７］
塩基性触媒としてのアンモニア水１ｍＬをさらに添加した以外は、試料７と同様にして表面処理剤を調製した。 [Sample 17]
A surface treatment agent was prepared in the same manner as in Sample 7, except that 1 mL of aqueous ammonia as a basic catalyst was further added.

［試料１８］
塩基性触媒としてのアンモニア水１ｍＬをさらに添加した以外は、試料８と同様にして表面処理剤を調製した。 [Sample 18]
A surface treatment agent was prepared in the same manner as in Sample 8 except that 1 mL of aqueous ammonia as a basic catalyst was further added.

〔試験例１〕接触角測定試験
第１面及びそれに対向する第２面を有し、第１面に対して塩素系溶剤（１，２−ジクロロエタン）を用いた脱脂処理が施されたガラス（被処理基材）を準備し、当該ガラスの第１面に対しスピンコート法（回転数：２０００ｒｐｍ，回転時間：３０ｓ，滴下量：０．３ｍＬ）により表面処理剤（試料１〜１８）の塗膜を形成することで、表面処理基材を得た。当該表面処理基材における水及びドデカンの接触角（ｄｅｇ）を、接触角計（協和界面科学社製，製品名：ＤｒｏｐＭａｓｔｅｒ３００）を用いて測定した。結果を表１に示す。表１において水接触角（０ｍｉｎ）及びドデカン接触角は、それぞれ、表面処理基材に水及びドデカンを滴下直後の接触角測定結果であり、水接触角（３０ｍｉｎ）は、表面処理基材に水を滴下してから３０分経過後の接触角測定結果である。なお、参考として、表面処理剤による表面処理を行う前のガラス（試料１９）における水及びドデカンの接触角（ｄｅｇ）の測定結果もあわせて表１に示す。 [Test Example 1] Contact angle measurement test A glass having a first surface and a second surface facing the first surface, and the first surface is degreased with a chlorine-based solvent (1,2-dichloroethane). The base material to be treated) is prepared, and the surface treatment agent (samples 1 to 18) is applied to the first surface of the glass by a spin coating method (rotation speed: 2000 rpm, rotation time: 30 s, dropping amount: 0.3 mL). By forming a film, a surface-treated substrate was obtained. The contact angle (deg) of water and dodecane on the surface-treated substrate was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name: DropMaster300). The results are shown in Table 1. In Table 1, the water contact angle (0 min) and the dodecane contact angle are the measurement results of the contact angle immediately after dropping water and dodecane on the surface-treated base material, respectively, and the water contact angle (30 min) is water on the surface-treated base material. It is a contact angle measurement result 30 minutes after dropping. For reference, Table 1 also shows the measurement results of the contact angle (deg) of water and dodecane on the glass (sample 19) before the surface treatment with the surface treatment agent.

Figure 2020139046
Figure 2020139046

上記表１に示すように、所定のフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物の共重合体（上記式（２−１）で示されるジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体）との反応生成物を含む表面処理剤は、優れた親水性及び撥油性を付与可能であることが確認された。また、所定のフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びカルボン酸の共重合体（上記式（３−１）で示されるジアリルエチルメチルアンモニウムエチルサルフェイト・マレイン酸共重合体、上記式（３−２）で示されるジアリルジメチルアンモニウムクロリド・マレイン酸共重合体）との反応生成物を含む表面処理剤は、優れた親水性及び撥油性を付与することができることが確認された。なお、試料１９（未処理ガラス）における水の接触角（３０ｍｉｎ）が接触角（０ｍｉｎ）よりも小さくなっているのは、揮発により水滴が小さくなったことによるものであった。 As shown in Table 1 above, a copolymer of a predetermined fluorine-containing compound, a quaternary ammonium salt of allylamine, and an amide compound (diallyldimethylammonium chloride / acrylamide copolymer represented by the above formula (2-1)). It was confirmed that the surface treatment agent containing the reaction product of the above can impart excellent hydrophilicity and oil repellency. Further, a copolymer of a predetermined fluorine-containing compound, a quaternary ammonium salt of allylamine and a carboxylic acid (diallylethylmethylammonium ethylsulfate / maleic acid copolymer represented by the above formula (3-1), the above formula ( It was confirmed that the surface treatment agent containing the reaction product with the diallyldimethylammonium chloride / maleic acid copolymer (shown in 3-2) can impart excellent hydrophilicity and oil repellency. The contact angle (30 min) of water in the sample 19 (untreated glass) was smaller than the contact angle (0 min) because the water droplets became smaller due to volatilization.

一方で、構成成分の一つがアミド化合物ではない上記式（１０）で示される３−クロロ−２−ヒドロキシプロピル化ジアリルアミン塩酸塩・ジアリルジメチルアンモニウムクロリド共重合体を含む表面処理剤（試料１１，１２）は、撥油性を付与可能であるものの、親水性を付与することができないことが確認された。また、構成成分の一つがアリルアミンの４級アンモニウム塩ではない上記式（１１）で示されるジアリルアミン塩酸塩・アクリルアミド共重合体を含む表面処理剤（試料１３，１４）においても同様に、撥油性を付与可能であるものの、親水性を付与することができないことが確認された。これらの結果から、所定のフッ素化合物との反応生成物とを形成する共重合体の構成成分が、アリルアミンの４級アンモニウム塩とアミド化合物又はカルボン酸とであることで、当該反応生成物を含む表面処理剤において優れた親水性及び撥油性を付与可能であることが明らかとなった。 On the other hand, a surface treatment agent (Samples 11 and 12) containing a 3-chloro-2-hydroxypropylated diallylamine hydrochloride / diallyldimethylammonium chloride copolymer represented by the above formula (10) in which one of the constituents is not an amide compound. ) Can impart oil repellency, but cannot impart hydrophilicity. Similarly, the surface treatment agents (samples 13 and 14) containing the diallylamine hydrochloride / acrylamide copolymer represented by the above formula (11), in which one of the constituents is not a quaternary ammonium salt of allylamine, also have oil repellency. It was confirmed that although it can be imparted, hydrophilicity cannot be imparted. From these results, the constituent components of the copolymer forming the reaction product with the predetermined fluorine compound are the quaternary ammonium salt of allylamine and the amide compound or the carboxylic acid, and the reaction product is contained. It has been clarified that the surface treatment agent can impart excellent hydrophilicity and oil repellency.

また、各表面処理剤（試料１〜１８）を目視した結果、触媒を含まない反応系で生成された反応生成物を含む表面処理剤（試料１〜１４）はいずれも無色透明であるのに対し、塩基性触媒（アンモニア水）を含む反応系で生成される反応生成物を含む表面処理剤（試料１５〜１８）は顕著に白濁していることが確認された。さらに、試料１〜１４の表面処理剤で表面処理が施されたガラス（被処理基材）の表面においては、無色透明であり、視認性が確保されているのに対し、試料１５〜１８の表面処理剤で表面処理が施されたガラス（被処理基材）の表面においては、わずかに白濁しており、視認性が不十分であることが確認された。この結果から、無触媒条件下で得られる反応生成物を含む表面処理剤であれば、無色透明の表面処理層を被処理基材上に形成可能であり、表面処理層を有する表面処理基材の視認性を確保可能であることが明らかとなった。 Further, as a result of visually observing each surface treatment agent (samples 1 to 18), the surface treatment agents (samples 1 to 14) containing the reaction products produced in the reaction system not containing the catalyst were all colorless and transparent. On the other hand, it was confirmed that the surface treatment agent (samples 15 to 18) containing the reaction product produced in the reaction system containing the basic catalyst (water ammonia) was significantly cloudy. Further, the surface of the glass (base material to be treated) surface-treated with the surface treatment agents of Samples 1 to 14 is colorless and transparent to ensure visibility, whereas Samples 15 to 18 have been treated. It was confirmed that the surface of the glass (base material to be treated) surface-treated with the surface treatment agent was slightly cloudy and the visibility was insufficient. From this result, if it is a surface treatment agent containing a reaction product obtained under non-catalytic conditions, a colorless and transparent surface treatment layer can be formed on the base material to be treated, and the surface treatment base material having the surface treatment layer. It became clear that the visibility of the above can be ensured.

本発明は、親水性と撥油性とが要求される製品の技術分野において有用である。 The present invention is useful in the technical field of products that require hydrophilicity and oil repellency.

Claims (14)

下記式（１）で示されるフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物又はカルボン酸の共重合体と、溶媒とを含有することを特徴とする表面処理剤。
Figure 2020139046
 上記式（１）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表し、ｘは１〜１００の整数であり、ｙは０〜１００の整数である。 A surface treatment agent containing a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a carboxylic acid, and a solvent.
Figure 2020139046
 In the above formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 are independent hydrogen atoms or monovalent organic groups, respectively. , X is an integer of 1 to 100, and y is an integer of 0 to 100. 前記共重合体が、下記式（２）で示される化学構造を有することを特徴とする請求項１に記載の表面処理剤。
Figure 2020139046
 上記式（２）中、Ｒ1’及びＲ2’は各々独立して炭素数１〜４のアルキル基を表し、Ｘはハロゲン化物イオン、無機アニオン又は有機アニオンを表す。 The surface treatment agent according to claim 1, wherein the copolymer has a chemical structure represented by the following formula (2).
Figure 2020139046
 In the above formula (2), R 1 'and R 2' represents an alkyl group having 1 to 4 carbon atoms each independently, X represents a halide ion, an inorganic anion or an organic anion. 前記共重合体が、下記式（３）で示される化学構造を有することを特徴とする請求項１に記載の表面処理剤。
Figure 2020139046
 上記式（３）中、Ｒ3’及びＲ4’は各々独立して炭素数１〜４のアルキル基を表し、Ｘはハロゲン化物イオン、無機アニオン又は有機アニオンを表す。 The surface treatment agent according to claim 1, wherein the copolymer has a chemical structure represented by the following formula (3).
Figure 2020139046
 In the above formula (3), R 3 'and R 4' represents an alkyl group having 1 to 4 carbon atoms each independently, X represents a halide ion, an inorganic anion or an organic anion. 前記フッ素含有化合物と前記共重合体との含有比（質量基準）が、１：１〜２５であることを特徴とする請求項１〜３のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 3, wherein the content ratio (mass standard) of the fluorine-containing compound to the copolymer is 1: 1 to 25. 前記溶媒が、炭素数１〜５のアルコール系溶媒であることを特徴とする請求項１〜４のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 4, wherein the solvent is an alcohol solvent having 1 to 5 carbon atoms. 前記アリルアミンの４級アンモニウム塩及びアミド化合物の共重合体の重量平均分子量が、１５００００以上であることを特徴とする請求項１〜５のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 5, wherein the copolymer of the quaternary ammonium salt of allylamine and the amide compound has a weight average molecular weight of 150,000 or more. 前記式（１）において、ｙが０であることを特徴とする請求項１〜６のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 6, wherein y is 0 in the formula (1). 前記式（１）において、Ｒ1で表されるフルオロアルキル基を含有する基が、下記式（４）で表される基であることを特徴とする請求項１〜７のいずれかに記載の表面処理剤。
Figure 2020139046
 上記式（４）中、ｐは０〜２の整数である。 The invention according to any one of claims 1 to 7, wherein the group containing the fluoroalkyl group represented by R 1 in the formula (1) is a group represented by the following formula (4). Surface treatment agent.
Figure 2020139046
 In the above equation (4), p is an integer of 0 to 2. 前記式（１）において、Ｒ2はメチル基であることを特徴とする請求項１〜８のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 8, wherein R 2 is a methyl group in the formula (1). 前記式（１）において、ｘが１〜１０の整数であることを特徴とする請求項１〜９のいずれかに記載の表面処理剤。 The surface treatment agent according to any one of claims 1 to 9, wherein x is an integer of 1 to 10 in the formula (1). 第１面及び当該第１面に対向する第２面を有する基部と、
前記基部の少なくとも前記第１面に設けられてなる表面処理層と
を備え、
前記表面処理層は、請求項１〜１０のいずれかに記載の表面処理剤を用いた表面処理が前記基部の前記第１面に施されることにより形成されてなるものであることを特徴とする表面処理基材。 A base having a first surface and a second surface facing the first surface,
A surface treatment layer provided on at least the first surface of the base portion is provided.
The surface treatment layer is characterized in that it is formed by applying a surface treatment using the surface treatment agent according to any one of claims 1 to 10 to the first surface of the base portion. Surface treatment base material to be used. 下記式（１）で示されるフッ素含有化合物と、アリルアミンの４級アンモニウム塩及びアミド化合物又はカルボン酸の共重合体と、溶媒とを混合することを特徴とする表面処理剤の製造方法。
Figure 2020139046
 上記式（１）中、Ｒ1はフルオロアルキル基を含有する基を表し、Ｒ2はアルキル基又はアルコキシアルキル基を表し、Ｒ3及びＲ4は各々独立して水素原子又は１価の有機基を表し、ｘは１〜１００の整数であり、ｙは０〜１００の整数である。 A method for producing a surface treatment agent, which comprises mixing a fluorine-containing compound represented by the following formula (1), a copolymer of a quaternary ammonium salt of allylamine and an amide compound or a carboxylic acid, and a solvent.
Figure 2020139046
 In the above formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, and R 3 and R 4 are independent hydrogen atoms or monovalent organic groups, respectively. , X is an integer of 1 to 100, and y is an integer of 0 to 100. 酸触媒及びアルカリ触媒のいずれをも混合させないことを特徴とする請求項１２に記載の表面処理剤の製造方法。 The method for producing a surface treatment agent according to claim 12, wherein neither an acid catalyst nor an alkali catalyst is mixed. 請求項１〜１０のいずれかに記載の表面処理剤を用いて被処理基材に表面処理を施すことを特徴とする表面処理方法。 A surface treatment method characterized by subjecting a substrate to be treated with a surface treatment using the surface treatment agent according to any one of claims 1 to 10.
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