JP2016180025A - Method for producing surface-hydrophilized base material - Google Patents
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Abstract
Description
本発明は表面親水化基材の製造方法に関する。 The present invention relates to a method for producing a surface-hydrophilized substrate.
表面撥水性の、例えばポリオレフィン成形体の表面を親水化する方法としては、ポリオレフィン成形体に重合開始基を導入した後、当該成形体上で特殊なモノマーを重合させる方法が知られている（例えば、特許文献１）。 As a method for hydrophilizing the surface of, for example, a polyolefin molded body having a surface water repellency, a method is known in which a polymerization initiator is introduced into the polyolefin molded body and then a special monomer is polymerized on the molded body (for example, Patent Document 1).
しかしながら、上記した方法では、特殊なモノマーを準備する必要がある上、当該特殊なポリマーをポリオレフィン成形体に対して重合開始基を介して結合させる必要があるため、処理が煩雑であった。 However, in the above-described method, it is necessary to prepare a special monomer, and it is necessary to bind the special polymer to the polyolefin molded body via a polymerization initiating group, so that the processing is complicated.
そこで、本発明の発明者等は、簡便に親水性を付与する技術として、放射線の照射により、アクリル酸などの親水性モノマーを水溶液の形態で、撥水性基材の表面に対して直接的に反応させることを試みたところ、撥水性表面における親水性モノマー水溶液の「はじき」という新たな問題が生じた。詳しくは、親水性モノマーの水溶液を撥水性基材の表面に適用すると、当該水溶液は基材の撥水性表面上で激しくはじかれるため、そのまま放射線を照射しても、撥水性基材の表面上全面に親水性を付与することは不可能であった。 Therefore, the inventors of the present invention, as a technique for easily imparting hydrophilicity, directly exposed a hydrophilic monomer such as acrylic acid in the form of an aqueous solution to the surface of the water-repellent substrate by irradiation with radiation. Attempts were made to cause the reaction to cause a new problem of “repelling” of the aqueous hydrophilic monomer solution on the water-repellent surface. Specifically, when an aqueous solution of a hydrophilic monomer is applied to the surface of a water-repellent substrate, the aqueous solution is repelled vigorously on the water-repellent surface of the substrate. It was impossible to impart hydrophilicity to the entire surface.
本発明は、撥水性基材の表面上全面に親水性を簡便に付与することができる表面親水化基材の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of the surface hydrophilization base material which can provide hydrophilicity simply to the whole surface on the surface of a water-repellent base material.
本発明は、少なくとも表面が撥水性である基材の表面に、親水性基含有重合性有機化合物を含む溶液を適用する工程；、
該溶液を適用した基材を放射線透過フィルムで被覆し、該溶液を表面全面に展開する工程；および
放射線を照射する工程；
を含むことを特徴とする表面親水化基材の製造方法に関する。
The present invention comprises a step of applying a solution containing a hydrophilic group-containing polymerizable organic compound to at least the surface of a substrate having a water-repellent surface;
Coating the substrate to which the solution is applied with a radiation transmitting film and spreading the solution over the entire surface; and irradiating with radiation;
It is related with the manufacturing method of the surface hydrophilization base material characterized by including.
本発明においては、親水性基含有重合性有機化合物を含む溶液を適用した基材を放射線透過フィルムで被覆して、該溶液を表面全面に展開するので、放射線の照射により、表面撥水性基材の該表面上全面に、親水性基含有重合性有機化合物を直接的に化学結合させることができる。従って、本発明によれば、表面撥水性基材の表面上全面に親水性を簡便に付与することができる。 In the present invention, a substrate to which a solution containing a hydrophilic group-containing polymerizable organic compound is applied is coated with a radiation transmitting film, and the solution is spread over the entire surface. The hydrophilic group-containing polymerizable organic compound can be directly chemically bonded to the entire surface of the surface. Therefore, according to the present invention, hydrophilicity can be easily imparted to the entire surface of the surface water-repellent substrate.
［表面親水化基材の製造方法］
本発明において表面親水化基材は以下の工程を含む方法により製造することができる：
少なくとも表面が撥水性である基材の表面に、親水性基含有重合性有機化合物（以下、単に「有機化合物Ａ」ということがある）を含む溶液を適用する工程（溶液適用工程）；
該溶液を適用した基材を放射線透過フィルムで被覆し、該溶液を表面全面に展開する工程（溶液展開工程）；および
放射線を照射する工程（放射線照射工程）。
[Method for producing surface hydrophilized substrate]
In the present invention, the surface hydrophilized substrate can be produced by a method including the following steps:
A step of applying a solution containing a hydrophilic group-containing polymerizable organic compound (hereinafter sometimes simply referred to as “organic compound A”) to the surface of a substrate having a water-repellent surface (solution application step);
A step of coating the substrate to which the solution is applied with a radiation transmitting film, and spreading the solution over the entire surface (solution development step); and a step of irradiating radiation (radiation irradiation step).
本発明において、放射線照射工程は、溶液適用工程および溶液展開工程を実施した後に実施してもよいし（第１実施態様）、または溶液適用工程および溶液展開工程を実施する前に実施してもよい（第２実施態様）。放射線照射工程を先に行う場合、生じたラジカル種の失活が生じるため、窒素雰囲気中で放射線照射する等の条件が必要となり、装置が複雑となる。したがって第１実施態様が好ましい。以下、まず、第１実施態様について詳しく説明する。 In the present invention, the radiation irradiation step may be performed after the solution application step and the solution development step are performed (first embodiment), or may be performed before the solution application step and the solution development step are performed. Good (second embodiment). When the radiation irradiation step is performed first, the generated radical species are deactivated, so that conditions such as radiation irradiation in a nitrogen atmosphere are required, and the apparatus becomes complicated. Therefore, the first embodiment is preferable. Hereinafter, first, the first embodiment will be described in detail.
（第１実施態様）
・溶液適用工程：
本工程においては、表面撥水性基材の表面に、有機化合物Ａを含む溶液を適用する。
(First embodiment)
・ Solution application process:
In this step, a solution containing the organic compound A is applied to the surface of the surface water-repellent substrate.
表面撥水性基材は少なくとも表面が撥水性を有するものである。このような基材が有する撥水性表面は、蒸留水による接触角ＣＡとして８０°超、特に８５°以上程度を通常、示す。撥水性表面の接触角ＣＡの上限値は特に限定されるものではないが、当該接触角ＣＡは通常、１７９°以下、特に１２０°以下である。 The surface water-repellent substrate has at least the surface water repellency. The water-repellent surface such substrates has is, 80 ° greater as the contact angle C A with distilled water, the extent especially 85 ° to the normal, shown. The upper limit value of the contact angle C A water-repellent surface is not particularly limited, but the contact angle C A normal, 179 ° or less, particularly 120 ° or less.
本明細書中、接触角ＣＡは撥水性表面において後述する方法により、５箇所で測定した値の平均値を用いている。 In the present specification, the contact angle C A by the method described below in the water-repellent surface and using an average value of values measured at 5 points.
このような表面撥水性基材は通常、ポリオレフィン樹脂を含むものである。ポリオレフィン樹脂として、例えば、エチレン、プロピレン、ブチレンからなる群から選択される１種以上のオレフィンのホモポリマーまたはコポリマーが挙げられる。ポリオレフィン樹脂の具体例として、例えば、ポリエチレン、ポリプロピレン等が挙げられ、好ましくはポリプロピレンである。表面撥水性基材は、上記接触角ＣＡを示す撥水性表面を有する限り、例えば、ポリエステル樹脂、ポリ塩化ビニル樹脂、ポリスチレン樹脂等の他のポリマーを含んでもよい。 Such a surface water-repellent substrate usually contains a polyolefin resin. Examples of the polyolefin resin include homopolymers or copolymers of one or more olefins selected from the group consisting of ethylene, propylene, and butylene. Specific examples of the polyolefin resin include, for example, polyethylene and polypropylene, and is preferably polypropylene. Surface water-repellent substrate, as long as the water-repellent surface indicating the contact angle C A, for example, polyester resins, polyvinyl chloride resins, may include other polymers such as polystyrene resin.
表面撥水性基材はいかなる全体形状を有していてもよいが、撥水性表面のより一層の親水化の観点からは、有機化合物Ａの溶液が適用される撥水性表面は平面形状を有することが好ましい。平面形状は、厳密に平面の形状だけでなく、エンボス加工された略平面形状等も含む概念で用いるものとする。表面撥水性基材の全体形状は好ましくはシート形状である。 The surface water-repellent substrate may have any overall shape, but from the viewpoint of further hydrophilization of the water-repellent surface, the water-repellent surface to which the solution of the organic compound A is applied has a planar shape. Is preferred. The planar shape is not only strictly a planar shape but also a concept including an embossed substantially planar shape and the like. The overall shape of the surface water-repellent substrate is preferably a sheet shape.
表面撥水性基材がシート形状を有するとき、その厚みは特に限定されず、例えば、１μｍ〜１０００μｍであり、好ましくは１０μｍ〜３００μｍである。 When the surface water-repellent substrate has a sheet shape, the thickness is not particularly limited, and is, for example, 1 μm to 1000 μm, preferably 10 μm to 300 μm.
表面撥水性基材は通常、ポリオレフィン樹脂および所望により添加される他のポリマーおよび添加剤を含む組成物を、押出成形法、射出成形法、圧縮成形法などの公知の成形法に供することにより、得ることができる。添加剤としては、プラスチック材料の分野で知られているあらゆる添加剤が使用可能であり、例えば、充填材、軟化剤、架橋剤、酸化防止剤等が挙げられる。 The surface water-repellent substrate is usually subjected to a known molding method such as an extrusion molding method, an injection molding method, or a compression molding method by using a composition containing a polyolefin resin and other polymers and additives that are optionally added. Can be obtained. As the additive, any additive known in the field of plastic materials can be used, and examples thereof include a filler, a softening agent, a crosslinking agent, and an antioxidant.
有機化合物Ａは、親水性基含有重合性有機化合物である。この親水性基含有重合性有機化合物としては、１分子あたり１以上の親水性基と１以上の不飽和結合を有する親水性基含有不飽和モノマー、ならびにそれらのオリゴマーおよびポリマーからなる群から選択される１種以上の有機化合物等が挙げられる。親水性基は、親水性を有する有機基のことであり、例えば、カルボキシル基、水酸基、アミノ基、スルホン酸基からなる群から選択することができる。好ましい親水性基はカルボキシル基である。 The organic compound A is a hydrophilic group-containing polymerizable organic compound. The hydrophilic group-containing polymerizable organic compound is selected from the group consisting of hydrophilic group-containing unsaturated monomers having one or more hydrophilic groups and one or more unsaturated bonds per molecule, and oligomers and polymers thereof. One or more organic compounds. The hydrophilic group is an organic group having hydrophilicity, and can be selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, and a sulfonic acid group, for example. A preferred hydrophilic group is a carboxyl group.
親水性基含有不飽和モノマーの好ましい具体例として、例えば、（メタ）アクリル酸、トランス−２−ブテン酸、シス−２−ブテン酸、３−ブテン酸、アリルアルコールが挙げられる。本明細書中、（メタ）アクリル酸はアクリル酸およびメタクリル酸を包含して意味するものとする。 Preferable specific examples of the hydrophilic group-containing unsaturated monomer include (meth) acrylic acid, trans-2-butenoic acid, cis-2-butenoic acid, 3-butenoic acid, and allyl alcohol. In the present specification, (meth) acrylic acid is meant to include acrylic acid and methacrylic acid.
有機化合物Ａを含む溶液の溶媒は、有機化合物Ａを溶解できる限り特に限定されず、水であっても、メタノール、エタノールなどの有機溶媒であってもよいが、水が好ましい。従来の方法では、水溶液は撥水性表面にはじかれるため、水溶液を用いて撥水性表面を親水化することはできなかったが、本発明においてはそのような水溶液を使用する場合であっても撥水性表面を容易かつ十分に親水化できるためであり、水溶液の場合に特に効果が発現される。 The solvent of the solution containing the organic compound A is not particularly limited as long as the organic compound A can be dissolved. Water or an organic solvent such as methanol or ethanol may be used, but water is preferable. In the conventional method, since the aqueous solution is repelled by the water-repellent surface, it was not possible to make the water-repellent surface hydrophilic using the aqueous solution. However, in the present invention, even when such an aqueous solution is used, the water-repellent surface is not repelled. This is because the aqueous surface can be easily and sufficiently hydrophilized, and the effect is particularly manifested in the case of an aqueous solution.
溶液中の有機化合物Ａ濃度は、特に限定されないが、より十分な親水化の観点から、１〜９９重量％が好ましく、より好ましくは５〜５０重量％である。 The concentration of the organic compound A in the solution is not particularly limited, but is preferably 1 to 99% by weight, more preferably 5 to 50% by weight from the viewpoint of sufficient hydrophilicity.
溶液には、界面活性剤を含有させることが好ましい。界面活性剤としては、アニオン性、カチオン性、ノニオン性および両性界面活性剤などの公知の界面活性剤が使用できる。界面活性剤の溶液中の濃度は通常、０．０１〜２重量％であり、０．１〜１．５重量％が好ましい。 The solution preferably contains a surfactant. As the surfactant, known surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used. The concentration of the surfactant in the solution is usually 0.01 to 2% by weight, preferably 0.1 to 1.5% by weight.
溶液の適用方法は、撥水性表面に溶液を供給できる限り特に限定されず、例えば、噴霧法、滴下法、塗布法等を採用することができる。 The application method of the solution is not particularly limited as long as the solution can be supplied to the water-repellent surface, and for example, a spray method, a dropping method, a coating method, or the like can be employed.
溶液の適用量は、次の溶液展開工程において、放射線透過フィルムと撥水性表面との間で溶液の十分な展開が達成される限り特に限定されず、通常は、適用される表面１ｍ２あたり１〜１００ｇ、特に５〜３０ｇ程度である。 The application amount of the solution is not particularly limited as long as sufficient development of the solution is achieved between the radiation transmissive film and the water-repellent surface in the next solution development step, and is usually 1 per 1 m 2 of the applied surface. -100 g, especially about 5-30 g.
・溶液展開工程：
本工程においては、溶液を適用した基材を放射線透過フィルム（以下、単位「フィルム」ということがある）で被覆し、該溶液を表面全面に展開する。展開とは、撥水性表面とフィルムとの間で溶液を広く延ばすことをいう。溶液を表面全面に展開するとは、撥水性表面の加工されるべき領域の全領域に溶液を展開するという意味であり、詳しくは撥水性表面とフィルムとの間において、はじき領域を発生させることなく、略一様に溶液を広く延ばす。本発明においては、このような展開により、十分な親水化が達成される。本工程を行わない場合、溶液は撥水性表面にはじかれるため、当該基材の表面上への一様な有機化合物の化学結合は困難である。
・ Solution development process:
In this step, the substrate to which the solution is applied is covered with a radiation transmitting film (hereinafter sometimes referred to as a unit “film”), and the solution is spread over the entire surface. Development refers to spreading the solution widely between the water repellent surface and the film. To spread the solution over the entire surface means to spread the solution over the entire area of the water-repellent surface to be processed, and in detail, without generating a repellent area between the water-repellent surface and the film. Widen the solution almost uniformly. In the present invention, sufficient hydrophilicity is achieved by such development. When this step is not performed, the solution is repelled by the water-repellent surface, and thus it is difficult to uniformly bond the organic compound onto the surface of the substrate.
フィルムの被覆に際しては、撥水性表面とフィルムとの間に気泡が入らないよう注意することが好ましい。 When coating the film, it is preferable to take care that no air bubbles enter between the water repellent surface and the film.
放射線透過フィルムは、放射線照射工程において有機化合物Ａの化学結合が達成される程度に、放射線を透過し得るフィルムであればよい。例えば、電子線を透過しながらも、電子線の影響を受けにくい、すなわちフィルム自体が架橋、崩壊又はグラフト重合しにくいものが好ましい。 The radiation transmissive film may be a film that can transmit radiation to the extent that chemical bonding of the organic compound A is achieved in the radiation irradiation step. For example, it is preferable to transmit the electron beam but not easily be affected by the electron beam, that is, the film itself is not easily crosslinked, disintegrated or graft polymerized.
放射線透過フィルムの具体例として、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリイミドフィルム、ポリフェニレンスルフィドフィルム等が挙げられる。放射線透過フィルムの厚みは、放射線を透過しつつ、かつ溶液を介して撥水性表面と密着可能な限り特に限定されず、通常は１〜２００μｍであり、好ましくは１０〜１００μｍである。 Specific examples of the radiation transmissive film include a polyethylene terephthalate (PET) film, a polyimide film, a polyphenylene sulfide film, and the like. The thickness of the radiation transmissive film is not particularly limited as long as it can transmit radiation and can be in close contact with the water-repellent surface via a solution.
放射線透過フィルムは、例えば、表面撥水性基材における少なくとも有機化合物Ａが化学結合する撥水性表面が凹凸のある形状を有する場合、当該形状に対応した形状を有するように、プレス成形等により付形して使用されてもよい。これにより、撥水性表面が凹凸のある形状を有する場合であっても、当該撥水性表面と当該付形フィルムとの間で溶液をより一層一様に展開できるようになる。 For example, when the water-repellent surface on which the surface of the surface water-repellent substrate is chemically bonded to at least the organic compound A has an uneven shape, the radiation-transmitting film is shaped by press molding or the like so as to have a shape corresponding to the shape. May be used. Thereby, even when the water-repellent surface has an uneven shape, the solution can be more uniformly developed between the water-repellent surface and the shaped film.
・放射線照射工程：
本工程では、撥水性基材の上に溶液を介して放射線透過フィルムを被せた状態で、撥水性基材に対してフィルム側から放射線を照射する。放射線を照射することにより、表面撥水性基材を構成するポリマーにラジカルを発生させつつ、これに対して有機化合物Ａが重合性部分、例えば不飽和結合に基づいて反応して化学結合が形成される。このとき、撥水性基材と化学結合を形成した有機化合物Ａに対して、さらに別の有機化合物Ａが連鎖的に不飽和結合に基づく反応を起こし、グラフト鎖を形成してもよい。従って、撥水性基材と化学結合を形成している有機化合物Ａは、前記親水性基含有不飽和モノマーに対応するモノマー形態を有していてもよいし、または親水性基含有不飽和モノマーのオリゴマーおよびポリマーに対応する形態を有していてもよい。
・ Radiation irradiation process:
In this step, the water-repellent substrate is irradiated with radiation from the film side in a state where a radiation-transmitting film is covered on the water-repellent substrate via a solution. By irradiating with radiation, radicals are generated in the polymer constituting the surface water-repellent substrate, while the organic compound A reacts on the basis of polymerizable moieties such as unsaturated bonds to form chemical bonds. The At this time, another organic compound A may cause a reaction based on an unsaturated bond in a chained manner with respect to the organic compound A that has formed a chemical bond with the water-repellent substrate, thereby forming a graft chain. Therefore, the organic compound A forming a chemical bond with the water-repellent substrate may have a monomer form corresponding to the hydrophilic group-containing unsaturated monomer, or the hydrophilic group-containing unsaturated monomer. You may have a form corresponding to an oligomer and a polymer.
表面に展開された有機化合物Ａの存在下、放射線を照射することにより、有機化合物Ａが表面撥水性基材内に滲入しながら、化学結合が形成され、結果として表面が親水性を有する改質表層部が形成される。 By irradiating with radiation in the presence of the organic compound A developed on the surface, the organic compound A penetrates into the surface water-repellent substrate, and a chemical bond is formed. As a result, the surface is hydrophilic. A surface layer portion is formed.
照射する放射線としては、表面撥水性基材を構成するポリマーにラジカルを発生させることができる限り特に限定されず、例えば、電子線、陽子線、重陽子線、α線、β線、Ｘ線、γ線、中性子線などが挙げられる。放射線は、照射装置の取扱い容易性の観点から、電子線が好ましい。 The radiation to be irradiated is not particularly limited as long as radicals can be generated in the polymer constituting the surface water-repellent substrate. For example, electron beam, proton beam, deuteron beam, α ray, β ray, X ray, Examples include gamma rays and neutron rays. The radiation is preferably an electron beam from the viewpoint of easy handling of the irradiation apparatus.
照射条件は、前記した表面接触角ＣＢが達成される限り特に限定されず、例えば、電子線を用いる場合、加速電圧１００〜８００ｋＶ、特に１５０〜３００ｋＶ、好ましくは１８０〜２７０ｋＶおよび照射線量５〜１０００ｋＧｙ、特に８〜２００ｋＧｙ、好ましくは１０〜１００ｋＧｙの条件下で照射を行う。 Irradiation conditions are not particularly limited as long as the surface contact angle C B is achieved, for example, when using an electron beam, the acceleration voltage 100～800KV, particularly 150～300KV, preferably 180~270kV and dose 5 Irradiation is performed under conditions of 1000 kGy, in particular 8 to 200 kGy, preferably 10 to 100 kGy.
・エイジング工程：
放射線を照射した後は通常、そのまま保持するエイジング（熟成）を行う。エイジング温度は通常、１０〜１００℃、好ましくは２０〜４０℃である。エイジング時間は通常、０．１〜１２０分間、好ましくは１〜６０分間である。
・ Aging process:
After irradiation, aging (aging) is usually performed. The aging temperature is usually 10 to 100 ° C, preferably 20 to 40 ° C. The aging time is usually 0.1 to 120 minutes, preferably 1 to 60 minutes.
・洗浄工程：
エイジングを行った後は通常、放射線透過フィルムを剥離し、前記基材を水洗する、水温は特に限定されず、通常は１０〜１００℃であり、好ましくは２０〜５０℃である。
・ Cleaning process:
After aging, the radiation temperature is usually peeled off and the substrate is washed with water. The water temperature is not particularly limited, and is usually 10 to 100 ° C, preferably 20 to 50 ° C.
水洗を行った後は、さらに水酸化ナトリウム水溶液などのアルカリ性水溶液に浸漬し、再度水洗を行うことが好ましい。アルカリ性水溶液による洗浄により、酸性官能基を中和し親水性を向上させることができるためである。 After washing with water, it is preferable to further immerse in an alkaline aqueous solution such as an aqueous sodium hydroxide solution and wash with water again. This is because washing with an alkaline aqueous solution can neutralize acidic functional groups and improve hydrophilicity.
（第２実施態様）
第２実施態様は、特記しない限り、放射線照射工程を実施した後、溶液適用工程および溶液展開工程を順次、実施すること以外、各工程の条件およびその他の説明は第１実施態様と同様である。
(Second embodiment)
In the second embodiment, unless otherwise specified, the conditions and other explanations of each step are the same as those in the first embodiment, except that the solution application step and the solution development step are sequentially performed after the radiation irradiation step. .
第２実施態様の放射線照射工程は、表面撥水性基材に対して放射線を照射すること以外、第１実施態様の放射線照射工程と同様である。第２実施態様の放射線照射工程においては、当該工程に続く溶液適用工程および溶液展開工程で有機化合物Ａが表面撥水性基材内に滲入しながら、化学結合が形成される程度に、撥水性表面が改質され、結果として表面撥水性基材を構成するポリマーにラジカルを発生させる。 The radiation irradiation process of the second embodiment is the same as the radiation irradiation process of the first embodiment except that the surface water-repellent substrate is irradiated with radiation. In the radiation irradiation process of the second embodiment, the water-repellent surface is such that a chemical bond is formed while the organic compound A penetrates into the surface water-repellent substrate in the solution application process and the solution development process subsequent to the process. As a result, radicals are generated in the polymer constituting the surface water-repellent substrate.
第２実施態様の溶液適用工程は、放射線を照射された基材の表面に、有機化合物Ａを含む溶液を適用すること以外、第１実施態様の溶液適用工程と同様である。 The solution application process of the second embodiment is the same as the solution application process of the first embodiment, except that the solution containing the organic compound A is applied to the surface of the substrate irradiated with radiation.
第２実施態様の溶液展開工程は、放射線の照射後に溶液を適用された基材の表面をフィルムで被覆すること以外、第１実施態様の溶液展開工程と同様である。本実施態様で使用されるフィルムは放射線透過性を有さなくてもよいこと以外、第１実施態様における放射線透過フィルムと同様である。第２実施態様の溶液展開工程では、フィルムによる被覆により、溶液が該表面全面に展開されるだけでなく、溶液中の有機化合物Ａが基材内に滲入しながら、化学結合が形成され、結果として表面が親水性を有する改質表層部が形成される。 The solution development step of the second embodiment is the same as the solution development step of the first embodiment, except that the surface of the substrate to which the solution is applied after irradiation with radiation is coated with a film. The film used in this embodiment is the same as the radiation transmissive film in the first embodiment, except that the film does not have to have radiation transparency. In the solution development step of the second embodiment, not only the solution is developed on the entire surface by coating with a film, but also a chemical bond is formed while the organic compound A in the solution permeates into the substrate. As a result, a modified surface layer having a hydrophilic surface is formed.
第２実施態様においては通常、溶液展開工程の後、第１実施態様においてと同様のエイジング工程および洗浄工程を実施する。 In the second embodiment, the aging process and the washing process similar to those in the first embodiment are usually performed after the solution development process.
［表面親水化基材］
本発明の方法により製造された表面親水化基材は、表面撥水性基材の表面上全面に、有機化合物Ａが直接的に化学結合している。
[Surface hydrophilized substrate]
In the surface-hydrophilized substrate produced by the method of the present invention, the organic compound A is directly chemically bonded to the entire surface of the surface water-repellent substrate.
表面撥水性基材の表面上全面に有機化合物Ａが化学結合するとは、有機化合物Ａを化学結合させるべく行った該基材表面上の加工領域全面において有機化合物Ａが化学結合しているという意味である。このため撥水性基材の表面上で一様に親水性が付与さている。例えば、前記した表面親水化基材の製造方法において、放射線透過フィルムによる被覆を行わない場合は、有機化合物Ａ溶液は撥水性表面にはじかれるため、当該基材の表面上への有機化合物Ａの化学結合による一様な親水性付与は困難である。 The organic compound A being chemically bonded to the entire surface of the surface water-repellent substrate means that the organic compound A is chemically bonded to the entire processing region on the surface of the substrate that is formed to chemically bond the organic compound A. It is. For this reason, hydrophilicity is imparted uniformly on the surface of the water-repellent substrate. For example, in the above-described method for producing a surface-hydrophilized substrate, when coating with a radiation transmissive film is not performed, the organic compound A solution is repelled by the water-repellent surface, so that the organic compound A is deposited on the surface of the substrate. It is difficult to impart uniform hydrophilicity by chemical bonding.
表面親水化基材は、詳しくは、表面撥水性基材の少なくとも一部の表層部分が改質されたものであり、その改質表層部内において有機化合物Ａが当該基材を構成するポリマーと化学結合を形成しているものと考えられる。前記した表面親水化基材の製造方法において、有機化合物Ａ溶液の展開および放射線の照射により、有機化合物Ａが表面撥水性基材に滲入しながら、化学結合が形成されるためである。従って、改質表層部は、最表面が有機化合物Ａの存在量が最も多く、深くなるほど当該存在量は少なくなる濃度勾配を有するものと考えられる。このため改質表層部の厚みは一概に規定できるものではなく、例えば、後述する表面接触角ＣＢが達成される限り特に限定されるものではない。本発明においては、改質表層部の上に有機化合物Ａからなる親水性コーティング層が形成されていてもよい。 Specifically, the surface hydrophilized base material is obtained by modifying at least a part of the surface layer portion of the surface water-repellent base material, and in the modified surface layer portion, the organic compound A is chemically coupled with the polymer constituting the base material. It is considered that a bond is formed. This is because, in the above-described method for producing a surface-hydrophilized substrate, the chemical compound is formed while the organic compound A penetrates into the surface water-repellent substrate by the development of the organic compound A solution and the irradiation of radiation. Therefore, it is considered that the modified surface layer portion has a concentration gradient in which the outermost surface has the largest amount of the organic compound A and becomes deeper as the depth becomes deeper. Thus the thickness of the modified surface portion is not indiscriminately be defined, for example, and is not particularly limited as long as the surface contact angle C B to be described later is achieved. In the present invention, a hydrophilic coating layer made of the organic compound A may be formed on the modified surface layer portion.
表面撥水性基材の表面に化学結合する有機化合物Ａの量は、撥水性基材の親水化が達成される限り特に限定されず、通常は５０ｍｇ／ｍ２以上、特に２００〜５０００ｍｇ／ｍ２であり、好ましくは２５０〜１０００ｍｇ／ｍ２である。 The amount of the organic compound A chemically bonded to the surface of the surface water-repellent substrate is not particularly limited as long as hydrophilicity of the water-repellent substrate is achieved, and is usually 50 mg / m 2 or more, particularly 200 to 5000 mg / m 2. by weight, preferably 250~1000mg / m 2.
本発明においては、上記のような処理により、表面撥水性基材の撥水性表面を親水化することができる。表面親水化基材の親水化表面における蒸留水による２５℃での接触角ＣＢは親水化前の接触角ＣＡより低減されていればよい。詳しくは、表面撥水性基材の撥水性表面における蒸留水による接触角ＣＡと、前記表面親水化基材の親水化表面における蒸留水による接触角ＣＢとの差（ＣＡ−ＣＢ）は通常、５°以上、特に２０°以上であり、好ましくは５０°以上、特に好ましくは６０°以上である。上記接触角の差の上限値は特に限定されるものではないが、当該接触角の差は通常、８５°以下、特に８０°以下である。 In the present invention, the water-repellent surface of the surface water-repellent substrate can be hydrophilized by the treatment as described above. The contact angle C B at 25 ° C. with distilled water on the hydrophilic surface of the surface-hydrophilized substrate may be reduced from the contact angle C A before hydrophilization. Specifically, the difference between the contact angle C A with distilled water in the water repellent surface of the surface water-repellent substrate, and the contact angle C B with distilled water in hydrophilic surface of the surface hydrophilic substrate (C A -C B) Is usually 5 ° or more, particularly 20 ° or more, preferably 50 ° or more, particularly preferably 60 ° or more. The upper limit value of the contact angle difference is not particularly limited, but the contact angle difference is usually 85 ° or less, particularly 80 ° or less.
本明細書中、接触角ＣＢは親水化表面において後述する方法により、任意の５箇所で測定した値の平均値を用いている。 Herein, the contact angle C B by the method described later in the hydrophilic surface and using an average value of values measured by any five locations.
［用途］
本発明の表面親水化基材は、表面に親水性が求められる部材またはその表面材料などの建築資材として有用である。
例えば、本発明の表面親水化基材を、床、特に風呂用床の床材またはその表面材料として用いると、表面撥水性基材を用いる場合と比較して、水湿潤時においてヒトが滑って転ぶのを防止できる。
[Usage]
The surface hydrophilized substrate of the present invention is useful as a building material such as a member whose surface is required to have hydrophilicity or a surface material thereof.
For example, when the surface hydrophilized base material of the present invention is used as a floor material, in particular, a floor material for a bath floor or a surface material thereof, compared with the case of using a surface water-repellent base material, a human slips when wet with water. Can prevent falling.
（実施例１）
アクリル酸および界面活性剤を水に溶解し、表１に示す所定濃度のアクリル酸水溶液を加工液として得た。界面活性剤はセブノールＫＴ−１００であり、濃度は１重量％であった。
ポリプロピレンシート（厚み：１００μｍ）の片面（接触角８７°）に加工液を２０ｇ／ｍ２で滴下し、その上から気泡が入らないよう注意しながら、ＰＥＴフィルム（厚み：７５μｍ）を被覆し、水溶液をシート表面（片面）の全面に展開した。
フィルムを被せた状態でフィルム側からシートに対して、電子線を加速電圧２５０ｋＶおよび所定の照射線量で照射した後、３５℃下で１時間エイジングさせた。
その後、フィルムを剥離し、シートを４０℃の水で濯いだ。さらに、シートを濃度１％のＮａＯＨ水溶液中に１０分間浸漬し、水で濯いだ後、自然乾燥させ、親水化基材を得た。
Example 1
Acrylic acid and a surfactant were dissolved in water, and an aqueous acrylic acid solution having a predetermined concentration shown in Table 1 was obtained as a processing liquid. The surfactant was Sebunol KT-100 and the concentration was 1% by weight.
A processing liquid is dropped at 20 g / m 2 on one side (contact angle 87 °) of a polypropylene sheet (thickness: 100 μm), and a PET film (thickness: 75 μm) is coated while being careful not to allow air bubbles to enter from above. The aqueous solution was developed on the entire surface (one side) of the sheet.
The film was covered with an electron beam from the film side with an acceleration voltage of 250 kV and a predetermined irradiation dose, and then aged at 35 ° C. for 1 hour.
Thereafter, the film was peeled off and the sheet was rinsed with 40 ° C. water. Further, the sheet was immersed in an aqueous NaOH solution having a concentration of 1% for 10 minutes, rinsed with water, and then naturally dried to obtain a hydrophilic substrate.
（実施例２〜６）
加工液の濃度および照射線量を表１に示すように変更したこと以外、実施例１と同様の方法により、親水化基材を得た。
(Examples 2 to 6)
A hydrophilized substrate was obtained by the same method as in Example 1 except that the concentration of the working fluid and the irradiation dose were changed as shown in Table 1.
（比較例１）
ポリプロピレンシートを加工することなく、そのまま評価した。当該ポリプロピレンシートに実施例１と同様の加工液を塗布したときの撥水状態を示す写真を図１に示す。図１においては、加工液が撥水性表面にはじかれて斑状に存在することがわかる。
(Comparative Example 1)
The polypropylene sheet was evaluated as it was without being processed. A photograph showing the water-repellent state when the same working fluid as in Example 1 was applied to the polypropylene sheet is shown in FIG. In FIG. 1, it can be seen that the processing liquid is repelled on the water-repellent surface and exists in the form of spots.
（評価）
・接触角
シートの加工面において、２０℃および湿度２５％にて、蒸留水１．８μＬを使用し接触角を測定した。任意の５箇所において接触角を測定し、それらの平均値を求めた。
(Evaluation)
Contact angle On the processed surface of the sheet, the contact angle was measured using 1.8 μL of distilled water at 20 ° C. and a humidity of 25%. The contact angles were measured at arbitrary five locations, and the average value thereof was determined.
本発明の親水化基材は、親水性を必要とする土木資材、車両用資材、建築資材等として又はその表面材料として有用である。 The hydrophilized substrate of the present invention is useful as a civil engineering material, a vehicle material, a building material, or the like that requires hydrophilicity or as a surface material thereof.
Claims (9)
該溶液を適用した基材を放射線透過フィルムで被覆し、該溶液を表面全面に展開する工程；および
放射線を照射する工程
を含むことを特徴とする表面親水化基材の製造方法。 Applying a solution containing a hydrophilic group-containing polymerizable organic compound to the surface of a substrate having a water-repellent surface at least;
A method for producing a surface-hydrophilized substrate, comprising: coating a substrate to which the solution is applied with a radiation transmitting film, and spreading the solution over the entire surface; and irradiating with radiation.
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