JP2022041343A - Temperature-sensitive water-repellent agent - Google Patents
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Abstract
Description
特許法第３０条第２項適用申請有り 令和１年１２月３日 ｈｔｔｐ：／／ｗｗｗ．ｎｉｔｔａ．ｃｏ．ｊｐ／ｌｐ／ｉｎｔｅｌｉｍｅｒ／There is an application for application of Article 30, Paragraph 2 of the Patent Act. December 3, 1st year of Reiwa http: // www. nitta. co. jp / lp / innerlimer /
本発明は、感温性撥水剤に関する。 The present invention relates to a temperature sensitive water repellent.
物品に撥水性を付与できる撥水剤が知られている（例えば、特許文献１参照）。また、撥水性が必要なときと不要なときがあり、何らかのトリガーによって撥水性を制御したいというニーズがある。 A water repellent that can impart water repellency to an article is known (see, for example, Patent Document 1). In addition, there are times when water repellency is necessary and times when it is not necessary, and there is a need to control water repellency by some kind of trigger.
本発明の課題は、温度によって撥水性を制御できる感温性撥水剤を提供することである。 An object of the present invention is to provide a temperature-sensitive water-repellent agent whose water repellency can be controlled by temperature.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
（１）融点未満の温度で結晶化し、且つ、前記融点以上の温度で流動性を示す側鎖結晶性ポリマーを含有するとともに、前記融点を境に水の接触角が変化する、感温性撥水剤。
（２）前記側鎖結晶性ポリマーが、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートをモノマー成分として含む、前記（１）に記載の感温性撥水剤。
（３）合成樹脂をさらに含有する、前記（１）または（２）に記載の感温性撥水剤。
（４）前記融点未満の温度における水の接触角が、前記融点以上の温度における水の接触角よりも大きい、前記（３）に記載の感温性撥水剤。
As a result of diligent research to solve the above problems, the present inventors have found a solution means having the following configurations, and have completed the present invention.
(1) A temperature-sensitive repellent that contains a side-chain crystalline polymer that crystallizes at a temperature below the melting point and exhibits fluidity at a temperature above the melting point, and the contact angle of water changes at the melting point. Liquid agent.
(2) The temperature-sensitive water repellent agent according to (1) above, wherein the side chain crystalline polymer contains (meth) acrylate having a linear alkyl group having 16 or more carbon atoms as a monomer component.
(3) The temperature-sensitive water repellent agent according to (1) or (2) above, which further contains a synthetic resin.
(4) The temperature-sensitive water repellent agent according to (3), wherein the contact angle of water at a temperature below the melting point is larger than the contact angle of water at a temperature above the melting point.
本発明によれば、温度によって撥水性を制御できるという効果がある。 According to the present invention, there is an effect that the water repellency can be controlled by the temperature.
＜感温性撥水剤＞
以下、本発明の一実施形態に係る感温性撥水剤（以下、「撥水剤」ということがある。）について詳細に説明する。
<Temperature sensitive water repellent>
Hereinafter, the temperature-sensitive water repellent agent (hereinafter, may be referred to as “water repellent agent”) according to the embodiment of the present invention will be described in detail.
本実施形態の撥水剤は、融点未満の温度で結晶化し、且つ、融点以上の温度で流動性を示す側鎖結晶性ポリマーを含有するとともに、融点を境に水の接触角が変化する。 The water repellent of the present embodiment contains a side chain crystalline polymer that crystallizes at a temperature below the melting point and exhibits fluidity at a temperature above the melting point, and the contact angle of water changes with the melting point as a boundary.
上述した構成によれば、温度によって撥水性を制御できるという効果が得られる。具体的に説明すると、上述した側鎖結晶性ポリマーは、融点を有するポリマーである。融点とは、ある平衡プロセスにより、最初は秩序ある配列に整合されていた重合体の特定部分が無秩序状態になる温度であり、示差熱走査熱量計（ＤＳＣ）を使用して、１０℃／分の測定条件で測定して得られる値のことである。側鎖結晶性ポリマーは、上述した融点未満の温度で結晶化し、且つ、融点以上の温度で相転移して流動性を示す。すなわち、側鎖結晶性ポリマーは、温度変化に対応して結晶状態と流動状態とを可逆的に起こす感温性を有する。本実施形態の撥水剤は、このような側鎖結晶性ポリマーを含有することから、側鎖結晶性ポリマーに由来する感温性を有する。 According to the above-mentioned configuration, the effect that the water repellency can be controlled by the temperature can be obtained. Specifically, the side chain crystalline polymer described above is a polymer having a melting point. Melting point is the temperature at which a particular portion of a polymer initially matched to an ordered sequence becomes disordered by a certain equilibrium process and is 10 ° C./min using a differential thermal scanning calorimeter (DSC). It is a value obtained by measuring under the measurement conditions of. The side chain crystalline polymer crystallizes at a temperature below the melting point described above, and undergoes a phase transition at a temperature above the melting point to exhibit fluidity. That is, the side chain crystalline polymer has a temperature sensitivity that reversibly causes a crystalline state and a flowing state in response to a temperature change. Since the water repellent agent of the present embodiment contains such a side chain crystalline polymer, it has a temperature sensitivity derived from the side chain crystalline polymer.
また、側鎖結晶性ポリマーは、融点を境に水の接触角が変化する。それゆえ、このような側鎖結晶性ポリマーを含有する本実施形態の撥水剤も、融点を境に水の接触角が変化する。したがって、本実施形態の撥水剤によれば、温度によって撥水性を制御できるという効果が得られる。また、所望の物品に対して上述した撥水性を付与することができる。側鎖結晶性ポリマーが温度変化に対応して結晶状態と流動状態とを可逆的に起こすことに起因して、繰り返し使用することもできる。 Further, in the side chain crystalline polymer, the contact angle of water changes at the melting point. Therefore, the water repellent agent of the present embodiment containing such a side chain crystalline polymer also changes the contact angle of water with respect to the melting point. Therefore, according to the water repellent agent of the present embodiment, the effect that the water repellency can be controlled by the temperature can be obtained. In addition, the above-mentioned water repellency can be imparted to a desired article. It can also be used repeatedly due to the fact that the side chain crystalline polymer reversibly causes a crystalline state and a flowing state in response to a temperature change.
撥水剤は、融点未満の温度における水の接触角が、融点以上の温度における水の接触角よりも大きくてもよく、また、小さくてもよい。撥水剤は、融点未満の温度における水の接触角と、融点以上の温度における水の接触角との差（絶対値）が、好ましくは５°よりも大きく、より好ましくは１０°以上である。上記した差（絶対値）の上限値は、特に限定されないが、好ましくは５５°以下である。水の接触角は、ＪＩＳ Ｒ３２５７：１９９９の静滴法に準じて測定される値である。 The water repellent may have a water contact angle at a temperature below the melting point larger or smaller than the water contact angle at a temperature above the melting point. In the water repellent, the difference (absolute value) between the contact angle of water at a temperature below the melting point and the contact angle of water at a temperature above the melting point is preferably larger than 5 °, more preferably 10 ° or more. .. The upper limit of the above difference (absolute value) is not particularly limited, but is preferably 55 ° or less. The contact angle of water is a value measured according to the static drip method of JIS R3257: 1999.
側鎖結晶性ポリマーは、融点未満の温度における水の接触角が、融点以上の温度における水の接触角よりも大きくてもよい。側鎖結晶性ポリマーは、融点未満の温度における水の接触角が、好ましくは８０～１２０°、融点以上の温度における水の接触角が、好ましくは７０～１１０°である。なお、側鎖結晶性ポリマーの水の接触角は、例示した数値範囲に限定されない。 The side chain crystalline polymer may have a water contact angle above the melting point that is greater than the water contact angle at temperatures below the melting point. The side chain crystalline polymer has a water contact angle of preferably 80 to 120 ° at a temperature below the melting point and preferably 70 to 110 ° of a water contact angle at a temperature above the melting point. The contact angle of water of the side chain crystalline polymer is not limited to the exemplified numerical range.
側鎖結晶性ポリマーの融点は、好ましくは１０～７０℃である。融点は、例えば、側鎖結晶性ポリマーを構成するモノマー成分の組成などを変えることによって調整できる。具体例を挙げると、側鎖結晶性ポリマーにおける側鎖の長さを変えると融点を調整できる。 The melting point of the side chain crystalline polymer is preferably 10 to 70 ° C. The melting point can be adjusted, for example, by changing the composition of the monomer components constituting the side chain crystalline polymer. To give a specific example, the melting point can be adjusted by changing the length of the side chain in the side chain crystalline polymer.
側鎖結晶性ポリマーは、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートをモノマー成分として含む。炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートは、その炭素数１６以上の直鎖状アルキル基が側鎖結晶性ポリマーにおける側鎖結晶性部位として機能する。すなわち、側鎖結晶性ポリマーは、側鎖に炭素数１６以上の直鎖状アルキル基を有する櫛形のポリマーであり、この側鎖が分子間力などによって秩序ある配列に整合されることにより結晶化する。なお、上述した（メタ）アクリレートとは、アクリレートまたはメタクリレートのことである。 The side chain crystalline polymer contains (meth) acrylate having a linear alkyl group having 16 or more carbon atoms as a monomer component. In a (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, the linear alkyl group having 16 or more carbon atoms functions as a side chain crystalline moiety in the side chain crystalline polymer. That is, the side chain crystalline polymer is a comb-shaped polymer having a linear alkyl group having 16 or more carbon atoms in the side chain, and the side chain is crystallized by being matched to an ordered arrangement by an intramolecular force or the like. do. The above-mentioned (meth) acrylate is acrylate or methacrylate.
炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートとしては、例えば、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、エイコシル（メタ）アクリレート、ベヘニル（メタ）アクリレートなどの炭素数１６～２２の線状アルキル基を有する（メタ）アクリレートが挙げられる。例示した（メタ）アクリレートは、１種のみを使用してもよいし、２種以上を併用してもよい。炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは１０～１００重量％、より好ましくは２０～１００重量％の割合で含まれる。側鎖結晶性ポリマーは、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートをモノマー成分中に最も多い割合で含んでもよい。 Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include cetyl (meth) acrylate, stearyl (meth) acrylate, eicocil (meth) acrylate, and behenyl (meth) acrylate, which have 16 to 16 carbon atoms. Examples thereof include (meth) acrylates having 22 linear alkyl groups. As the exemplified (meth) acrylate, only one kind may be used, or two or more kinds may be used in combination. The (meth) acrylate having a linear alkyl group having 16 or more carbon atoms is preferably contained in the monomer component constituting the side chain crystalline polymer in a proportion of preferably 10 to 100% by weight, more preferably 20 to 100% by weight. Is done. The side chain crystalline polymer may contain (meth) acrylate having a linear alkyl group having 16 or more carbon atoms in the highest proportion in the monomer component.
側鎖結晶性ポリマーを構成するモノマー成分には、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートと共重合し得る他のモノマーが含まれていてもよい。他のモノマーとしては、例えば、炭素数１～８のアルキル基を有する（メタ）アクリレート、極性モノマーなどが挙げられる。 The monomer component constituting the side chain crystalline polymer may contain other monomers that can be copolymerized with the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms. Examples of other monomers include (meth) acrylates having an alkyl group having 1 to 8 carbon atoms, polar monomers and the like.
炭素数１～８のアルキル基を有する（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、アクリル酸２－エチルヘキシルなどが挙げられる。例示した（メタ）アクリレートは、１種のみを使用してもよいし、２種以上を併用してもよい。炭素数１～８のアルキル基を有する（メタ）アクリレートは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは７０重量％以下、より好ましくは１～７０重量％の割合で含まれる。 Examples of the (meth) acrylate having an alkyl group having 1 to 8 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl acrylate. Can be mentioned. As the exemplified (meth) acrylate, only one kind may be used, or two or more kinds may be used in combination. The (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferably contained in the monomer component constituting the side chain crystalline polymer in a proportion of preferably 70% by weight or less, more preferably 1 to 70% by weight.
極性モノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸などのカルボキシル基を有するエチレン性不飽和単量体；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシヘキシル（メタ）アクリレートなどのヒドロキシル基を有するエチレン性不飽和単量体などが挙げられる。例示した極性モノマーは、１種のみを使用してもよいし、２種以上を併用してもよい。極性モノマーは、側鎖結晶性ポリマーを構成するモノマー成分中に好ましくは１０重量％以下、より好ましくは１～１０重量％の割合で含まれる。 Examples of the polar monomer include ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; 2-hydroxyethyl (meth) acrylate and 2-hydroxyl. Examples thereof include ethylenically unsaturated monomers having a hydroxyl group such as propyl (meth) acrylate and 2-hydroxyhexyl (meth) acrylate. As the exemplified polar monomer, only one kind may be used, or two or more kinds may be used in combination. The polar monomer is contained in the monomer component constituting the side chain crystalline polymer in a proportion of preferably 10% by weight or less, more preferably 1 to 10% by weight.
側鎖結晶性ポリマーの好ましい組成としては、炭素数１６以上の直鎖状アルキル基を有する（メタ）アクリレートが２０～９０重量％、炭素数１～８のアルキル基を有する（メタ）アクリレートが５～７０重量％、および極性モノマーが５～１０重量％である。 The preferred composition of the side chain crystalline polymer is 20 to 90% by weight of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms and 5 the (meth) acrylate having an alkyl group having 1 to 8 carbon atoms. ~ 70% by weight, and 5-10% by weight of polar monomer.
モノマー成分の重合方法としては、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法などが挙げられる。溶液重合法を採用する場合には、モノマー成分と溶媒とを混合し、必要に応じて重合開始剤、連鎖移動剤などを添加し、撹拌しながら４０～９０℃程度で２～１０時間程度反応させればよい。 Examples of the polymerization method of the monomer component include a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. When the solution polymerization method is adopted, the monomer component and the solvent are mixed, a polymerization initiator, a chain transfer agent, etc. are added as necessary, and the reaction is carried out at about 40 to 90 ° C. for about 2 to 10 hours with stirring. Just let me do it.
側鎖結晶性ポリマーの重量平均分子量は、好ましくは１０００以上、より好ましくは１０００～１００００００である。重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定し、得られた測定値をポリスチレン換算した値である。 The weight average molecular weight of the side chain crystalline polymer is preferably 1000 or more, more preferably 1000 to 1000000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and obtained by converting the obtained measured value into polystyrene.
撥水剤は、側鎖結晶性ポリマーに由来する感温性および融点を境にした水の接触角の変化が得られる割合で、側鎖結晶性ポリマーを含有すればよい。例えば、撥水剤は、側鎖結晶性ポリマーのみを含有してもよい。言い換えれば、撥水剤は、側鎖結晶性ポリマー単体で構成されてもよい。 The water repellent agent may contain the side chain crystalline polymer at a ratio that allows the temperature sensitivity derived from the side chain crystalline polymer and the change in the contact angle of water with respect to the melting point to be obtained. For example, the water repellent may contain only side chain crystalline polymers. In other words, the water repellent may be composed of the side chain crystalline polymer alone.
撥水剤は、側鎖結晶性ポリマーに加えて他の部材をさらに含有してもよい。他の部材としては、例えば、合成樹脂などが挙げられる。すなわち、撥水剤は、合成樹脂をさらに含有してもよい。 The water repellent may further contain other members in addition to the side chain crystalline polymer. Examples of other members include synthetic resins and the like. That is, the water repellent may further contain a synthetic resin.
合成樹脂としては、例えば、ポリエチレンテレフタレート樹脂（ＰＥＴ）、ポリ塩化ビニル樹脂、エチレン－メチルメタクリレート共重合樹脂、ポリカーボネート、メチルメタクリレート樹脂、アクリル樹脂、エポキシ樹脂、ポリアミド樹脂、ポリウレタン、ポリビニルブチラール、ポリビニルアセテート、エチレン酢酸ビニル共重合樹脂（ＥＶＡ）、ポリオレフィン系樹脂などが挙げられる。ポリオレフィン系樹脂としては、例えば、ポリエチレン樹脂などが挙げられる。なお、合成樹脂としては、例示したものに限定されない。 Examples of the synthetic resin include polyethylene terephthalate resin (PET), polyvinyl chloride resin, ethylene-methylmethacrylate copolymer resin, polycarbonate, methylmethacrylate resin, acrylic resin, epoxy resin, polyamide resin, polyurethane, polyvinyl butyral, polyvinyl acetate, and the like. Examples thereof include ethylene vinyl acetate copolymer resin (EVA) and polyolefin resin. Examples of the polyolefin resin include polyethylene resin and the like. The synthetic resin is not limited to the exemplified one.
撥水剤が合成樹脂を含有する場合、撥水剤は、融点未満の温度における水の接触角が、融点以上の温度における水の接触角よりも大きくてもよい。 When the water repellent contains a synthetic resin, the water repellent may have a water contact angle at a temperature below the melting point greater than a water contact angle at a temperature above the melting point.
合成樹脂の含有量は、側鎖結晶性ポリマーの含有量よりも多くてもよい。この場合には、融点を境に水の接触角が大きく変化し易い。具体的には、合成樹脂の含有量が側鎖結晶性ポリマーの含有量よりも多い場合、撥水剤は、融点未満の温度における水の接触角と、融点以上の温度における水の接触角との差（絶対値）が、好ましくは３０°よりも大きく、より好ましくは３５°以上である。上記した差（絶対値）の上限値は、特に限定されないが、好ましくは５５°以下である。 The content of the synthetic resin may be higher than the content of the side chain crystalline polymer. In this case, the contact angle of water tends to change significantly with the melting point as the boundary. Specifically, when the content of the synthetic resin is higher than the content of the side chain crystalline polymer, the water repellent has a contact angle of water at a temperature below the melting point and a contact angle of water at a temperature above the melting point. The difference (absolute value) is preferably larger than 30 °, more preferably 35 ° or more. The upper limit of the above difference (absolute value) is not particularly limited, but is preferably 55 ° or less.
合成樹脂の含有量が側鎖結晶性ポリマーの含有量よりも多い場合、側鎖結晶性ポリマーの含有量は、合成樹脂１００重量部に対して、好ましくは１～２０重量部、より好ましくは１～１０重量部である。 When the content of the synthetic resin is higher than the content of the side chain crystalline polymer, the content of the side chain crystalline polymer is preferably 1 to 20 parts by weight, more preferably 1 with respect to 100 parts by weight of the synthetic resin. ~ 10 parts by weight.
合成樹脂の重量平均分子量は、側鎖結晶性ポリマーの重量平均分子量よりも大きくてもよい。この場合には、融点を境に水の接触角が大きく変化し易い。なお、合成樹脂の重量平均分子量は、好ましくは１００００～２００００００である。 The weight average molecular weight of the synthetic resin may be larger than the weight average molecular weight of the side chain crystalline polymer. In this case, the contact angle of water tends to change significantly with the melting point as the boundary. The weight average molecular weight of the synthetic resin is preferably 10,000 to 2000000.
本実施形態の撥水剤の使用形態は、特に限定されない。例えば、物品に対して塗布（コーティング）やスプレーするような形態で使用してもよいし、シート状またはテープ状などの形態で使用してもよい。撥水性を付与する物品としては、所望のものが採用可能であり、特に限定されない。 The form of use of the water repellent agent of this embodiment is not particularly limited. For example, it may be used in the form of coating or spraying on an article, or may be used in the form of a sheet or tape. As the article for imparting water repellency, a desired one can be adopted and is not particularly limited.
本実施形態の撥水剤は、離型剤としても使用可能である。例えば、本実施形態の撥水剤をＰＥＴフィルムの片面に塗布すれば、粘着テープのリリースライナーのような離型処理ＰＥＴとして使用可能である。また、離型処理が必要な型に対して塗布やスプレーするような形態でも使用可能である。なお、リリースライナーの例では、離型剤の性能評価方法の１つである水の接触角において、撥水性が高いほど（水をはじくほど）、テープの離型性も高い傾向がある。本実施形態の撥水剤を離型剤として使用する場合には、感温性撥水剤を感温性離型剤と言い換えてもよい。 The water repellent agent of the present embodiment can also be used as a mold release agent. For example, if the water repellent agent of the present embodiment is applied to one side of a PET film, it can be used as a release-treated PET such as a release liner of an adhesive tape. It can also be used in the form of coating or spraying on a mold that requires mold release treatment. In the example of the release liner, the higher the water repellency (the more water is repelled), the higher the mold release property of the tape tends to be in the contact angle of water, which is one of the methods for evaluating the performance of the release agent. When the water repellent of the present embodiment is used as a mold release agent, the temperature sensitive water repellent may be paraphrased as a temperature sensitive mold release agent.
以下、合成例および実施例を挙げて本発明を詳細に説明するが、本発明は以下の合成例および実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to synthetic examples and examples, but the present invention is not limited to the following synthetic examples and examples.
（合成例１：合成樹脂）
まず、表１に示すモノマーを表１に示す割合で反応容器に加えた。表１に示すモノマーは、以下のとおりである。
ＥＨＡ：２－エチルへキシルアクリレート
Ｃ１Ａ：メチルアクリレート
ＨＥＡ：２－ヒドロキシエチルアクリレート
(Synthesis Example 1: Synthetic resin)
First, the monomers shown in Table 1 were added to the reaction vessel at the ratios shown in Table 1. The monomers shown in Table 1 are as follows.
EHA: 2-ethylhexyl acrylate C1A: methyl acrylate HEA: 2-hydroxyethyl acrylate
次に、重合開始剤として日油社製の「パーブチルＮＤ」をモノマー混合物１００重量部に対して０．５重量部の割合で反応容器に加えた後、固形分濃度が３０重量％になるように酢酸エチル：ヘプタン＝７０：３０（重量比）の混合溶媒を反応容器に加え、混合液を得た。得られた混合液を５５℃で４時間撹拌することによって各モノマーを共重合させ、合成樹脂（アクリル樹脂）を得た。 Next, after adding "Perbutyl ND" manufactured by Nichiyu Co., Ltd. as a polymerization initiator to the reaction vessel at a ratio of 0.5 part by weight with respect to 100 parts by weight of the monomer mixture, the solid content concentration becomes 30% by weight. A mixed solvent of ethyl acetate: heptane = 70:30 (weight ratio) was added to the reaction vessel to obtain a mixed solution. The obtained mixed solution was stirred at 55 ° C. for 4 hours to copolymerize each monomer to obtain a synthetic resin (acrylic resin).
（合成例２：側鎖結晶性ポリマー）
まず、表１に示すモノマーを表１に示す割合で反応容器に加えた。表１に示すモノマーは、以下のとおりである。
Ｃ２２Ａ：ベヘニルアクリレート
Ｃ１８Ａ：ステアリルアクリレート
Ｃ１Ａ：メチルアクリレート
ＡＡ：アクリル酸
(Synthesis Example 2: Side Chain Crystalline Polymer)
First, the monomers shown in Table 1 were added to the reaction vessel at the ratios shown in Table 1. The monomers shown in Table 1 are as follows.
C22A: Behenyl acrylate C18A: Stearyl acrylate C1A: Methyl acrylate AA: Acrylic acid
次に、重合開始剤として日油社製の「パーヘキシルＰＶ」をモノマー混合物１００重量部に対して０．５重量部の割合で反応容器に加えた後、固形分濃度が３０重量％になるように酢酸エチル：ヘプタン＝７０：３０（重量比）の混合溶媒を反応容器に加え、混合液を得た。得られた混合液を８０℃で３時間撹拌することによって各モノマーを共重合させ、側鎖結晶性ポリマーを得た。 Next, after adding "Perhexyl PV" manufactured by Nichiyu Co., Ltd. as a polymerization initiator to the reaction vessel at a ratio of 0.5 parts by weight with respect to 100 parts by weight of the monomer mixture, the solid content concentration becomes 30% by weight. A mixed solvent of ethyl acetate: heptane = 70:30 (weight ratio) was added to the reaction vessel to obtain a mixed solution. The obtained mixed solution was stirred at 80 ° C. for 3 hours to copolymerize each monomer to obtain a side chain crystalline polymer.
得られた合成樹脂および側鎖結晶性ポリマーの重量平均分子量および融点を表１に示す。重量平均分子量は、ＧＰＣで測定して得られた測定値をポリスチレン換算した値である。融点は、ＤＳＣを用いて１０℃／分の測定条件で測定した値である。 Table 1 shows the weight average molecular weight and melting point of the obtained synthetic resin and side chain crystalline polymer. The weight average molecular weight is a value obtained by converting the measured value obtained by measuring with GPC into polystyrene. The melting point is a value measured using a DSC under measurement conditions of 10 ° C./min.
［実施例１および比較例１］
＜試験片の作製＞
まず、合成例１～２で得られた合成樹脂および側鎖結晶性ポリマーを表２に示す組み合わせにした後、酢酸エチルによって固形分濃度が２８重量％となるように調整して塗布液を得た。なお、比較例１は、合成例１で得られた合成樹脂単体である。実施例１は、合成例１で得られた合成樹脂１００重量部に対して、合成例２で得られた側鎖結晶性ポリマーを５重量部の割合で混合した混合物である。
[Example 1 and Comparative Example 1]
<Preparation of test piece>
First, the synthetic resin and side chain crystalline polymer obtained in Synthesis Examples 1 and 2 are combined as shown in Table 2, and then adjusted to a solid content concentration of 28% by weight with ethyl acetate to obtain a coating liquid. rice field. In addition, Comparative Example 1 is a simple substance of the synthetic resin obtained in Synthetic Example 1. Example 1 is a mixture of 100 parts by weight of the synthetic resin obtained in Synthesis Example 1 and 5 parts by weight of the side chain crystalline polymer obtained in Synthesis Example 2.
次に、得られた塗布液を厚さ１００μｍのＰＥＴからなるフィルム状の基材の片面に塗布した。そして、９０℃×１０分の条件で乾燥させて、基材の片面に厚さ４０μｍの樹脂層が積層されたテープ状の試験片を得た。 Next, the obtained coating liquid was applied to one side of a film-like substrate made of PET having a thickness of 100 μm. Then, it was dried under the condition of 90 ° C. × 10 minutes to obtain a tape-shaped test piece in which a resin layer having a thickness of 40 μm was laminated on one side of the base material.
＜評価＞
得られた試験片について、水の接触角を評価した。評価方法を以下に示すとともに、その結果を表２に示す。
<Evaluation>
The contact angle of water was evaluated for the obtained test piece. The evaluation method is shown below, and the results are shown in Table 2.
（水の接触角）
試験片の樹脂層に対する水の接触角を測定した。具体的には、ＪＩＳ Ｒ３２５７：１９９９の静滴法に準じて測定した。測定器は、協和界面科学社製の接触角計「ＤＭｓ－４０１」を用いた。
(Water contact angle)
The contact angle of water with respect to the resin layer of the test piece was measured. Specifically, the measurement was carried out according to the intravenous drip method of JIS R3257: 1999. As the measuring instrument, a contact angle meter "DMs-401" manufactured by Kyowa Interface Science Co., Ltd. was used.
表２から明らかなように、実施例１は、融点を境に水の接触角が変化していることがわかる。 As is clear from Table 2, in Example 1, it can be seen that the contact angle of water changes with respect to the melting point.
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