JP2013127070A - Hydrophilic coating material and hydrophilic coated product - Google Patents
Hydrophilic coating material and hydrophilic coated product Download PDFInfo
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- JP2013127070A JP2013127070A JP2013012842A JP2013012842A JP2013127070A JP 2013127070 A JP2013127070 A JP 2013127070A JP 2013012842 A JP2013012842 A JP 2013012842A JP 2013012842 A JP2013012842 A JP 2013012842A JP 2013127070 A JP2013127070 A JP 2013127070A
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- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 1
- RQAGEUFKLGHJPA-UHFFFAOYSA-N prop-2-enoylsilicon Chemical compound [Si]C(=O)C=C RQAGEUFKLGHJPA-UHFFFAOYSA-N 0.000 abstract 1
- 229920000557 Nafion® Polymers 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
本発明は、スルホン酸をグラフト重合させた４フッ化エチレン樹脂（以下、「ナフィオン（米国デュポン社の登録商標）」ともいう。）を含有する親水性塗料に関するもので、詳しくはプラスチック材や金属製素材（基材）に対する接着性を向上した親水性塗料と、同親水性塗料が基材の表面に塗布された親水性塗布体に関する。 The present invention relates to a hydrophilic paint containing a tetrafluoroethylene resin grafted with sulfonic acid (hereinafter also referred to as “Nafion (registered trademark of US DuPont)”). The present invention relates to a hydrophilic paint having improved adhesion to a manufacturing material (base material) and a hydrophilic coated body in which the hydrophilic paint is applied to the surface of the base material.
サイディングをはじめ各種基材の表面に親水性を付与し、汚染防止効果や帯電防止効果などを生じさせる方法の一つに、スルホン酸をグラフト重合させた４フッ化エチレン樹脂（ナフィオン）を主体とする親水性塗料を塗布する方法がある。この方法で親水性塗料が基材の表面に造膜された塗布体は、非光励起作用状態（光が照射されない状態）において静的接触角あるいは動的後退接触角のいずれかが３０°以下となる親水性作用を発揮する。 One of the methods to impart hydrophilicity to the surface of various base materials such as siding, and to produce anti-contamination effect and anti-static effect, mainly consists of tetrafluoroethylene resin (Nafion) grafted with sulfonic acid. There is a method of applying a hydrophilic paint. The coated body in which the hydrophilic coating is formed on the surface of the base material by this method has either a static contact angle or a dynamic receding contact angle of 30 ° or less in a non-photoexcited state (a state where no light is irradiated). It exhibits a hydrophilic action.
一方、いわゆる公知の光触媒（酸化チタンなどの金属酸化物）を使用する方法では、下記のような問題点がある。すなわち、
１．裏反応が生じるため光触媒を含むクリヤーの塗布に先立って、裏反応から下地を保護すべきバリアーコートを更に塗布しなければならず、その付加工程のための設備を新設しなければならない。
On the other hand, the method using a so-called known photocatalyst (metal oxide such as titanium oxide) has the following problems. That is,
1. Since a back reaction occurs, prior to the application of the clear containing the photocatalyst, a barrier coat to protect the base from the back reaction must be further applied, and equipment for the additional process must be newly installed.
２．光照射によりはじめて親水性が発現するため、製造および出荷時に親水性の出荷検査が行いにくい。 2. Since hydrophilicity is manifested only by light irradiation, it is difficult to carry out a hydrophilic shipping inspection at the time of manufacture and shipment.
しかしながら、ナフィオン（登録商標）を主体とする親水性塗料の場合には、以下のような解決すべき課題ある。すなわち、
ナフィオン（登録商標）は本来、フッ素樹脂で接着性を具備しておらず、高分子構造に含まれるスルホン酸基がマイナスイオンで、プラスイオンと引き合う傾向があるので、プラスチック材や金属製素材などの基材に対しその弱いイオン同士の吸引力で、ある程度接着している。ただし、耐摩耗性を発揮し得るほどの接着性はなかった。
However, in the case of a hydrophilic paint mainly composed of Nafion (registered trademark), there are problems to be solved as follows. That is,
Nafion (registered trademark) is originally a fluororesin and does not have adhesiveness, and the sulfonic acid group contained in the polymer structure is a negative ion and tends to attract positive ions, so plastic materials, metal materials, etc. It adheres to a certain extent to the base material by the suction force between the weak ions. However, there was not enough adhesiveness to exhibit wear resistance.
本発明は上述の点に鑑みなされたもので、ナフィオン（登録商標）を主体とする親水性塗料のもつ接着性に劣るという弱点を克服して接着性の向上を図り、プラスチック材や金属製素材などの表面が平滑な基材表面へ塗布し、造膜することで、親水性を付与して汚染防止効果や帯電防止効果を発現させ、優れた耐摩耗性を発揮させることができる親水性塗料と同塗料を用いた親水性塗布体を提供しようとするものである。 The present invention has been made in view of the above-described points, and overcomes the weakness of the hydrophilic coating mainly composed of Nafion (registered trademark) to improve the adhesiveness, thereby improving the adhesiveness. Applying to the surface of a substrate with a smooth surface, etc., and forming a film, it is possible to impart hydrophilicity to express antifouling and antistatic effects and to exhibit excellent wear resistance. It is intended to provide a hydrophilic coated body using the same paint.
上記の目的を達成するために本発明（請求項１）に係る親水性塗料は、スルホン酸をグラフト重合させた４フッ化エチレン樹脂を含有する親水性塗料において、アクリルシリコン樹脂を樹脂成分中の２０〜７０質量％の範囲で含有させたことを特徴とする。 In order to achieve the above object, the hydrophilic paint according to the present invention (Claim 1) is a hydrophilic paint containing a tetrafluoroethylene resin obtained by graft polymerization of sulfonic acid. It is contained in the range of 20 to 70% by mass.
上記の構成を有する親水性塗料によれば、アクリルシリコン樹脂の含有量が全樹脂成分（ナフィオン中の樹脂成分を含む）の２０質量％を下回ると、基材に対する十分な接着性が確保できなくなる一方、全樹脂成分の７０質量％を上回ると、親水性塗料の主体であるナフィオン（登録商標）の有する親水性に代表される、いわゆる光触媒効果が有効に発揮されなくなるからである。そして、アクリルシリコン樹脂を前記のとおり全樹脂成分中の２０〜７０質量％の範囲で含有させたことによって、ナフィオンの極めて低い接着力が補われる。また、ナフィオンのスルホン酸の共有結合を形成しにくいという性状を生かし、ナフィオンと相溶し、かつ基材の表面と結合しやすい樹脂成分であるアクリルシリコン樹脂を共存させることにより、接着力が大幅に向上し、加工性や耐摩耗性も向上する。この結果、非光励起作用状態で親水性を基材の表面に付与し、汚染防止効果や帯電防止効果などを発揮する。 According to the hydrophilic paint having the above structure, when the content of the acrylic silicone resin is less than 20% by mass of the total resin components (including the resin component in Nafion), sufficient adhesion to the substrate cannot be ensured. On the other hand, if it exceeds 70% by mass of the total resin components, the so-called photocatalytic effect represented by the hydrophilicity of Nafion (registered trademark), which is the main component of the hydrophilic paint, cannot be effectively exhibited. And the extremely low adhesive force of Nafion is supplemented by containing acrylic silicon resin in the range of 20-70 mass% in all the resin components as mentioned above. In addition, taking advantage of the property that Nafion's sulfonic acid covalent bond is difficult to form, and by coexisting with an acrylic silicon resin that is compatible with Nafion and easily binds to the surface of the substrate, adhesion is greatly improved. To improve the workability and wear resistance. As a result, hydrophilicity is imparted to the surface of the base material in a non-photoexcited state, and an anti-contamination effect or an anti-static effect is exhibited.
請求項２に記載のように、前記親水性塗料の顔料成分中に光触媒を含むことができる。 As described in claim 2, a photocatalyst can be included in the pigment component of the hydrophilic paint.
このように構成することにより、請求項１に記載の親水性塗料において、ナフィオンを分解することなく、消臭、抗菌、大気浄化等の光触媒効果を奏するようになる。また、顔料成分である上記光触媒は、チタニアゾル、ゼオライトで表面被覆された酸化チタン、シリカで表面被覆された酸化チタン、およびアパタイトで表面被覆された酸化チタンから選ばれる１〜４種のうちいずれか１種あるいは２種以上の混合物とすることが好ましい。 By comprising in this way, in the hydrophilic coating material of Claim 1, there exists a photocatalytic effect, such as deodorizing, antibacterial, and air purification, without decomposing | disassembling Nafion. Further, the photocatalyst as a pigment component is any one of 1 to 4 types selected from titania sol, titanium oxide surface-coated with zeolite, titanium oxide surface-coated with silica, and titanium oxide surface-coated with apatite. It is preferable to use one or a mixture of two or more.
請求項３に記載の親水性塗布体は、請求項１または２に記載の親水性塗料を基材表面に塗布し、８０〜２００℃の温度下で加熱することにより前記基材の表面に造膜させたことを特徴とする。 A hydrophilic coated body according to claim 3 is formed on the surface of the base material by applying the hydrophilic paint according to claim 1 or 2 to the surface of the base material and heating the base material at a temperature of 80 to 200 ° C. It is characterized by having a film.
上記の構成を有する親水性塗布体によれば、塩化ビニル樹脂の耐熱温度が８０℃近辺であるため、８０℃以上で加熱し焼き付けるものとする一方、ナフィオンおよび熱硬化性フッ素樹脂については２００℃が上限温度である。より具体的には、本発明に係る親水性塗料を基材の表面に塗布した塗布体を、雰囲気温度８０℃〜２００℃のオーブンに入れて５〜３０分間焼き付けるか、塗布体搬送用コンベアを備えた、温風の吐出温度が８０℃〜２００℃の風速の早いハイベロシティーオーブンで１〜３分間焼き付けるかすることができる。 According to the hydrophilic coated body having the above-described configuration, since the heat resistant temperature of the vinyl chloride resin is around 80 ° C., it should be heated and baked at 80 ° C. or higher, while Nafion and thermosetting fluororesin are 200 ° C. Is the upper limit temperature. More specifically, the coated body in which the hydrophilic paint according to the present invention is applied to the surface of the base material is placed in an oven having an atmospheric temperature of 80 ° C. to 200 ° C. and baked for 5 to 30 minutes, or a conveyor for transporting the coated body is used. It can be baked for 1 to 3 minutes in a high velocity oven equipped with a hot air discharge temperature of 80 ° C. to 200 ° C. and a high wind speed.
上記の構成からなる親水性塗料および同塗料を用いた親水性塗布体には、次のような優れた効果がある。 The hydrophilic paint having the above structure and the hydrophilic coated body using the paint have the following excellent effects.
ナフィオン（登録商標）は親水性ポリマーで、一般的な光触媒塗料と異なり受光しなくても、つまり非光励起作用状態で親水性を発揮し、汚染防止効果や帯電防止効果なども奏するが、上記したとおり接着性が低いために、プラスチック材や金属材のような表面が平滑な基材に塗布した際に塗膜が形成されても簡単に剥離するので、実施が困難であった。これに対し、本発明の親水性塗料によれば、 含有されているナフィオンには反応性官能基がスルホン酸しかなく、しかもこのスルホン酸がイオン性が強くて共有結合を形成しにくいという性状を生かすことで、ナフィオンと相溶しかつ下地となる基材の表面と結合しやすい、アクリルシリコン樹脂を共存させることにより、ナフィオンの接着性の低さを十分に補うことができる。加えて、親水性塗料の接着力が向上されることにより、本発明の親水性塗料が塗布された塗布体の加工性や耐摩擦性の向上も同時に達成することができる。 Nafion (registered trademark) is a hydrophilic polymer, and unlike conventional photocatalytic paints, it does not receive light, that is, exhibits hydrophilicity in a non-photoexcited state, and also exhibits anti-contamination and antistatic effects. As described above, since the adhesiveness is low, even if a coating film is formed when applied to a substrate having a smooth surface such as a plastic material or a metal material, it is easily peeled off, so that the implementation is difficult. On the other hand, according to the hydrophilic paint of the present invention, the contained Nafion has only a reactive functional group having a sulfonic acid, and the sulfonic acid has a strong ionicity and is difficult to form a covalent bond. By making use of it, the low adhesion of Nafion can be sufficiently compensated by the coexistence of an acrylic silicon resin that is compatible with Nafion and easily binds to the surface of the base material. In addition, by improving the adhesive strength of the hydrophilic paint, it is possible to simultaneously improve the workability and friction resistance of the coated body to which the hydrophilic paint of the present invention is applied.
以下、本発明の親水性塗料について実施の形態を説明する。 Hereinafter, embodiments of the hydrophilic paint of the present invention will be described.
実施例１
熱硬化性フッ素樹脂とその硬化剤を樹脂成分とする。
a)熱硬化型フッ素樹脂(大日本インキ化学工業(株)製の商品名「フルオネートK702」)
２０
b)硬化剤用メラミン樹脂(大日本インキ化学工業(株)製の商品名「スーパーベッカミンL105-60」) ５
c)ナフィオン(登録商標)溶液(米国デュポン社製の商品名「ナフィオンDE2020」)
５０
d)酢酸N-ブチル ２５
a)の不揮発分は５０質量％であり、b)の不揮発分は６０質量％であるから、a)とb)を合計した架橋型フッ素樹脂とその硬化剤成分は１３質量部となる。また、c)の不揮発分は２０質量％であるから、当該塗料樹脂成分中の架橋型フッ素樹脂とその硬化剤成分の含有量は５６．５質量％となる。
Example 1
A thermosetting fluororesin and its curing agent are used as resin components.
a) Thermosetting fluororesin (trade name “Fluonate K702” manufactured by Dainippon Ink and Chemicals, Inc.)
20
b) Melamine resin for curing agent (trade name “Super Becamine L105-60” manufactured by Dainippon Ink and Chemicals, Inc.)
c) Nafion (registered trademark) solution (trade name `` Nafion DE2020 '' manufactured by DuPont, USA)
50
d) N-butyl acetate 25
Since the non-volatile content of a) is 50% by mass and the non-volatile content of b) is 60% by mass, the cross-linked fluororesin in which a) and b) are combined and its curing agent component is 13 parts by mass. Further, since the non-volatile content of c) is 20% by mass, the content of the crosslinkable fluororesin and its curing agent component in the paint resin component is 56.5% by mass.
この溶液（親水性塗料）を、ポリエステル樹脂焼付け塗装板にスプレーで塗装した。塗布量は１００ｇ/ｍ2とし、それを１４０℃―１０分（温度１４０℃で１０分間加熱）の雰囲気下で焼き付けた。
比較例１
実施例１のc)ナフィオン溶液量を１０とし、塗料樹脂成分中の架橋型フッ素樹脂とその硬化剤成分の含有量を８６．７質量％とした以外は、実施例１と同様に試料を作製した。
実施例２
アクリルシリコン樹脂を樹脂成分とする。
This solution (hydrophilic paint) was applied to a polyester resin baked paint plate by spraying. The coating amount was 100 g / m 2, and it was baked in an atmosphere of 140 ° C. for 10 minutes (heating at 140 ° C. for 10 minutes).
Comparative Example 1
Example 1 c) A sample was prepared in the same manner as in Example 1 except that the amount of Nafion solution was 10, and the content of the cross-linked fluororesin and the curing agent component in the coating resin component was 86.7% by mass. did.
Example 2
Acrylic silicon resin is used as a resin component.
以下の配合に従い塗料を調製した。 A paint was prepared according to the following formulation.
a)アクリルシリコン樹脂(昭和高分子製の商品名「ポリゾールAP3900」) ４０
b)エチレングリコー １０
c)ナフィオン溶液（米国デュポン社製の商品名「ナフィオンDE2020」） ３０
d)水 ２０
a)の不揮発分は５０質量％であり、c)の不揮発分は２０質量％であるから、当該塗料樹脂成分中のアクリルシリコン樹脂の含有量は７７質量％となる。
a) Acrylic silicone resin (trade name “Polysol AP3900” manufactured by Showa Polymer) 40
b) Ethylene glycol 10
c) Nafion solution (trade name “Nafion DE2020” manufactured by DuPont, USA) 30
d) Water 20
Since the non-volatile content of a) is 50% by mass and the non-volatile content of c) is 20% by mass, the content of the acrylic silicon resin in the paint resin component is 77% by mass.
この溶液を塩ビ板にスプレーで塗装した。塗布量は１００ｇ/ｍ2とし、それを８０℃―１０分の雰囲気下で乾燥させた。
比較例２
実施例２におけるa)アクリルシリコン樹脂を８とし、c)ナフィオン溶液を９０とすることにより、塗料樹脂成分中のアクリルシリコン樹脂の含有量を１８．２質量％とした以外は実施例２と同様に試料を作製した。
This solution was applied to a PVC plate by spraying. The coating amount was 100 g / m 2 and it was dried in an atmosphere at 80 ° C. for 10 minutes.
Comparative Example 2
Example 2 is the same as Example 2 except that the content of the acrylic silicon resin in the paint resin component is 18.2% by mass by setting a) the acrylic silicon resin to 8 and c) the Nafion solution to 90. A sample was prepared.
実施例３
（硬化剤にシランカップリング剤を用いた実施例である）
a)熱硬化型フッ素樹脂(大日本インキ化学工業(株)製の商品名「フルオネートK702」)
３０
b)イソシアネート系シランカップリング剤(モメンティブパーフォーマンスケミカルズ
ジャパン社製の商品名「Y-5187」)
３
b)ナフィオン(登録商標)溶液(米国デュポン社製の商品名「ナフィオンDE2020」)
４０
d)酢酸N-ブチル ２６
e)硬化促進触媒「ジブチル錫ジアセテート０．１％溶液」 １
a)の不揮発分は５０質量％であり、b)の不揮発分はほぼ１００質量％であるから、a)とb)を合計した架橋型フッ素樹脂とその硬化剤成分は１８質量部となる。また、c)の不揮発分は２０質量％であるから、当該塗料樹脂成分中の架橋型フッ素樹脂とその硬化剤成分の含有量は６４．３質量％となる。
Example 3
(This is an example using a silane coupling agent as the curing agent)
a) Thermosetting fluororesin (trade name “Fluonate K702” manufactured by Dainippon Ink and Chemicals, Inc.)
30
b) Isocyanate-based silane coupling agent (trade name “Y-5187” manufactured by Momentive Performance Chemicals Japan)
3
b) Nafion (registered trademark) solution (trade name `` Nafion DE2020 '' manufactured by DuPont, USA)
40
d) N-butyl acetate 26
e) Curing accelerating catalyst "dibutyltin diacetate 0.1% solution" 1
Since the non-volatile content of a) is 50% by mass and the non-volatile content of b) is approximately 100% by mass, the total amount of the cross-linked fluororesin and the curing agent component thereof is 18 parts by mass. Further, since the non-volatile content of c) is 20% by mass, the content of the cross-linked fluororesin and the curing agent component in the paint resin component is 64.3% by mass.
この溶液（親水性塗料）を、ポリエステル樹脂焼付け塗装板にスプレーで塗装した。塗布量は１００ｇ/ｍ2とし、それを１４０℃―１０分（温度１４０℃で１０分間加熱）の雰囲気下で焼き付けた。 This solution (hydrophilic paint) was applied to a polyester resin baked paint plate by spraying. The coating amount was 100 g / m 2, and it was baked in an atmosphere of 140 ° C. for 10 minutes (heating at 140 ° C. for 10 minutes).
なお、シランカップリング剤以外に、（ブロック）イソシアネート、メラミン樹脂、ポリアミド、酸無水物を使用できることは言うまでもなく、またシランカップリング剤を含む上記のいずれかの硬化剤から選択される２種〜５種の混合物を使用することもできる。
実施例４
（光触媒を含有させた実施例である）
熱硬化性フッ素樹脂とその硬化剤を樹脂成分とする。
In addition to the silane coupling agent, it goes without saying that (block) isocyanate, melamine resin, polyamide, and acid anhydride can be used, and two kinds selected from the above-mentioned curing agents including the silane coupling agent are used. Five mixtures can also be used.
Example 4
(This is an example containing a photocatalyst)
A thermosetting fluororesin and its curing agent are used as resin components.
a)熱硬化型フッ素樹脂(大日本インキ化学工業(株)製の商品名「フルオネートK702」)
２０
b)硬化剤用メラミン樹脂(大日本インキ化学工業(株)製の商品名「スーパーベッカミンL105-60」) ５
c)ナフィオン(登録商標）溶液(米国デュポン社製の商品名「ナフィオンDE2020」) ５０
d)酢酸N-ブチル
１０
e)光触媒酸化チタンスラリー液（石原産業（株）製品）「ＳＴＳ−１００」 １５
a)の不揮発分は５０質量％であり、b)の不揮発分は６０質量％であるから、a)とb)を合計した架橋型フッ素樹脂とその硬化剤成分は１３質量部となる。また、c)の不揮発分は２０質量％であるから、当該塗料樹脂成分中の架橋型フッ素樹脂とその硬化剤成分の含有量は５６．５質量％となる。また、ＳＴＳ−１００の不揮発分が２０質量％であるから不揮発分全体に占める光触媒濃度は１１．５質量％となる。
a) Thermosetting fluororesin (trade name “Fluonate K702” manufactured by Dainippon Ink and Chemicals, Inc.)
20
b) Melamine resin for curing agent (trade name “Super Becamine L105-60” manufactured by Dainippon Ink and Chemicals, Inc.)
c) Nafion (registered trademark) solution (trade name “Nafion DE2020” manufactured by DuPont, USA) 50
d) N-butyl acetate
10
e) Photocatalytic titanium oxide slurry (product of Ishihara Sangyo Co., Ltd.) “STS-100” 15
Since the non-volatile content of a) is 50% by mass and the non-volatile content of b) is 60% by mass, the cross-linked fluororesin in which a) and b) are combined and its curing agent component is 13 parts by mass. Further, since the non-volatile content of c) is 20% by mass, the content of the crosslinkable fluororesin and its curing agent component in the paint resin component is 56.5% by mass. Moreover, since the non-volatile content of STS-100 is 20 mass%, the photocatalyst density | concentration which occupies for the whole non-volatile content will be 11.5 mass%.
この溶液（親水性塗料）を、ポリエステル樹脂焼付け塗装板にスプレーで塗装した。塗布量は１００ｇ/ｍ2とし、それを１４０℃―１０分（温度１４０℃で１０分間加熱）の雰囲気下で焼き付けた。 This solution (hydrophilic paint) was applied to a polyester resin baked paint plate by spraying. The coating amount was 100 g / m 2, and it was baked in an atmosphere of 140 ° C. for 10 minutes (heating at 140 ° C. for 10 minutes).
下記の表１は比較性能試験結果を示すものである。 Table 1 below shows the comparative performance test results.
・接着性
碁盤目テープ剥離試験：碁盤目セロテープ（登録商標）剥離で100/100の良好な接着性を確認して「○」と判定した。逆にチョーキングあるいは塗膜の白濁があり、その面での碁盤目セロテープ（登録商標）剥離が100/100より悪い場合を「×」と判定した。
・親水性
動的・後退接触角を測定した。動的・後退接触角：３０°以下を○、８０°以上を×とした。手順としては、まず水平に静置した試料表面に水滴を２μｌ滴下し、１分経過後に更に４μｌ滴下して追加した。１分経過後にその追加分の４μｌを吸引して、更に１分経過後にその界面の接触角を測定した。
・加工性
基材を１８０°折り曲げてそのときのクラック発生をルーペで確認。クラック発生なしを○、クラックが発生したものを×とした。
・耐摩擦性
テーバー磨耗試験。荷重１ｋｇで２００回転時の減量が２ｍｇ以下であれば○とし、同条件下での減量が２ｍｇを超える場合には×とする。
・上記各実施例または各比較例の塗料を塗布した基材の種類
実施例１、実施例３、実施例４および比較例１はポリエステル塗装鋼板（高温で焼付け可能）、実施例２、比較例２は塩ビ板（低温乾燥のみ可能）である。
・メチレンブルー分解活性
この分媒活性はＪＩＳ Ｒ １７０３−２に定義されている。消臭・抗菌・大気浄化等の光触媒効果を再現性のある数値として表記しうる代表的な尺度が、メチレンブルーを用いた分解活性指数であるが、このメチレンブルーは光照射による劣化が極めて少なく、逆にラジカル（遊離基）と選択的に反応するため、光触媒反応でラジカルが生じると急速に脱色するという特性を有している。光触媒反応の効果と目される消臭・抗菌・大気浄化作用は、すべて発生するラジカルにより惹起されるものであるから、メチレンブルーの分解とこれらの効果の間には密接な相関関係が存在する。
・ Adhesiveness Cross-cut tape peeling test: 100/100 good adhesiveness was confirmed by cross-cutting cello tape (registered trademark) peeling and judged as “◯”. On the other hand, a case where there was choking or cloudiness of the coating film, and the peeling of the cellar cellotape (registered trademark) on that surface was worse than 100/100, was judged as “x”.
・ Hydrophilicity Dynamic and receding contact angles were measured. Dynamic and receding contact angle: O for 30 ° or less and x for 80 ° or more. As a procedure, first, 2 μl of water droplets were dropped on the surface of a sample that was allowed to stand horizontally, and 4 μl was further dropped after 1 minute. After 1 minute, 4 μl of the additional amount was sucked, and after another 1 minute, the contact angle of the interface was measured.
・ Machinability Bend the substrate 180 ° and confirm the occurrence of cracks with a loupe. The case where no crack was generated was indicated as “◯”, and the case where a crack occurred was indicated as “X”.
・ Abrasion resistance Taber abrasion test. When the weight loss at 200 revolutions is 2 mg or less with a load of 1 kg, it is marked as ◯, and when the weight loss under the same condition exceeds 2 mg, it is marked as x.
-Types of base materials to which the paints of the above examples or comparative examples are applied Examples 1, 3, 4, and 1 are polyester-coated steel sheets (can be baked at high temperatures), Example 2, and Comparative Examples 2 is a vinyl chloride plate (only low temperature drying is possible).
-Methylene blue decomposition activity This solvent separation activity is defined in JIS R 1703-2. A representative measure that can express the photocatalytic effects such as deodorant, antibacterial, and air purification as reproducible numerical values is the decomposition activity index using methylene blue. Since it reacts selectively with radicals (free radicals), it has the property of rapidly decoloring when radicals are generated by photocatalytic reactions. Since the deodorizing, antibacterial, and air purification effects that are considered to be the effects of the photocatalytic reaction are all caused by radicals generated, there is a close correlation between the decomposition of methylene blue and these effects.
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| JP2020142432A (en) * | 2019-03-06 | 2020-09-10 | 株式会社村上開明堂 | Laminate |
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