JP6797511B2 - Aqueous infrared / ultraviolet shielding coating agent and infrared / ultraviolet shielding treatment method using this - Google Patents
Aqueous infrared / ultraviolet shielding coating agent and infrared / ultraviolet shielding treatment method using this Download PDFInfo
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- JP6797511B2 JP6797511B2 JP2015117513A JP2015117513A JP6797511B2 JP 6797511 B2 JP6797511 B2 JP 6797511B2 JP 2015117513 A JP2015117513 A JP 2015117513A JP 2015117513 A JP2015117513 A JP 2015117513A JP 6797511 B2 JP6797511 B2 JP 6797511B2
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- 238000000034 method Methods 0.000 title claims description 12
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- 239000011347 resin Substances 0.000 claims description 45
- 239000010419 fine particle Substances 0.000 claims description 41
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- 238000000576 coating method Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000006096 absorbing agent Substances 0.000 claims description 10
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- 239000007787 solid Substances 0.000 claims description 10
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- 238000002834 transmittance Methods 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001651 Cyanoacrylate Polymers 0.000 claims description 3
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
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- 150000003673 urethanes Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
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- 239000011787 zinc oxide Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 239000003960 organic solvent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- 230000008961 swelling Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 231100000989 no adverse effect Toxicity 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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Description
本発明は、赤外線・紫外線遮蔽効果を有する水性コーティング剤と、これを利用した赤外線・紫外線遮蔽処理方法に関する。 The present invention relates to an aqueous coating agent having an infrared / ultraviolet shielding effect and an infrared / ultraviolet shielding treatment method using the same.
ビル、工場、及び住宅等の一般的な建造物においては、自然光を採光するために、主に窓ガラスが採用されている。窓ガラスから差し込む自然光は主として太陽光であるが、この太陽光に含まれる赤外線は、物質の温度を上昇させる働きを持つ。したがって、主に夏場において、ガラスを通じて太陽光が当たる室内等では、赤外線による温度上昇が原因で、室内を冷却する冷房の効果が阻害されてしまうことが知られている。また、冬場においては、室内で暖房器具から発せられる赤外線が窓ガラスを透過して屋外へと出て行ってしまい、暖房の効果も低減してしまう原因ともなっている。 In general buildings such as buildings, factories, and houses, windowpanes are mainly used to take in natural light. The natural light that enters through the window glass is mainly sunlight, and the infrared rays contained in this sunlight have the function of raising the temperature of the substance. Therefore, it is known that, mainly in the summer, in a room or the like where sunlight is exposed through glass, the effect of cooling the room is hindered due to the temperature rise due to infrared rays. Further, in winter, infrared rays emitted from a heater indoors pass through the window glass and go out to the outside, which is a cause of reducing the effect of heating.
さらに、太陽光には紫外線も含まれるが、この紫外線は室内の調度品や装飾品（畳、木材、襖等）の劣化を促進し、人間の皮膚にも炎症を起こすことが知られている。したがって、採光という目的を達成するため透過性を維持しつつ、窓ガラスには赤外線・紫外線を遮蔽できる効果を持たせることが望ましい。 Furthermore, sunlight also contains ultraviolet rays, which are known to accelerate the deterioration of indoor furniture and ornaments (tatami mats, wood, sliding doors, etc.) and cause inflammation of human skin. .. Therefore, in order to achieve the purpose of daylighting, it is desirable to give the window glass an effect of shielding infrared rays and ultraviolet rays while maintaining transparency.
そこで近年では、赤外線及び紫外線を遮ることのできるフィルムやコーティング剤によって窓ガラスの表面を被覆し、赤外線や紫外線から室内を遮蔽しようとしている。例えば、特許文献１においては、赤外線を吸収する錫ドープ酸化インジウムや、紫外線を吸収する酸化チタン微粒子等を被膜成分と共に有機溶剤（例えばイソプロピルアルコールや混合キシレン）に加えて混合し、ガラスへのコーティング剤としたものが記載されている。特許文献２においては、赤外線を吸収するインジウム錫酸化物を含有し、赤外線吸収能を持つシリコーン塗料（溶媒としてイソプロピルアルコールを使用）が示されている。特許文献３においては、水性エマルジョン中に赤外線を吸収する錫ドープ酸化インジウム、紫外線を吸収する微粒子状の紫外線吸収剤が含まれた、水性の近赤外線・紫外線遮蔽塗料が示されている。 Therefore, in recent years, the surface of the window glass is coated with a film or coating agent capable of blocking infrared rays and ultraviolet rays, and an attempt is made to shield the room from infrared rays and ultraviolet rays. For example, in Patent Document 1, tin-doped indium oxide that absorbs infrared rays, titanium oxide fine particles that absorb ultraviolet rays, and the like are added to an organic solvent (for example, isopropyl alcohol or mixed xylene) together with a coating component and mixed to coat the glass. The one used as an agent is described. Patent Document 2 discloses a silicone paint (using isopropyl alcohol as a solvent) containing indium tin oxide that absorbs infrared rays and having infrared absorbing ability. Patent Document 3 discloses a water-based near-infrared / ultraviolet shielding coating material containing tin-doped indium oxide that absorbs infrared rays and a fine-grained ultraviolet absorber that absorbs ultraviolet rays in an aqueous emulsion.
ここで、特許文献１のコーティング剤は、紫外線・赤外線を吸収し、遮断することが可能である。しかし、有機溶剤を使用しているため、ＶＯＣ（揮発性有機化合物）が発生して臭気を発してしまう。さらに、使用者がＶＯＣに過度に曝されると、健康上の問題を引き起こす可能性もある。 Here, the coating agent of Patent Document 1 is capable of absorbing and blocking ultraviolet rays and infrared rays. However, since an organic solvent is used, VOC (volatile organic compound) is generated and an odor is emitted. In addition, excessive exposure of users to VOCs can cause health problems.
また、特許文献２のシリコーン塗料も、有機溶剤を使っている点で特許文献１と同じ課題を有する。しかも、シリコーンを使用しているため、温度が高い場所で使用すると、シリコーンが不規則な箇所で硬化してしまい、塗膜に白濁が生じてしまうという問題があった。 Further, the silicone paint of Patent Document 2 has the same problem as that of Patent Document 1 in that it uses an organic solvent. Moreover, since silicone is used, when it is used in a place where the temperature is high, there is a problem that the silicone is cured in an irregular place and the coating film becomes cloudy.
一方で、特許文献３では有機溶剤を使用していないため、臭気等の問題はない。しかし、紫外線吸収微粒子を使用している。これでは、塗料の塗付後、時間の経過と共に紫外線吸収微粒子が被膜表面に浮き出してしまい、粉を吹いたようにざらついて見た目も触感も変わってしまう、いわゆるブリードアウトを起こしてしまうという問題があった。しかも、硬化助剤を使用しているため、保存安定性や取り扱いにも難がある。 On the other hand, since Patent Document 3 does not use an organic solvent, there is no problem such as odor. However, it uses UV-absorbing fine particles. This causes the problem that UV-absorbing fine particles emerge on the surface of the film over time after the paint is applied, causing so-called bleed-out, which makes the film look and feel as if it were blown. there were. Moreover, since a curing aid is used, there are difficulties in storage stability and handling.
そこで、本発明の目的とするところは、上記課題を解決するものであって、紫外線・赤外線の遮蔽効果を有しつつ、ＶＯＣが発生せず、かつブリードアウトや白濁の問題も生じない、水性赤外線・紫外線遮蔽コーティング剤と、これを利用した赤外線・紫外線遮蔽処理方法を提供することにある。 Therefore, an object of the present invention is to solve the above-mentioned problems, and it is water-based, which has an ultraviolet / infrared shielding effect, does not generate VOC, and does not cause bleed-out or cloudiness problems. The purpose of the present invention is to provide an infrared ray / ultraviolet ray shielding coating agent and an infrared ray / ultraviolet ray shielding treatment method using the same.
そのための手段として、本発明は、被膜形成樹脂成分と、紫外線吸収剤と、赤外線吸収剤とを含有する水性赤外線・紫外線遮蔽コーティング剤である。当該被膜形成樹脂成分はポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンのうち少なくとも一方であり、前記紫外線吸収剤は紫外線吸収ポリマーであり、前記赤外線吸収剤は無機系赤外線吸収微粒子である。 As a means for that purpose, the present invention is an aqueous infrared / ultraviolet shielding coating agent containing a film-forming resin component, an ultraviolet absorber, and an infrared absorber. The film-forming resin component is at least one of a polyurethane aqueous emulsion and a modified polyurethane aqueous emulsion, the ultraviolet absorber is an ultraviolet absorbing polymer, and the infrared absorber is an inorganic infrared absorbing fine particle.
前記紫外線吸収ポリマーは、ベンゾトリアゾール系単量体、ベンゾエート系単量体、ベンゾフェノン系単量体、トリアジン系単量体、及びシアノアクリレート系単量体の中から選ばれる少なくともいずれか一種の単量体と、アクリル酸エステル、メタクリル酸エステル、及びビニル系単量体の中から選ばれる少なくとも一種の単量体との共重合体とすることが好ましい。 The ultraviolet absorbing polymer is a single amount of at least one selected from benzotriazole-based monomers, benzoate-based monomers, benzophenone-based monomers, triazine-based monomers, and cyanoacrylate-based monomers. It is preferable that the polymer is a copolymer of the body and at least one monomer selected from acrylic acid ester, methacrylic acid ester, and vinyl-based monomer.
前記紫外線吸収ポリマーの含有量は、固形分比率で５〜４０質量％が好ましい。前記無機系赤外線吸収剤微粒子の含有量は、１０〜３０質量％が好ましい。 The content of the ultraviolet absorbing polymer is preferably 5 to 40% by mass in terms of solid content ratio. The content of the inorganic infrared absorber fine particles is preferably 10 to 30% by mass.
無機系赤外線吸収微粒子は、水中に分散している水分散体の状態で添加することが望ましい。微粒子状の無機系赤外線吸収剤を、水性赤外線・紫外線遮蔽コーティング剤内に均一に分散することができ、赤外線及び紫外線の遮蔽（吸収）効果が高まるためである。 It is desirable to add the inorganic infrared absorbing fine particles in the form of an aqueous dispersion dispersed in water. This is because the fine-grained inorganic infrared absorber can be uniformly dispersed in the aqueous infrared / ultraviolet shielding coating agent, and the infrared and ultraviolet shielding (absorbing) effect is enhanced.
上記水性赤外線・紫外線遮蔽コーティング剤を、窓ガラス等のガラス基材のほか、透明樹脂パネルや透明樹脂フィルム等の有機系透明基材の内面及び外面の少なくとも一方面に塗布し、硬化剤を使用せずに被膜を形成することで、赤外線・紫外線遮蔽処理を施す方法も提供することができる。 The above-mentioned water-based infrared / ultraviolet shielding coating agent is applied to at least one of the inner and outer surfaces of a glass base material such as window glass and an organic transparent base material such as a transparent resin panel or a transparent resin film, and a curing agent is used. It is also possible to provide a method of applying an infrared / ultraviolet shielding treatment by forming a film without forming a film.
本発明の水性赤外線・紫外線遮蔽コーティング剤は、有意な赤外線及び紫外線遮蔽機能を有する。そのため、これを窓ガラスや透明樹脂パネル等へ塗布し、その被膜を形成することで、断熱効果及び家具等の劣化防止効果を得ることができる。具体的には、夏場には日射中の赤外線を吸収することによって、室内への熱侵入を防ぐ。冬場には、屋内からの暖房器具の赤外線による熱を屋外に逃がさない。同時に、紫外線が遮蔽されることで、室内調度品や内装品の変色を防止できると共に、皮膚への紫外線の影響も低減させることができる。 The aqueous infrared / ultraviolet shielding coating agent of the present invention has a significant infrared / ultraviolet shielding function. Therefore, by applying this to a window glass, a transparent resin panel, or the like to form a film thereof, it is possible to obtain a heat insulating effect and an effect of preventing deterioration of furniture or the like. Specifically, in the summer, it absorbs infrared rays during sunlight to prevent heat from entering the room. In winter, the infrared heat of the heater from indoors is not released to the outside. At the same time, by shielding the ultraviolet rays, it is possible to prevent discoloration of the interior furniture and interior parts and reduce the influence of the ultraviolet rays on the skin.
そのうえで、本発明の水性赤外線・紫外線遮蔽コーティング剤は、各成分の分散媒体として水を使用した水性コーティング剤なので、ＶＯＣが発生しない。したがって、作業環境や人体への悪影響は無い。また、紫外線吸収剤として、被膜形成樹脂成分に対して相溶性を有する紫外線吸収ポリマーを使用しているため、ブリードアウトが発生しない。且つ、形成される被膜は無機基材及び有機基材共に密着性が良好であり、耐候性や耐摩傷性も向上する。また、シリコーンを含有していないため、高温雰囲気下における白濁といった問題も生じない。 In addition, since the aqueous infrared / ultraviolet shielding coating agent of the present invention is an aqueous coating agent using water as a dispersion medium for each component, VOC does not occur. Therefore, there is no adverse effect on the working environment or the human body. Further, since an ultraviolet absorbing polymer having compatibility with the film-forming resin component is used as the ultraviolet absorber, bleed-out does not occur. In addition, the formed film has good adhesion to both the inorganic base material and the organic base material, and the weather resistance and scratch resistance are also improved. Moreover, since it does not contain silicone, there is no problem of cloudiness in a high temperature atmosphere.
また、常温硬化型（一液硬化型）なので硬化剤を使用する必要は無く、保存安定性や施工性に有利である。しかも、例え既設の窓ガラス等へも、そのままローラー、刷毛、吹き付け等の一般的な塗布方法で塗布するだけで、一般家庭においても簡単に被膜を形成できる。 Moreover, since it is a room temperature curing type (one-component curing type), it is not necessary to use a curing agent, which is advantageous in storage stability and workability. Moreover, a film can be easily formed even in a general household by simply applying it to an existing window glass or the like by a general coating method such as a roller, a brush, or a spray.
＜水性赤外線・紫外線遮蔽コーティング剤＞
本発明の水性赤外線・紫外線遮蔽コーティング剤（以下、単にコーティング剤と称すことがある）は、被膜形成樹脂成分と、紫外線吸収剤として紫外線吸収ポリマーと、赤外線吸収剤として無機系赤外線吸収微粒子とを含有することを基本構成とする。
<Aqueous infrared / ultraviolet shielding coating agent>
The water-based infrared / ultraviolet shielding coating agent of the present invention (hereinafter, may be simply referred to as a coating agent) contains a film-forming resin component, an ultraviolet absorbing polymer as an ultraviolet absorber, and inorganic infrared absorbing fine particles as an infrared absorber. The basic composition is to contain it.
≪被膜形成樹脂成分≫
被膜形成樹脂成分は、コーティング剤のベース材料である。被膜形成樹脂成分としては、ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンの少なくとも一方、又は双方を使用する。ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンは、常温硬化型の樹脂成分である。したがって、コーティング剤に硬化剤を添加する必要は無く、常温乾燥によって被膜を形成できる。また、ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンは、硬化後に透明被膜を形成する。しかも、無機系のガラス基材だけではなく、樹脂パネルや樹脂フィルムといった種々の有機系基材への密着性にも優れているため、塗布対象が広く汎用性が高い。なお、被膜形成樹脂成分としてポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョン以外の樹脂成分を使用した場合、後述の紫外線吸収剤や赤外線吸収剤との相性が悪い。そのため、形成される被膜の密着性や透明性に問題が生じるばかりか、白濁やブリードアウトが生じる可能性がある。
≪Film forming resin component≫
The film-forming resin component is the base material of the coating agent. As the film-forming resin component, at least one or both of a polyurethane aqueous emulsion and a modified polyurethane aqueous emulsion is used. Polyurethane aqueous emulsions and modified polyurethane aqueous emulsions are room temperature curable resin components. Therefore, it is not necessary to add a curing agent to the coating agent, and a film can be formed by drying at room temperature. In addition, the polyurethane aqueous emulsion and the modified polyurethane aqueous emulsion form a transparent film after curing. Moreover, since it is excellent in adhesion not only to inorganic glass base materials but also to various organic base materials such as resin panels and resin films, it has a wide range of coating targets and is highly versatile. When a resin component other than the polyurethane aqueous emulsion and the modified polyurethane aqueous emulsion is used as the film-forming resin component, the compatibility with the ultraviolet absorber and the infrared absorber described later is poor. Therefore, not only the adhesion and transparency of the formed film may be problematic, but also cloudiness and bleed-out may occur.
変性ポリウレタン水性エマルジョンとしては、アクリル変性ポリウレタン水性エマルジョン、ポリカーボネート変性ポリウレタン水性エマルジョン、エステル変性ポリウレタン水性エマルジョン、エーテル変性ポリウレタンエマルジョン、エポキシ変性ポリウレタンエマルジョン等を挙げることができる。これらの変性ポリウレタン水性エマルジョンは、１種を単独で使用してもよく、２種以上を混用することもできる。 Examples of the modified polyurethane aqueous emulsion include acrylic modified polyurethane aqueous emulsion, polycarbonate modified polyurethane aqueous emulsion, ester modified polyurethane aqueous emulsion, ether modified polyurethane emulsion, and epoxy modified polyurethane emulsion. One of these modified polyurethane aqueous emulsions may be used alone, or two or more thereof may be mixed.
このようなポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンの市販品としては、例えば、ＧＳＩクレオス社製の「ＴＵＲＢＯＳＥＴ ２０２５」、アデカ社製の「アデカボンタイターシリーズ（品番：ＨＵＸ−２３２，ＨＵＸ−３２０，ＨＵＸ−３８０，ＨＵＸ−４０１，ＨＵＸ−５２２など）」、楠本化成社製の「ＮＥＯＲＥＺシリーズ（品番：Ｒ−９７２，Ｒ−９６７，Ｒ−６００，Ｒ−９６０３など）」、第一工業製薬社製の「スーパーフレックスシリーズ（品番：５００，５５０，６１０，６５０など）」、及び大日本インキ化学工業社製の「ハイドランシリーズ（品番：ＨＷ−３１１，ＨＷ−３５０，ＨＷ−１５０など）」等が挙げられる。 Commercially available products of such polyurethane aqueous emulsions and modified polyurethane aqueous emulsions include, for example, "TURBOSET 2025" manufactured by GSI Creos and "Adeka Bontiter series (product numbers: HUX-232, HUX-320, HUX) manufactured by Adeka Corporation. -380, HUX-401, HUX-522, etc.) ”,“ NEOREZ series (product number: R-972, R-967, R-600, R-9603, etc.) ”manufactured by Kusumoto Kasei Co., Ltd. "Superflex series (product numbers: 500, 550, 610, 650, etc.)" and "Hydran series (product numbers: HW-311, HW-350, HW-150, etc.)" manufactured by Dainippon Ink and Chemicals Co., Ltd. Can be mentioned.
ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンは、樹脂固形分換算で、コーティング剤中に３０質量％以上、好ましくは４０質量％以上、より好ましくは４５質量％以上含有されていればよい。樹脂固形分換算で３０質量％未満では、形成される被膜の密着性や耐擦傷性が不足する虞があるほか、他の成分の含有量が相対的に多くなって透明性が低下する虞もある。一方、ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンの含有量の上限は、特に制限されない。 The aqueous polyurethane emulsion and the modified aqueous polyurethane emulsion may be contained in the coating agent in an amount of 30% by mass or more, preferably 40% by mass or more, and more preferably 45% by mass or more in terms of resin solid content. If it is less than 30% by mass in terms of resin solid content, the adhesion and scratch resistance of the formed film may be insufficient, and the content of other components may be relatively large, resulting in a decrease in transparency. is there. On the other hand, the upper limit of the content of the polyurethane aqueous emulsion and the modified polyurethane aqueous emulsion is not particularly limited.
≪紫外線吸収ポリマー≫
紫外線吸収ポリマーは分散媒を水とし、ポリマー分子を構成する共重合モノマーセグメントの一つとして、紫外線吸収性（紫外線吸収基）を有する単量体を用いている。これにより、紫外線吸収ポリマー全体として紫外線吸収性能を有する。また、紫外線吸収ポリマーは、被膜形成樹脂成分との相溶性を有する。したがって、コーティング剤中において紫外線吸収ポリマーは被膜形成樹脂成分と相溶している。これにより、従来のように紫外線吸収微粒子を使用した場合のブリードアウトを避けることができる。且つ、形成される被膜の密着性や、耐候性及び耐擦傷性の向上にも寄与する。
≪UV absorbing polymer≫
The ultraviolet absorbing polymer uses water as a dispersion medium and uses a monomer having ultraviolet absorbing properties (ultraviolet absorbing group) as one of the copolymerization monomer segments constituting the polymer molecule. As a result, the ultraviolet absorbing polymer as a whole has an ultraviolet absorbing performance. In addition, the ultraviolet absorbing polymer has compatibility with the film-forming resin component. Therefore, the ultraviolet absorbing polymer is compatible with the film-forming resin component in the coating agent. As a result, it is possible to avoid bleeding out when ultraviolet absorbing fine particles are used as in the conventional case. At the same time, it also contributes to the improvement of the adhesion of the formed film, the weather resistance and the scratch resistance.
紫外線吸収性を有する単量体としては、ベンゾトリアゾール系単量体、ベンゾエート系単量体、ベンゾフェノン系単量体、トリアジン系単量体、及びシアノアクリレート系単量体の中から選ばれる少なくとも一種の単量体とする。一方、当該紫外線吸収性を有する単量体と共重合するその他の単量体としては、アクリル酸エステル、メタクリル酸エステル、及びビニル系単量体の中から選ばれる少なくとも一種の単量体とすることができる。このような紫外線吸収ポリマーの市販品としては、例えば新中村化学工業社製の「ニューコートシリーズ（ニューコートＵＶＡ−１０１，ＵＶＡ−１０２，ＵＶＡ−１０３，ＵＶＡ−１０４，ＵＶＡ−２０４Ｗ等）」、一方社油脂工業（株）製の「ＵＬＳ−７００、ＵＬＳ−１７００等」などが挙げられる。 As the monomer having ultraviolet absorption, at least one selected from benzotriazole-based monomer, benzoate-based monomer, benzophenone-based monomer, triazine-based monomer, and cyanoacrylate-based monomer. It is a monomer of. On the other hand, as the other monomer copolymerizing with the ultraviolet-absorbing monomer, at least one monomer selected from acrylic acid ester, methacrylic acid ester, and vinyl-based monomer is used. be able to. Examples of commercially available products of such ultraviolet absorbing polymers include "New Coat Series (New Coat UVA-101, UVA-102, UVA-103, UVA-104, UVA-204W, etc.)" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. On the other hand, "ULS-700, ULS-1700, etc." manufactured by Yushi Kogyo Co., Ltd. can be mentioned.
紫外線吸収ポリマー中、紫外線吸収性を有する単量体の構成比は５〜６０質量％が好ましく、より好ましくは２０〜５０質量％である。紫外線吸収性を有する単量体の構成比が５質量％未満では、紫外線吸収性を有意に発現し難い。これを補うためにコーティング剤への紫外線吸収ポリマーの配合量を多くすると、形成される被膜において後述の悪影響を及ぼす。一方、紫外線吸収性を有する単量体の構成比が６０質量％を超えると、被膜形成樹脂成分への相溶性が低下し、形成される被膜の密着性等が悪化する虞がある。 Among the ultraviolet absorbing polymers, the composition ratio of the monomer having ultraviolet absorbing property is preferably 5 to 60% by mass, more preferably 20 to 50% by mass. If the composition ratio of the monomer having ultraviolet absorption is less than 5% by mass, it is difficult to significantly exhibit ultraviolet absorption. Increasing the amount of the ultraviolet absorbing polymer compounded in the coating agent to compensate for this has an adverse effect described later on the formed film. On the other hand, if the composition ratio of the monomer having ultraviolet absorption exceeds 60% by mass, the compatibility with the film-forming resin component may decrease, and the adhesion of the formed film may deteriorate.
コーティング剤中における紫外線吸収ポリマーの含有量は、固形分（ポリマー分）で３〜４０質量％が好ましく、５〜３５質量％がより好ましい。紫外線吸収ポリマーの含有量が３質量％未満では、被膜の紫外線吸収性能が不足する虞がある。一方、４０質量％を超えると、他の成分の相対的な含有量が低下して、被膜の密着性や赤外線吸収性能が低下する虞がある。なお、コーティング剤を調整する際は、水分散状態の紫外線吸収ポリマーとして、被膜形成樹脂成分１００重量部に対して１０〜１００質量部程度を目安として配合すればよい。 The content of the ultraviolet absorbing polymer in the coating agent is preferably 3 to 40% by mass, more preferably 5 to 35% by mass in terms of solid content (polymer content). If the content of the ultraviolet absorbing polymer is less than 3% by mass, the ultraviolet absorbing performance of the coating film may be insufficient. On the other hand, if it exceeds 40% by mass, the relative content of other components may decrease, and the adhesion of the coating film and the infrared absorption performance may decrease. When adjusting the coating agent, the ultraviolet absorbing polymer in the water-dispersed state may be blended in an amount of about 10 to 100 parts by mass with respect to 100 parts by weight of the film-forming resin component.
≪無機系赤外線吸収微粒子≫
無機系赤外線吸収微粒子（以下、単に赤外線吸収微粒子と称す）としては、例えば、アンチモンドープ酸化錫微粒子、アンチモンドープ酸化亜鉛微粒子、及びインジウムドープ酸化錫微粒子を挙げることができる。これらの赤外線吸収微粒子は、１種のみを単独で使用することもできるし、２種以上を混用することもできる。
≪Inorganic infrared absorbing fine particles≫
Examples of the inorganic infrared absorbing fine particles (hereinafter, simply referred to as infrared absorbing fine particles) include antimony-doped tin oxide fine particles, antimony-doped zinc oxide fine particles, and indium-doped tin oxide fine particles. Only one kind of these infrared absorbing fine particles can be used alone, or two or more kinds can be mixed.
赤外線吸収微粒子は、被膜形成樹脂成分に対して相溶性が無いため、コーティング剤中に分散している。そこで、形成される被膜の透明性（可視光線透過率）を損なわないために、できるだめ粒径が小さいことが好ましい。具体的には、メジアン径（５０％積算径）が４００ｎｍ以下が好ましく、より好ましくは３５０ｎｍ以下である。赤外線吸収微粒子の粒径の下限は、特に制限されない。 Since the infrared absorbing fine particles are not compatible with the film-forming resin component, they are dispersed in the coating agent. Therefore, in order not to impair the transparency (visible light transmittance) of the formed film, it is preferable that the resulting fine particle size is small. Specifically, the median diameter (50% integrated diameter) is preferably 400 nm or less, more preferably 350 nm or less. The lower limit of the particle size of the infrared absorbing fine particles is not particularly limited.
一方、赤外線吸収微粒子の粒径が小さいほど、コーティング剤へ添加した際に凝集し易く、均一分散性が低下する。そこで、赤外線吸収微粒子は、予め水中に分散された水分散体の状態で添加することが好ましい。これにより、赤外線吸収微粒子がコーティング剤中に均一に分散し、得られる被膜の赤外線吸収性能や密着性等が向上する。このような赤外線吸収微粒子水分散体の市販品としては、例えば三菱マテリアル社製の「透明導電性分散
（品番：ＴＤＬ−Ｓ）」や、日産化学社製の「セルナックス（品番：ＣＸ−Ｚ３３０Ｈ）」等が挙げられる。
On the other hand, the smaller the particle size of the infrared absorbing fine particles, the easier it is to aggregate when added to the coating agent, and the lower the uniform dispersibility. Therefore, it is preferable to add the infrared absorbing fine particles in the form of an aqueous dispersion previously dispersed in water. As a result, the infrared absorbing fine particles are uniformly dispersed in the coating agent, and the infrared absorbing performance and adhesion of the obtained coating film are improved. Commercially available products of such infrared absorbing fine particle water dispersion include, for example, "Transparent Conductive Dispersion (Product No .: TDL-S)" manufactured by Mitsubishi Materials, Ltd. and "Celnax (Product No .: CX-Z330H) manufactured by Nissan Chemical Industries, Ltd." ) ”And so on.
コーティング剤中における赤外線吸収微粒子の含有量は、１０〜３０質量％が好ましく、１５〜２５質量％がより好ましい。赤外線吸収微粒子の含有量が１０質量％未満では、被膜の赤外線吸収性能が不足する虞がある。一方、３０質量％を超えると、被膜の透明性や密着性等が低下する虞がある。なお、コーティング剤を調整する際は、水分散体として被膜形成樹脂成分１００重量部に対して１０〜５０質量部程度を目安として配合すればよい。 The content of the infrared absorbing fine particles in the coating agent is preferably 10 to 30% by mass, more preferably 15 to 25% by mass. If the content of the infrared absorbing fine particles is less than 10% by mass, the infrared absorbing performance of the coating film may be insufficient. On the other hand, if it exceeds 30% by mass, the transparency and adhesion of the coating film may decrease. When adjusting the coating agent, it may be blended as an aqueous dispersion in an amount of about 10 to 50 parts by mass with respect to 100 parts by weight of the film-forming resin component.
≪その他の成分≫
なお、形成される被膜の透明性や密着性等に悪影響を及ぼさず、特にブリードアウトも生じない範囲の極微量であれば、コーティング剤へ予備的に紫外線吸収微粒子を添加してもよい。紫外線吸収微粒子としては、ガリウムドープ酸化亜鉛、酸化亜鉛、酸化セリウム、酸化チタン等の金属酸化物微粒子を挙げることができる。この場合も、均一分散性を向上させるため、予め水中に分散している水分散体の状態で配合する。紫外線吸収微粒子水分散体の市販品としては、ＢＹＫ社製の「NANOBYK（品番：NANOBYK-3810、NANOBYK-3820、NANOBYK-3840など）」、ハクスイテック社製「パゼット（品番：CK、GK、GK-40、23-K）」などが挙げられる。
≪Other ingredients≫
In addition, UV absorbing fine particles may be preliminarily added to the coating agent as long as the amount is very small, which does not adversely affect the transparency and adhesion of the formed film and does not cause bleed-out. Examples of the ultraviolet absorbing fine particles include metal oxide fine particles such as gallium-doped zinc oxide, zinc oxide, cerium oxide, and titanium oxide. Also in this case, in order to improve the uniform dispersibility, the mixture is mixed in the state of an aqueous dispersion previously dispersed in water. Commercially available products of UV-absorbing fine particle water dispersion include "NANOBYK (product number: NANOBYK-3810, NANOBYK-3820, NANOBYK-3840, etc.)" manufactured by BYK, and "Pazette (product number: CK, GK, GK-) manufactured by HakusuiTech. 40, 23-K) ”and so on.
また、本発明の作用効果を阻害しない範囲で、増粘剤、レベリング剤、界面活性剤、消泡剤、着色剤、酸化防止剤、造膜助剤等の添加剤を、必要に応じて添加することもできる。但し、シリコーンは添加しない。使用環境によっては、被膜が白濁する虞があるからである。 In addition, additives such as thickeners, leveling agents, surfactants, defoamers, colorants, antioxidants, and film-forming aids are added as necessary within the range that does not impair the action and effect of the present invention. You can also do it. However, silicone is not added. This is because the film may become cloudy depending on the usage environment.
＜適用対象＞
コーティング剤の適用対象としては、典型的には窓ガラス等のガラス基材が挙げられる。ガラス基材としては、一般的な無機ガラスはもちろん、有機ガラスにも同様に適用できる。本発明のコーティング剤は、無機系基材のみならず有機系基材に対しても良好な密着性を有するからである。そのため、例えばアクリル樹脂やポリカーボネート樹脂等からなる透明樹脂パネルにも適用可能である。透明樹脂パネルとしては、建造物における採光用のパネルのほか、サンバイザーや眼鏡等の日用品も挙げられる。さらに、例えばＰＥＴフィルム等のポリエステルフィルムや、アクリルフィルム等の透明樹脂フィルムにも適用可能である。透明樹脂フィルムとしては、窓ガラスや透明樹脂パネルの表面に貼着された各種透明樹脂フィルムのほか、ビニール傘等の日用品も挙げられる。
<Applicable target>
The application target of the coating agent is typically a glass base material such as a window glass. As the glass base material, it can be similarly applied to organic glass as well as general inorganic glass. This is because the coating agent of the present invention has good adhesion not only to an inorganic base material but also to an organic base material. Therefore, it can be applied to a transparent resin panel made of, for example, an acrylic resin or a polycarbonate resin. Examples of the transparent resin panel include daily necessities such as sun visors and eyeglasses, as well as panels for daylighting in buildings. Further, it can be applied to a polyester film such as a PET film and a transparent resin film such as an acrylic film. Examples of the transparent resin film include various transparent resin films attached to the surface of window glass and transparent resin panels, as well as daily necessities such as vinyl umbrellas.
コーティング剤を硬化させて形成される被膜は、透明性（可視光線透過率）が高く、適用対象である基材の透明性を担保することができる。適用対象は、透明性を有する限り、有色透明と無色透明とを問わない。また、コーティング剤は、建造物等に既設の基材に適用することもできるし、建造物等へ設置する前の製造工場にて適用してもよい。 The film formed by curing the coating agent has high transparency (visible light transmittance), and can ensure the transparency of the base material to be applied. The target of application is not limited to colored transparent and colorless transparent as long as it has transparency. Further, the coating agent may be applied to an existing base material in a building or the like, or may be applied in a manufacturing factory before being installed in the building or the like.
＜被膜形成方法＞
コーティング剤は、適用対象へ塗布し、硬化剤を使用せずにそのまま常温乾燥（自然乾燥）にて被膜を形成することができる。温風やヒータ熱等を使用することで、硬化速度を短縮することもできる。コーティング剤の塗布方法は特に限定されないが、ローラー塗布、刷毛塗り、スポンジ塗布、噴霧、流延法など、一般家庭でも比較的容易に塗布できる方法を採用することが好ましい。塗布面は、適用対象である基材の一方面のみでもよいし、一方面及び他方面の双方でもよい。形成される被膜は、無機系基材及び有機系基材に対して密着性が良好で、耐擦傷性に優れるため、窓拭き等の一般的な清掃作業によって傷付いたり剥がれたりすることはない。
<Film formation method>
The coating agent can be applied to an application target and a film can be formed by drying at room temperature (natural drying) as it is without using a curing agent. The curing speed can be shortened by using warm air, heater heat, or the like. The method of applying the coating agent is not particularly limited, but it is preferable to adopt a method that can be applied relatively easily even in ordinary households, such as roller coating, brush coating, sponge coating, spraying, and casting method. The coating surface may be only one surface of the base material to be applied, or may be both one surface and the other surface. The formed film has good adhesion to inorganic and organic substrates and has excellent scratch resistance, so it will not be scratched or peeled off by general cleaning work such as window cleaning. ..
以下、本発明の具体的な実施例について説明するが、本発明はこれに限られることはない。
＜実施例１＞
実施例１では、無機系の赤外線吸収微粒子としてアンチモンドープ酸化亜鉛微粒子ゾル（日産化学工業社製「セルナックス」（品番：ＣＸ−Ｚ３３０Ｈ 固形分：３０％））を３０質量部、被膜形成樹脂成分としてエステル変性ポリウレタン水性エマルジョン（ＧＳＩクレオス社製「ＴＵＲＢＯＳＥＴ」（品番：２０２５ 樹脂固形分約３８％））を７０質量部、紫外線吸収剤として紫外線吸収ポリマー（新中村化学社製「ＵＶＡ−２０４Ｗ」（ポリマー分約３０％）を１０質量部混合し、１５分間撹拌した。その後、得られた撹拌混合液に、消泡剤（ＢＹＫケミー社製「ＢＹＫ−１６１０」）を０．２質量部、レベリング剤（ネオス社製「フタージェント」（品番：１００Ｃ））を０．１質量部、及び増粘剤（アデカ社製「アデカノール」（品番：ＵＨ−７５６ＶＦ））を０．８質量部添加し、さらに１５分撹拌した。
Specific examples of the present invention will be described below, but the present invention is not limited thereto.
<Example 1>
In Example 1, 30 parts by mass of an antimony-doped zinc oxide fine particle sol (“Celnax” (product number: CX-Z330H solid content: 30%) manufactured by Nissan Chemical Industries, Ltd.) was used as an inorganic infrared absorbing fine particle, and a film-forming resin component was used. 70 parts by mass of ester-modified polyurethane aqueous emulsion (“TURBOSET” manufactured by GSI Creos (product number: 2025 resin solid content: about 38%)), and UV absorbing polymer (“UVA-204W” manufactured by Shin-Nakamura Chemical Co., Ltd.) as an ultraviolet absorber. 10 parts by mass (polymer content: about 30%) was mixed and stirred for 15 minutes. Then, 0.2 parts by mass of a defoaming agent (“BYK-1610” manufactured by BYK Chemie) was leveled in the obtained stirring mixture. Add 0.1 parts by mass of the agent (Neos's "Futergent" (product number: 100C)) and 0.8 parts by mass of the thickener (Adeca's "Adecanol" (product number: UH-756VF)). The mixture was further stirred for 15 minutes.
以上のように調整した実施例１のコーティング剤を、市販の４インチ無泡ローラー毛丈６ｍｍを用いて４ｍｍ厚の板ガラス上に塗布し、１週間自然乾燥させて被膜を形成し、試験片とした。 The coating agent of Example 1 adjusted as described above was applied onto a plate glass having a thickness of 4 mm using a commercially available 4-inch non-foaming roller with a hair length of 6 mm, and was naturally dried for one week to form a film. did.
＜実施例２＞
実施例２では、無機系の赤外線吸収微粒子としてアンチモンドープ酸化錫微粒子水分散液（三菱マテリアル社製「ＴＤＬ−Ｓ」（固形分約１８％））を４０質量部、被膜形成樹脂成分としてポリウレタン水性エマルジョン（アデカ社製「アデカボンタイター」（品番：ＨＵＸ−５２２ 樹脂固形分約３０％））を６０質量部、紫外線吸収剤として紫外線吸収ポリマー（新中村化学社製「ＵＶＡ−２０４Ｗ」）を１０質量部混合し、１５分間撹拌した。その後、得られた撹拌混合液に、消泡剤（ＢＹＫケミー社製「ＢＹＫ−１６１０」）を０．２質量部、レベリング剤（ネオス社製「フタージェント」（品番：１００Ｃ））を０．１質量部、及び増増粘剤（アデカ社製「アデカノール」（品番：ＵＨ−７５６ＶＦ））を０．８質量部添加し、さらに１５分撹拌した。得られた実施例２のコーティング剤を、実施例１と同様にして被膜を形成し、試験片とした。
<Example 2>
In Example 2, 40 parts by mass of an antimony-doped tin oxide fine particle aqueous dispersion (“TDL-S” (solid content: about 18%) manufactured by Mitsubishi Materials Co., Ltd.) was used as an inorganic ultraviolet absorbing fine particle, and polyurethane was aqueous as a film-forming resin component. 60 parts by mass of emulsion (Adeca Bontiter (product number: HUX-522 resin solid content: about 30%)) and 10 UV absorbing polymers (UVA-204W manufactured by Shin-Nakamura Chemical Co., Ltd.) as UV absorbers. The mixture was mixed by mass and stirred for 15 minutes. Then, in the obtained stirring mixture, 0.2 parts by mass of an antifoaming agent ("BYK-1610" manufactured by BYK Chemie) and a leveling agent ("Futergent" manufactured by Neos Co., Ltd. (product number: 100C)) were added to 0. 1 part by mass and 0.8 parts by mass of a thickener (“Adecanol” manufactured by Adeka Corporation (product number: UH-756VF)) were added, and the mixture was further stirred for 15 minutes. The obtained coating agent of Example 2 was used to form a film in the same manner as in Example 1 to obtain a test piece.
＜実施例３＞
実施例３では、無機系の赤外線吸収微粒子としてアンチモンドープ酸化錫微粒子水分散液（三菱マテリアル社製「ＴＤＬ−Ｓ」）を４０質量部、被膜形成樹脂成分としてポリウレタン水性エマルジョン（アデカ社製「アデカボンタイター」（品番：ＨＵＸ−５２２））を６０質量部、紫外線吸収剤として紫外線吸収ポリマー（新中村化学社製「ＵＶＡ−２０４Ｗ」）を５０質量部混合し、１５分間撹拌した。その後、得られた撹拌混合液に、消泡剤（ＢＹＫケミー社製「ＢＹＫ−１６１０」）を０．２質量部、レベリング剤（ネオス社製「フタージェント」（品番：１００Ｃ））を０．１質量部、及び増増粘剤（アデカ社製「アデカノール」（品番：ＵＨ−７５６ＶＦ））を０．８質量部添加し、さらに１５分撹拌した。得られた実施例３のコーティング剤を、実施例１と同様にして被膜を形成し、試験片とした。
<Example 3>
In Example 3, 40 parts by mass of an antimony-doped tin oxide fine particle aqueous dispersion (“TDL-S” manufactured by Mitsubishi Materials) was used as an inorganic ultraviolet absorbing fine particle, and a polyurethane aqueous emulsion (“Adeca” manufactured by Adeca) was used as a film-forming resin component. 60 parts by mass of "Bontiter" (product number: HUX-522) and 50 parts by mass of an ultraviolet absorbing polymer ("UVA-204W" manufactured by Shin-Nakamura Chemical Co., Ltd.) as an ultraviolet absorber were mixed and stirred for 15 minutes. Then, in the obtained stirring mixture, 0.2 parts by mass of an antifoaming agent ("BYK-1610" manufactured by BYK Chemie) and a leveling agent ("Futergent" manufactured by Neos Co., Ltd. (product number: 100C)) were added to 0. 1 part by mass and 0.8 parts by mass of a thickener (“Adecanol” manufactured by Adeka Corporation (product number: UH-756VF)) were added, and the mixture was further stirred for 15 minutes. The obtained coating agent of Example 3 was used to form a film in the same manner as in Example 1 to prepare a test piece.
＜実施例４＞
実施例１のコーティング剤を、市販の４インチ無泡ローラー毛丈６ｍｍを用いて２ｍｍ厚のアクリル板上に塗布し、１週間自然乾燥させて被膜を形成し、試験片とした。
<Example 4>
The coating agent of Example 1 was applied onto a 2 mm thick acrylic plate using a commercially available 4-inch foamless roller with a hair length of 6 mm, and allowed to air dry for 1 week to form a film, which was used as a test piece.
＜比較例１＞
比較例１では、無機系の赤外線吸収微粒子としてアンチモンドープ酸化亜鉛微粒子ゾル（日産化学工業社製「セルナックス」（品番：ＣＸ−Ｚ３３０Ｈ））を３０質量部、被膜形成樹脂成分としてアクリル水性エマルジョン（高圧ガス社製「ぺガール」（品番：７５６ 樹脂固形分約４５％））を７０質量部、紫外線吸収剤として紫外線吸収ポリマー（新中村化学社製「ＵＶＡ−２４０Ｗ」）を１０質量部混合し、１５分間撹拌した。その後、得られた撹拌混合液に、消泡剤（ＢＹＫケミー社製「ＢＹＫ−１６１０」）を０．２質量部、レベリング剤（ネオス社製「フタージェント」（品番：１００Ｃ））を０．１質量部、及び増粘剤（アデカ社製「アデカノール」（品番：ＵＨ−７５６ＶＦ））を０．８質量部添加し、さらに１５分撹拌した。得られた比較例１のコーティング剤を、実施例１と同様にして被膜を形成し、試験片とした。
<Comparative example 1>
In Comparative Example 1, 30 parts by mass of antimony-doped zinc oxide fine particle sol (“Celnax” (product number: CX-Z330H) manufactured by Nissan Chemical Industry Co., Ltd.) was used as an inorganic ultraviolet absorbing fine particle, and an acrylic aqueous emulsion (as a film forming resin component) was used. 70 parts by mass of "Pegal" (product number: 756 resin solid content about 45%) manufactured by High Pressure Gas Co., Ltd. and 10 parts by mass of UV absorbing polymer ("UVA-240W" manufactured by Shin-Nakamura Chemical Co., Ltd.) as an ultraviolet absorber are mixed. , Stirred for 15 minutes. Then, in the obtained stirring mixture, 0.2 parts by mass of an antifoaming agent ("BYK-1610" manufactured by BYK Chemie) and a leveling agent ("Futergent" manufactured by Neos Co., Ltd. (product number: 100C)) were added to 0. 1 part by mass and 0.8 parts by mass of a thickener (“Adecanol” manufactured by Adeka Corporation (product number: UH-756VF)) were added, and the mixture was further stirred for 15 minutes. The obtained coating agent of Comparative Example 1 was used as a test piece by forming a film in the same manner as in Example 1.
＜比較例２＞
比較例２では、無機系の赤外線吸収剤としてアンチモンドープ酸化亜鉛微粒子ゾル（日産化学工業社製「セルナックス」（品番：ＣＸ−Ｚ３３０Ｈ））を３０質量部、被膜形成樹脂成分としてエステル変性ポリウレタン水性エマルジョン（ＧＳＩクレオス社製「ＴＵＲＢＯＳＥＴ」（品番：２０２５））を７０質量部、紫外線吸収剤として無機系紫外線吸収剤（ＢＹＫ社製「ＢＹＫＮＡＮＯ」（品番：３８４０））を２質量部混合し、１５分間撹拌した。その後、得られた撹拌混合液に、消泡剤（ＢＹＫケミー社製「ＢＹＫ−１６１０」）を０．２質量部、レベリング剤（ネオス社製「フタージェント」（品番：１００Ｃ））を０．１質量部、及び増粘剤（アデカ社製「アデカノール」（品番：ＵＨ−７５６ＶＦ））を０．８質量部添加し、さらに１５分撹拌した。得られた比較例２のコーティング剤を、実施例１と同様にして被膜を形成し、試験片とした。
※有機基材に適用した実施例もあると好ましいです。
<Comparative example 2>
In Comparative Example 2, 30 parts by mass of antimony-doped zinc oxide fine particle sol (“Celnax” (product number: CX-Z330H) manufactured by Nissan Chemical Industries, Ltd.) was used as an inorganic ultraviolet absorber, and ester-modified polyurethane was aqueous as a film-forming resin component. 70 parts by mass of an emulsion ("TURBOSET" (product number: 2025) manufactured by GSI Creos) and 2 parts by mass of an inorganic UV absorber ("BYKNANO" (product number: 3840) manufactured by BYK) as an ultraviolet absorber are mixed and 15 parts by mass. Stir for minutes. Then, in the obtained stirring mixture, 0.2 parts by mass of an antifoaming agent ("BYK-1610" manufactured by BYK Chemie) and a leveling agent ("Futergent" manufactured by Neos Co., Ltd. (product number: 100C)) were added to 0. 1 part by mass and 0.8 parts by mass of a thickener (“Adecanol” manufactured by Adeka Corporation (product number: UH-756VF)) were added, and the mixture was further stirred for 15 minutes. The obtained coating agent of Comparative Example 2 was used as a test piece by forming a film in the same manner as in Example 1.
* It is preferable that there are examples applied to organic substrates.
上記で得られた各試験片の被膜について、各種物性を下記の方法および基準で評価した。その結果を、各コーティング剤の組成と共に表１に示す。 Various physical properties of the coating film of each test piece obtained above were evaluated by the following methods and criteria. The results are shown in Table 1 together with the composition of each coating agent.
＜透明性＞
目視により、作成したコーティング膜の透明性の評価を行った。その際の評価基準は、次の通りである。
○：透明性が維持された ×：白濁した
<Transparency>
The transparency of the prepared coating film was visually evaluated. The evaluation criteria at that time are as follows.
◯: Transparency was maintained ×: Cloudy
＜耐候性（耐湿潤冷熱繰り返し試験）＞
ＪＩＳＫ ５６００ ７−４に基づき、小型低温恒湿機（ＳＨ−６４２）を用いて、あいち産業科学技術センターにて４００時間の促進耐候性試験（耐湿潤冷熱繰り返し試験）を行った。
湿潤状態：５０±１℃、９５％ＲＨ、１８時間
低温状態：−２０±２℃、３時間
標準状態：２３±２℃、３時間
高温状態：５０±２℃ ３時間のサイクル試験を３０回行った。
また、その際の評価基準は次の通りである。
○：塗膜の膨れ、剥がれは見られなかった ×：塗膜の膨れ、剥がれが見られた
<Weather resistance (wet and cold resistance repeated test)>
Based on JISK 5600 7-4, a 400-hour accelerated weather resistance test (wet and cold resistance repeated test) was conducted at the Aichi Industrial Science and Technology Center using a small low-temperature humidity controller (SH-642).
Wet condition: 50 ± 1 ° C, 95% RH, 18 hours Low temperature condition: -20 ± 2 ° C, 3 hours Standard condition: 23 ± 2 ° C, 3 hours High temperature condition: 50 ± 2 ° C 3
The evaluation criteria at that time are as follows.
◯: No swelling or peeling of the coating film was observed. ×: Swelling or peeling of the coating film was observed.
＜ＶＯＣ（ホルムアルデヒド放散量測定）＞
１平方メートルあたり４０ｇの塗布量において、ＪＩＳ Ａ １９０１（２００９）の小型チャンバー法により（一財）塗料検査協会で測定を行った。
<VOC (measurement of formaldehyde emission)>
The coating amount of 40 g per square meter was measured by the Paint Inspection Association by the small chamber method of JIS A 1901 (2009).
また、各試験片の可視光透過率、紫外線透過率、及び赤外線透過率を、ＪＩＳ Ａ ５７５９に基づき測定した。その結果を表２に示す。なお、実施例１については、その分光スペクトルも図１に示す。
表１の結果から、実施例１〜４においては、被膜の透明性及び耐候性が良好であり、ＶＯＣであるホルムアルデヒドの発生もなかった。また、表２の結果から、実施例１〜４においては、良好な可視光透過率を保ちながらも、紫外線及び赤外線に関しては透過率が大幅に下がっており、赤外線・紫外線吸収性能に優れていることが確認された。一方で、表１，２の結果から、比較例１は被膜形成樹脂成分がポリウレタン水性エマルジョン又は変性ポリウレタン水性エマルジョンではなく、アクリル水性エマルジョンであったため、透明性が損なわれ、耐候性試験においても膨れ、剥がれが見られた。また、比較例２は、紫外線吸収剤として紫外線吸収ポリマーでない、従来の紫外線吸収微粒子を用いたため、透明性が損なわれ、耐候試験においても膨れ、剥がれが見られた。
From the results in Table 1, in Examples 1 to 4, the transparency and weather resistance of the coating film were good, and formaldehyde, which is a VOC, was not generated. Further, from the results in Table 2, in Examples 1 to 4, the transmittance of ultraviolet rays and infrared rays was significantly reduced while maintaining good visible light transmittance, and the infrared rays / ultraviolet rays absorption performance was excellent. It was confirmed that. On the other hand, from the results in Tables 1 and 2, in Comparative Example 1, since the film-forming resin component was not a polyurethane aqueous emulsion or a modified polyurethane aqueous emulsion but an acrylic aqueous emulsion, the transparency was impaired and the film swelled in the weather resistance test. , Peeling was seen. Further, in Comparative Example 2, since the conventional ultraviolet absorbing fine particles, which are not the ultraviolet absorbing polymer, were used as the ultraviolet absorber, the transparency was impaired, and swelling and peeling were observed in the weather resistance test.
Claims (6)
前記被膜形成樹脂成分が、ポリウレタン水性エマルジョン及び変性ポリウレタン水性エマルジョンのうち少なくとも一方の常温硬化型樹脂成分であり、
前記常温硬化型樹脂成分は、常温乾燥によって硬化剤を使用する必要なく被膜を形成する樹脂であり、
前記紫外線吸収剤が、前記被膜形成樹脂成分と相溶している紫外線吸収ポリマーであり、
前記被膜が、ＪＩＳ Ａ ５７５９に基づき測定した可視光透過率が７７．８％以上８５．５％以下となる透明性が維持されたものであり、
前記紫外線吸収ポリマーが、
ベンゾトリアゾール系単量体、ベンゾエート系単量体、ベンゾフェノン系単量体、トリアジン系単量体、及びシアノアクリレート系単量体の中から選ばれる少なくとも一種の単量体と、
アクリル酸エステル、メタクリル酸エステル、及びビニル系単量体の中から選ばれる少なくとも一種の単量体との共重合体であり、
前記赤外線吸収剤が、無機系赤外線吸収微粒子である、水性赤外線・紫外線遮蔽コーティング剤。 Aqueous infrared / ultraviolet shielding coating agent (containing silicone or transparent silicon-modified urethane) containing a film-forming resin component, an ultraviolet absorber, and an infrared absorber and using water as a dispersion medium for each component. (Excluding those containing resin emulsion, but one or both)
The film-forming resin component is at least one of a polyurethane aqueous emulsion and a modified polyurethane aqueous emulsion, which is a room temperature curable resin component.
The room temperature curable resin component is a resin that forms a film by drying at room temperature without the need to use a curing agent.
The ultraviolet absorber is an ultraviolet absorbing polymer that is compatible with the film-forming resin component.
The coating film maintains the transparency such that the visible light transmittance measured based on JIS A 5759 is 77.8% or more and 85.5% or less.
The ultraviolet absorbing polymer
At least one monomer selected from benzotriazole-based monomers, benzoate-based monomers, benzophenone-based monomers, triazine-based monomers, and cyanoacrylate-based monomers, and
It is a copolymer with at least one monomer selected from acrylic acid ester, methacrylic acid ester, and vinyl-based monomer.
An aqueous infrared / ultraviolet shielding coating agent in which the infrared absorber is an inorganic infrared absorbing fine particle.
The aqueous infrared / ultraviolet shielding coating agent according to any one of claims 1 to 4 is applied to at least one of the inner surface and the outer surface of the organic transparent base material to form a film without using a curing agent. , Infrared / ultraviolet shielding treatment method.
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