JP4165784B2 - Outdoor seat - Google Patents

Description

【００１４】
エチレンイミン変性ポリマーは側鎖にグラフト１級アミノ基を有するため、プライマー層２は軟質ＰＶＣ等のシート本体１および中間層３に対して良好な密着性を発揮する。また、アクリル主鎖を有するものは耐候性に優れているので屋外用シートとしての用途に特に適している。
【００１５】
なお、ポリエチレンイミンはモノエタノールアミン（H2NCH2CH2OH）を出発物質として製造されるエチレンイミンを原料とする開環重合体またはその誘導体であり、式２ないし４に示される化学構造を有する。
【００１６】
【式２】

【００１７】
【式３】

【００１８】
【式４】

【００１９】
中間層３は式５に示される化学構造を有するシリコーンワニスよりなる。ここでシリコーンワニスとは、CH3SiO3/2, (CH3)2SiO, (CH3)SiO2, (CH3)3SiO1/2NO 等のメチル基を組み合わせた共重合体であるメチルシリコーン系、これらメチル基のほかC6H5SiO2/3, (C6H5)2SiO, (CH3)(C6H5)SiO 等のフェニル基を組み合わせた共重合体であるメチルフェニルシリコーン系、あるいはこれらとアルキッド樹脂、ポリエステル樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂等との共重合体である変性シリコーン系の樹脂塗料を意味するものである。
【００２０】
【式５】

【００２１】
中間層３は前記エチレンイミン変性ポリマーが側鎖にグラフト１級アミノ基を持つことによってプライマー層２との密着性が良好であり、シリコーン樹脂同士のイオン結合によってシリコーン樹脂塗料層４との密着性も良好である。
【００２２】
シリコーン樹脂塗料層４には光触媒粒子が含有される。光触媒粒子としては酸化チタン（チタニア）、特に無定形チタニアが好適に用いられるが、その他、ZnO、SnO2、XrTiO3、WO3、Bi2O3、Fe2O3等の金属酸化物を用いてもよい。これらの光触媒粒子は紫外線を受けて酸化還元反応を励起することによってシート表面に付着した塵埃物質を分解除去すると共に、シート表面を親水性に維持することによって防汚性を与える。また、シリコーン樹脂塗料層４にさらにシリカを含有させると、シート表面の親水性をより向上させることができるので、好ましい態様である。
【００２３】
以下、本発明の実施例を比較例と対比して説明することにより、本発明の屋外用シートが優れた防汚性を有するものであることを実証する。
【００２４】
ＰＶＣ樹脂（重合度：１４００）１００重量部に対して可塑剤としてＤＯＰを６０重量部、安定剤としてバリウム亜鉛化合物を４重量部、顔料として酸化チタンを２０重量部加え、カレンダーで０．５ｍｍの厚さにしたものをシート本体１とし、このシート本体１の表面に、アクリル共重合体とポリエチレンイミンのグラフト化物を０．１ｍｍ厚に塗布してプライマー層２を形成し、プライマー層２の表面に、メチル基を含有するシリコーンワニスを２μｍ厚に塗布して中間層３を形成し、さらに、中間層３の表面に、無定形チタニアおよび無定形シリカを含有させたシリコーン樹脂を塗布して塗料層４を形成して、本発明の実施例となる屋外用シートを得た。
【００２５】
比較例として、上記実施例と同じシート本体１の表面にプライマー層２を形成することなく直接上記実施例と同様にして中間層３および塗料層４を形成して得たもの（比較例１）、上記実施例と同じシート本体１の表面にアクリル・フッ素共重合体による樹脂塗料を０．１ｍｍ厚に塗布してトップ層としたもの（比較例２）、および、上記実施例と同じシート本体１の表面に５０μｍ厚のフッ化ビニリデン／アクリル共押出しフィルムをラミネートしたもの（比較例３）を準備した。
【００２６】
そして、これら実施例および比較例１〜３のシートの防汚性を比較するため、ＪＩＳ−Ｌ１０２３に準拠した汚れ試験による初期防汚性、ＳＷＯＭ（サンシャインウェザーメーター：スガ試験機）照射1000時間後の防汚性および南面30度屋外暴露後の防汚性をそれぞれ目視にて評価した。その結果を図２に示す。
【００２７】
図２に示される結果から明らかなように、本発明の実施例によるシートはいずれの項目においても優れた防汚性を示しており、従来技術による比較例のシートに比べて格段に優れた防汚性を有することが実証された。
【００２８】
【発明の効果】
本発明によれば、シート本体と光触媒粒子を含有するシリコーン樹脂塗料層との間に、エチレンイミン変性ポリマーを主体とするプライマー層およびシリコーンワニスを主体とする中間層が介在されてなるため、耐候性および防汚性に優れると共に層間剥離を生じない屋外用シートが提供される。
【図面の簡単な説明】
【図１】本発明の一実施例による屋外用シートの構成を示す断面図である。
【図２】本発明の実施例および比較例による屋外用シートの防汚性を評価した結果を示す表である。
【符号の説明】
１ シート本体
２ プライマー層
３ 中間層
４ 光触媒粒子含有シリコーン樹脂塗料層[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an outdoor sheet, and more particularly to a sheet having weather resistance and antifouling properties suitable for use in a tent, a greenhouse, and the like.
[0002]
[Prior art]
In general, soft PVC is used as a sheet used for such applications, and in recent years, soft PVC is used as a base material and the surface thereof is made of an acrylic resin, an acrylic / fluorine copolymer, vinylidene fluoride (PVDF), or the like. Although products with improved weather resistance have been commercialized by applying single-layer or multiple-layer coatings or heat-sealing two-layer coextruded films of acrylic and PVDF, antifouling properties are not always sufficient and long There was a problem of deterioration over time due to the use of the period.
[0003]
In order to solve this problem, in Japanese Patent Application Laid-Open No. 9-78454, a hydrophilic surface layer containing photocatalyst particles is provided on the surface of a sheet main body, and further, redox by a photocatalyst is provided between the sheet main body and the hydrophilic surface layer. It has been proposed to provide an intermediate layer that protects the sheet body from reaction. According to this prior art, since the hydrophilic surface layer is formed, the sheet surface can be self-cleaned with rainwater or the like, and the photocatalyst particles are contained so that the hydrophilicity is restored by ultraviolet irradiation. It is supposed that hydrophilicity can be maintained over a period. Furthermore, when the photocatalyst particles undergo an oxidation-reduction reaction when irradiated with ultraviolet rays, the dirt component adhering to the surface can be decomposed, and by providing the intermediate layer, the sheet body is protected from the oxidation-reduction reaction by the photocatalyst particles.
[0004]
[Problems to be solved by the invention]
By the way, in the above prior art, the formation of the intermediate layer is not an essential requirement, but when the hydrophilic surface layer is directly laminated on the surface of the sheet body, the sheet body deteriorates due to the oxidation-reduction reaction by the photocatalyst. Therefore, in practice, it is considered indispensable to interpose an intermediate layer serving as a barrier layer between the sheet main body and the hydrophilic surface layer.
[0005]
However, when soft PVC is used as the sheet main body, the plasticizer contained in the soft PVC leaches out to the surface, so that the adhesion with the intermediate layer becomes insufficient. According to the above prior art, an aluminum vapor deposition film or a film containing aluminum particles is used for the intermediate layer, but in any case, adhesion is greatly impaired by the plasticizer leached on the surface of the soft PVC, causing delamination. Cause.
[0006]
In addition, when an aluminum vapor deposition film or a film containing aluminum particles is used as an intermediate layer, the adhesion between the intermediate layer and the hydrophilic surface layer is not good, and delamination between them becomes a problem.
[0007]
[Means for Solving the Problems]
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problems in the prior art described above, and to provide an outdoor sheet having a novel configuration that is excellent in weather resistance and antifouling properties and does not cause delamination.
[0008]
That is, in the outdoor sheet according to the present invention, a silicone resin paint layer containing photocatalyst particles is formed on the surface of the sheet body through a primer layer mainly composed of ethyleneimine-modified polymer and an intermediate layer mainly composed of silicone varnish. It is characterized by.
[0009]
The sheet body is preferably soft PVC and the photocatalytic particles are preferably titania.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows the structure of an outdoor sheet according to the present invention, in which a paint layer 4 is formed on the surface of a sheet body 1 with a primer layer 2 and an intermediate layer 3 interposed therebetween.
[0011]
As the sheet body 1, a soft PVC film, a fluorine-based film, a PET film, an OPP film, or the like can be used. However, according to the present invention, when a soft PVC is used as described later, a plasticizer is leached on the surface. Therefore, it is preferable to use soft PVC that is advantageous in terms of workability and cost.
[0012]
The primer layer 2 formed on the surface of the sheet body 1 is mainly composed of an ethyleneimine-modified polymer. Here, the ethyleneimine-modified polymer is obtained by grafting polyethyleneimine (PEI) to the side chain of an acrylic polymer or the like as the main chain, and has a chemical structure represented by Formula 1.
[0013]
[Formula 1]

[0014]
Since the ethyleneimine-modified polymer has a graft primary amino group in the side chain, the primer layer 2 exhibits good adhesion to the sheet body 1 such as soft PVC and the intermediate layer 3. Moreover, since the thing which has an acrylic principal chain is excellent in a weather resistance, it is especially suitable for the use as an outdoor sheet | seat.
[0015]
Polyethyleneimine is a ring-opening polymer made from ethyleneimine produced from monoethanolamine (H2NCH2CH2OH) as a starting material or a derivative thereof, and has a chemical structure represented by formulas 2 to 4.
[0016]
[Formula 2]

[0017]
[Formula 3]

[0018]
[Formula 4]

[0019]
The intermediate layer 3 is made of a silicone varnish having a chemical structure represented by Formula 5. Here, the silicone varnish is a methyl silicone-based copolymer combining methyl groups such as CH3SiO3 / 2, (CH3) 2SiO, (CH3) SiO2, (CH3) 3SiO1 / 2NO, etc., in addition to these methyl groups, C6H5SiO2 / 3, (C6H5) 2SiO, (CH3) (C6H5) SiO and other phenyl group-based copolymers of methylphenyl silicone, or alkyd resin, polyester resin, epoxy resin, acrylic resin, urethane resin, etc. This means a modified silicone resin coating which is a copolymer of the above.
[0020]
[Formula 5]

[0021]
The intermediate layer 3 has good adhesion to the primer layer 2 because the ethyleneimine-modified polymer has a graft primary amino group in the side chain, and adhesion to the silicone resin coating layer 4 by ionic bond between silicone resins. Is also good.
[0022]
The silicone resin paint layer 4 contains photocatalyst particles. As the photocatalyst particles, titanium oxide (titania), particularly amorphous titania, is preferably used, but other metal oxides such as ZnO, SnO2, XrTiO3, WO3, Bi2O3, and Fe2O3 may be used. These photocatalyst particles receive ultraviolet rays to excite the oxidation-reduction reaction to decompose and remove dust substances adhering to the sheet surface, and to impart antifouling properties by maintaining the sheet surface hydrophilic. Further, when the silicone resin coating layer 4 further contains silica, the hydrophilicity of the sheet surface can be further improved, which is a preferable embodiment.
[0023]
Hereinafter, it demonstrates that the outdoor sheet | seat of this invention has the outstanding antifouling property by describing the Example of this invention in contrast with a comparative example.
[0024]
60 parts by weight of DOP as a plasticizer, 4 parts by weight of a barium zinc compound as a stabilizer, and 20 parts by weight of titanium oxide as a pigment are added to 100 parts by weight of a PVC resin (degree of polymerization: 1400), and 0.5 mm by calendar The sheet body 1 is formed to have a thickness, and a primer layer 2 is formed on the surface of the sheet body 1 by applying a grafted product of an acrylic copolymer and polyethyleneimine to a thickness of 0.1 mm. Further, a silicone varnish containing a methyl group is applied to a thickness of 2 μm to form an intermediate layer 3, and a silicone resin containing amorphous titania and amorphous silica is further applied to the surface of the intermediate layer 3. Layer 4 was formed to obtain an outdoor sheet serving as an example of the present invention.
[0025]
As a comparative example, the intermediate layer 3 and the paint layer 4 were directly formed in the same manner as in the above example without forming the primer layer 2 on the surface of the same sheet body 1 as in the above example (Comparative Example 1). The same sheet body as in the above example was coated with a resin coating made of an acrylic / fluorine copolymer to a thickness of 0.1 mm on the surface of the same sheet body (Comparative Example 2), and the same sheet body as in the above example 1 was prepared by laminating a vinylidene fluoride / acrylic coextruded film having a thickness of 50 μm on the surface (Comparative Example 3).
[0026]
And in order to compare the antifouling property of the sheet | seat of these Examples and Comparative Examples 1-3, the initial antifouling property by the dirt test based on JIS-L1023, 1000 hours after irradiation of SWOM (Sunshine weather meter: Suga test machine) The antifouling property and the antifouling property after outdoor exposure at 30 ° on the south side were evaluated visually. The result is shown in FIG.
[0027]
As is apparent from the results shown in FIG. 2, the sheets according to the examples of the present invention show excellent antifouling properties in all items, and the resistance is much superior to the sheets of comparative examples according to the prior art. It was proved to be soiling.
[0028]
【The invention's effect】
According to the present invention, a primer layer mainly composed of an ethyleneimine-modified polymer and an intermediate layer mainly composed of a silicone varnish are interposed between the sheet main body and the silicone resin paint layer containing photocatalyst particles. Provided is an outdoor sheet that has excellent properties and antifouling properties and does not cause delamination.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of an outdoor seat according to an embodiment of the present invention.
FIG. 2 is a table showing the results of evaluating the antifouling properties of outdoor sheets according to examples and comparative examples of the present invention.
[Explanation of symbols]
1 Sheet body 2 Primer layer 3 Intermediate layer 4 Photocatalyst particle-containing silicone resin paint layer

Claims (3)

An outdoor sheet characterized in that a silicone resin paint layer containing photocatalyst particles is formed on the surface of the sheet body through a primer layer mainly composed of an ethyleneimine-modified polymer and an intermediate layer mainly composed of a silicone varnish. . The outdoor sheet according to claim 1, wherein the sheet body is soft PVC. The outdoor sheet according to claim 1, wherein the photocatalyst particles are titania.

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