JP3768211B2 - Anti-fouling soft vinyl chloride sheet for accordion doors - Google Patents
Anti-fouling soft vinyl chloride sheet for accordion doors Download PDFInfo
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- JP3768211B2 JP3768211B2 JP2003277970A JP2003277970A JP3768211B2 JP 3768211 B2 JP3768211 B2 JP 3768211B2 JP 2003277970 A JP2003277970 A JP 2003277970A JP 2003277970 A JP2003277970 A JP 2003277970A JP 3768211 B2 JP3768211 B2 JP 3768211B2
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- vinyl chloride
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- soft vinyl
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 30
- 230000003373 anti-fouling effect Effects 0.000 title claims description 27
- 239000011941 photocatalyst Substances 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000012790 adhesive layer Substances 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052586 apatite Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 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 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229910021647 smectite Inorganic materials 0.000 claims description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims 1
- 241000473391 Archosargus rhomboidalis Species 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
この発明は、防汚性に優れた室内間仕切り部材、例えばアコーデオンドアの防汚性に優れたアコーデオンドア用軟質塩化ビニルシートに関する。 The present invention relates to an indoor partition member excellent in antifouling property, for example, a soft vinyl chloride sheet for an accordion door excellent in antifouling property of an accordion door.
合成樹脂シートから作られたの室内の間仕切り部材としてアコーデオンドアなど種々提案されている。特に、合成樹脂としては加工性、柔軟性、防炎性及び経済性が優れることから軟質塩化ビニルが室内の内外装部品に多く利用されている。しかし、利用されている軟質塩化ビニルの場合は、使用されている可塑剤が長期間に亘り、シートの表面に移行しやすく、表面の汚れの原因となっていた。特に、表面に汚れが付着しやすく、付着した汚れが除去し難いといった欠点があった。
このような軟質塩化ビニルの表面の汚れを防止するために内部の可塑剤の移行を防止する方法としてエポキシ変性シリコーンプレポリマーやポリエステル樹脂を使用するものが知られている（特許文献１、特許文献２）。また、汚れ防止する方法として表面自由エネルギーの低い非粘着性に優れた表面を形成させる目的でフッ素系化合物をシートの表面に塗布するフッ素樹脂、珪素樹脂、オレフィン樹脂などの樹脂皮膜をコーティング若しくはラミネートする方法などが知られている（特許文献３）。
その他、繊維布の表面に塩化ビニルを塗布または含浸させたものの表面に汚れの付着を防止するフッ素系樹脂や生じた汚れを分解させる光触媒皮膜を形成させる方法が知られている（特許文献４、特許文献５、特許文献６）。
また、耐汚れ性を改善するためにフッ素樹脂である四フッ化エチレン樹脂と光触媒と併用する発明が知られている（特許文献７）。
Various accordion doors and the like have been proposed as room partition members made of synthetic resin sheets. In particular, as a synthetic resin, soft vinyl chloride is widely used for indoor and exterior parts because of its excellent processability, flexibility, flameproofness and economy. However, in the case of soft vinyl chloride being used, the plasticizer used tends to migrate to the surface of the sheet for a long period of time, causing the surface to become dirty. In particular, there is a drawback in that dirt easily adheres to the surface, and the attached dirt is difficult to remove.
As a method for preventing migration of an internal plasticizer in order to prevent such a soft vinyl chloride surface from being soiled, a method using an epoxy-modified silicone prepolymer or a polyester resin is known (Patent Document 1, Patent Document). 2). In addition, as a method for preventing contamination, coating or laminating a resin film such as a fluororesin, a silicon resin, or an olefin resin, in which a fluorine-based compound is applied to the surface of the sheet for the purpose of forming a surface having low surface free energy and excellent non-adhesiveness A method of performing this is known (Patent Document 3).
In addition, there is known a method of forming a fluorine-based resin for preventing the adhesion of dirt or a photocatalyst film for decomposing the produced dirt on the surface of the fiber cloth coated or impregnated with vinyl chloride (Patent Document 4, Patent Document 5 and Patent Document 6).
Moreover, in order to improve dirt resistance, the invention used together with the tetrafluoroethylene resin which is a fluororesin, and a photocatalyst is known (patent document 7).
また、特許文献６に記載される「防汚性シート」は、可塑剤の移行防止層と光触媒防汚層とを有し、これらの層の間にポリシロキサンとアクリルシリコーン樹脂との混合物を含む接着層を備えた塩化ビニルシートが開示されているが、この防汚性シートは屋外にて使用する産業用のものである。繊維材料を基布とし、その表面に塩化ビニル樹脂を塗布したものである。可塑剤移行防止層はアクリル系樹脂を使用しているが、充分な移行防止にはなっていなかった。そのために表面に金属蒸着層を形成したものである。
特許文献７の四フッ化エチレン樹脂と光触媒との組み合わせたものは、四フツ化エチレン樹脂、光触媒ともに不溶成分であるため皮膜を形成させるには何らかのバインダー成分を必要とし、光触媒に分解しない安定な成分で、十分な基材との密着性と四フツ化エチレン樹脂および光触媒を固定化させるためには相当量のバインダー成分を配合する必要がある。その結果、防汚性機能を有する四フツ化エチレン樹脂および光触媒の配合比率が低減することで満足な防汚性を確保できないことが多い。また、バインダーによっては透明性、柔軟性を確保できない場合もある。
Further, the “antifouling sheet” described in Patent Document 6 has a plasticizer migration prevention layer and a photocatalyst antifouling layer, and contains a mixture of polysiloxane and acrylic silicone resin between these layers. A vinyl chloride sheet with an adhesive layer is disclosed, but this antifouling sheet is for industrial use outdoors. A fiber material is used as a base fabric, and a vinyl chloride resin is applied to the surface. The plasticizer migration prevention layer uses an acrylic resin, but was not sufficient to prevent migration. Therefore, a metal vapor deposition layer is formed on the surface.
Since the combination of the tetrafluoroethylene resin and the photocatalyst of Patent Document 7 is an insoluble component in both the tetrafluoroethylene resin and the photocatalyst, some binder component is required to form a film, and it does not decompose into a photocatalyst. It is necessary to add a considerable amount of a binder component in order to fix the sufficient adhesion to the base material and the tetrafluoroethylene resin and the photocatalyst. As a result, satisfactory antifouling properties cannot often be ensured by reducing the blending ratio of the tetrafluoroethylene resin having the antifouling function and the photocatalyst. Moreover, transparency and flexibility may not be ensured depending on the binder.
後者の光触媒に関しては、光が当たる箇所においては有機物の分解作用が継続的に発現することから満足し得る防汚効果を得られるものの、室内の光（特に紫外線）が十分に当たらない場所においてはその効果が十分に現れない。加えて、光触媒自体に吸着性があるため、状況によっては未処理の塩化ビニルシートよりも汚染される場合もある。
さらに、改善内容として前述した２つの方法を融合、すなわち、非粘着性樹脂に光触媒を添加させた皮膜を表面に形成させる方法も容易に類推される。しかしながら、光触媒の強力な酸化作用により多くの樹脂が分解されることから、唯一分解されない候補としては四フツ化エチレン樹脂と光触媒との組合せが挙げられ、特開平１０−８８０６１号公報等にて既に提案されている。
With regard to the latter photocatalyst, it is possible to obtain a satisfactory antifouling effect because the decomposition action of organic matter continuously develops in places where light is exposed, but in places where indoor light (especially ultraviolet rays) is not sufficiently exposed The effect does not appear sufficiently. In addition, since the photocatalyst itself is adsorptive, it may be more contaminated than an untreated vinyl chloride sheet depending on the situation.
Furthermore, it is easy to analogize a method in which the above-described two methods are combined as an improvement, that is, a film in which a photocatalyst is added to a non-adhesive resin is formed on the surface. However, since many resins are decomposed by the strong oxidizing action of the photocatalyst, the only candidate that is not decomposed is a combination of a tetrafluoroethylene resin and a photocatalyst, which has already been disclosed in JP-A-10-88061 and the like. Proposed.
本発明は光触媒の酸化チタンと、光触媒に分解されずしかも高い非粘着性を有する四フツ化エチレン樹脂の濃度を高くした表面層を形成させることで、外覿、柔軟性を損なうことなく室内において継続的な優れた防汚性を有するパーティション用軟質塩化ビニルシートを提案するものである。 The present invention forms a surface layer with a high concentration of photocatalyst titanium oxide and a highly non-adhesive tetratetrafluoroethylene resin that is not decomposed into a photocatalyst, so that it can be used indoors without damaging the outer casing and flexibility. A soft vinyl chloride sheet for partitions having continuous excellent antifouling properties is proposed.
この発明は、比較的に汚れを防止し長期間にわたり、防汚性を有するアコーデオンドア用塩化ビニルシートを提供するものである。
この発明の課題は、非粘着性樹脂に長期間安定な光触媒を添加させた防汚性アコーデオンドア用軟質塩化ビニルシートを提供することである。
このような防汚性の表面層を実現させるために、接着層の成分、付着量および上塗りの付着量を中心に検討した。
The present invention provides a vinyl chloride sheet for an accordion door that is relatively resistant to contamination and has antifouling properties over a long period of time.
An object of the present invention is to provide an antifouling accordion door soft vinyl chloride sheet obtained by adding a long-term stable photocatalyst to a non-adhesive resin.
In order to realize such an antifouling surface layer, studies were made focusing on the components of the adhesive layer, the amount of adhesion, and the amount of adhesion of the topcoat.
この発明は、前記課題を達成するために以下の構成としたものである。
軟質塩化ビニルシートの表面上にシリコン変性アクリル樹脂を塗布、乾燥させて接着層を形成し、この接着層上に、光触媒である酸化チタンと四フツ化エチレン樹脂とを含む溶液を上塗り塗布して、乾燥させて上塗り層を形成して防汚性を付与させた防汚性アコーデオンドア用軟質塩化ビニルシー卜の構成である。
The present invention has the following configuration in order to achieve the above object.
A silicone-modified acrylic resin is applied on the surface of the soft vinyl chloride sheet, and dried to form an adhesive layer. On this adhesive layer, a solution containing photocatalyst titanium oxide and tetrafluoroethylene resin is overcoated. This is a structure of a soft vinyl chloride sheet for antifouling accordion doors, which is dried to form an overcoat layer to impart antifouling properties.
この発明の前記課題は、軟質塩化ビニルシートの表面上にシリコン変性アクリル樹脂を固形分で１ｇ／ｍ2 以下、望ましくは０.８ｇ／ｍ2以下に塗布、乾燥させて接着層を形成し、この接着層上に、光触媒である酸化チタンと四フツ化エチレン樹脂とを含む溶液を固形分で０.８ｇ／ｍ2 以下になるように上塗り塗布、乾燥させて上塗り層を形成し、防汚性を付与させた構成によって達成できる。 The object of the present invention is to apply a silicon-modified acrylic resin on the surface of a soft vinyl chloride sheet to a solid content of 1 g / m 2 or less, preferably 0.8 g / m 2 or less, and dry to form an adhesive layer. On this adhesive layer, a solution containing titanium oxide, which is a photocatalyst, and tetrafluoroethylene resin is overcoated so as to have a solid content of 0.8 g / m 2 or less, and dried to form an overcoated layer. This can be achieved by a configuration imparted with sex.
また、前記課題は、前記上塗り層を形成するに当たって前記光触媒酸化チタンと四フッ化エチレン樹脂を含有する溶液にバインダーとして二酸化珪素、シリコンアルコキシオリゴマー、アパタイト又はスメクタイトを１〜５０重量％含有させた構成、及び前記シリコン変性アクリル樹脂がシリコン構造を有するシランで変性したものである構成によって達成できる。
In addition, in the formation of the overcoat layer, the problem is that the solution containing the photocatalytic titanium oxide and the tetrafluoroethylene resin contains 1 to 50% by weight of silicon dioxide, silicon alkoxy oligomer, apatite, or smectite as a binder. And the silicon-modified acrylic resin is modified with a silane having a silicon structure.
ここで、前記接着層を形成するシリコン変性アクリル樹脂は、アクリル樹脂がシリコン構造を有するシランによって変性されたもので、このシリコン変性アクリル樹脂は、密着性、透明性、柔軟性に優れ、また、この接着層の上に塗布する上塗り層における光触媒酸化チタンと四フツ化エチレンからなる光触媒効果による分解が進行しない。 Here, the silicon-modified acrylic resin that forms the adhesive layer is one in which the acrylic resin is modified by a silane having a silicon structure, and this silicon-modified acrylic resin is excellent in adhesion, transparency, and flexibility, Decomposition due to the photocatalytic effect consisting of photocatalytic titanium oxide and ethylene tetrafluoride does not proceed in the overcoat layer applied on the adhesive layer.
実使用に際しては当該樹脂を水分散もしくは溶剤希釈した塗料の形態で塗布されるが、塗布方法については特に限定されるものではなく、デッピング、スプレー、ローラー、フロー等々いかなる方法でもよい。
付着量については、光触媒酸化チタンと四フツ化エチレンからなる上塗り塗装後の光触媒効果に基づいて検討した結果、付着量が固形分で１g／ｍ2 を超えると光触媒による分解効果が低減することが判った。この結果から、接着層の付着量としては１ｇ／ｍ2 以下、望ましくは０.８ｇ／ｍ2 以下の非常に薄膜にすることとした。
In actual use, the resin is applied in the form of a paint in which the resin is dispersed in water or diluted with a solvent. However, the application method is not particularly limited, and any method such as dipping, spraying, roller, or flow may be used.
The amount of adhesion was examined based on the photocatalytic effect after top coating consisting of photocatalytic titanium oxide and ethylene tetrafluoride. As a result, if the amount of adhesion exceeds 1 g / m 2 in solids, the decomposition effect by the photocatalyst may be reduced. understood. From this result, the adhesion amount of the adhesive layer was determined to be a very thin film of 1 g / m 2 or less, preferably 0.8 g / m 2 or less.
上塗り層は光触媒酸化チタンと四フツ化エチレンを含有する溶液で、溶媒としては水、溶剤のいずれでもよく、塗布方法に関しても接着層同様いかなる方法でもよい。ここで密着性を改善するためにバインダー成分を添加してもいいが、防汚性確保の点から固形分比で５０重量％以下が好ましい。 The topcoat layer is a solution containing photocatalytic titanium oxide and ethylene tetrafluoride, and the solvent may be either water or a solvent. The coating method may be any method similar to the adhesive layer. Here, a binder component may be added to improve the adhesion, but the solid content ratio is preferably 50% by weight or less from the viewpoint of ensuring antifouling properties.
なお、バインダー成分としては光触媒で分解されずしかも結着力のあるものであればいかなるものでもよく、例えば二酸化ケイ素、シリコーンアルコキシオリゴマー、アパタイト スメクタイト等が挙げられる。また、四フツ化エチレン樹脂の含有量が多くなると密着性が悪化することから、四フツ化エチレン樹脂の含有量は固形分比で２０重量％以下が望ましい。上塗りの付着量については、密着性を検討した結果から上塗り溶液中の固形分が０.５ｇ／ｍ2 以下になるように塗布、乾燥させることで良好な密着性が得られることが判明した。 The binder component is not particularly limited as long as it is not decomposed by a photocatalyst and has a binding force, and examples thereof include silicon dioxide, silicone alkoxy oligomer, apatite smectite and the like. Moreover, since adhesiveness deteriorates when the content of the tetrafluoroethylene resin increases, the content of the tetrafluoroethylene resin is desirably 20% by weight or less in terms of solid content. With respect to the amount of the top coat adhered, it was found from the results of examining the adhesion that good adhesion can be obtained by applying and drying so that the solid content in the top coat solution is 0.5 g / m 2 or less.
接着層の付着量が固形分で０.１〜１ｇ／ｍ2 以下の領域で光触媒による分解効果が良好に発現する原因としては、断定はできないが次のように推定される。１ｇ／ｍ2 を超える厚さになった場合、上塗り塗装後の光触媒酸化チタンの大部分が接着層に埋まったよう形態になり、その結果、光触媒の分解作用が周囲の接着層を分解するために働き、表面付着物への分解が進行しないと考えられる。上塗りの密着性においては固形分が０.０１〜０.５ｇ／ｍ2 以下の領域で良好な理由については、上塗りは凝集力がない成分であるため接着層に接している（もしくは少し埋まっている）極近郊部分しか密着しないためと考えられる。 The reason why the decomposition effect by the photocatalyst can be satisfactorily exhibited in the region where the adhesion amount of the adhesive layer is 0.1 to 1 g / m 2 or less in terms of solid content cannot be determined, but is estimated as follows. When the thickness exceeds 1 g / m 2 , most of the photocatalytic titanium oxide after the top coat is embedded in the adhesive layer, and as a result, the decomposition action of the photocatalyst decomposes the surrounding adhesive layer. It is thought that the decomposition into surface deposits does not proceed. Regarding the adhesiveness of the top coat, the reason why the solid content is good in the region of 0.01 to 0.5 g / m 2 or less is that the top coat is a component having no cohesive force and is in contact with the adhesive layer (or slightly buried). This is thought to be due to the close contact with the very suburbs.
この発明の防汚性アコーデオンドア用軟質塩化ビニルシートは、屋内において使用するために、軽量であり、耐油性を余り問題とせず、空気中の塵埃による油による汚れを早期に分解する量の光触媒で充分である。
本発明、すなわち軟質塩化ビニルシートにシリコン変性アクリル樹脂を固形分で１ｇ／ｍ2以下、望ましくは０.８ｇ／ｍ2以下に塗布、乾燥させた接着層の上に、光触媒酸化チタンおよび四フツ化エチレン樹脂を含む溶液を固形分で０．５ｇ／ｍ2以下になるよう塗布、乾燥させることにより、外覿および柔軟性を損なうことなしに、室内においても継続的な優れた防汚性を有するパーティション用軟質塩化ビニルシートの実現が可能となる。
The antifouling accordion door soft vinyl chloride sheet according to the present invention is a light-weighted photocatalyst for use indoors, which is light in weight, does not have much oil resistance, and quickly decomposes dirt due to dust in the air. Is enough.
On the adhesive layer of the present invention, that is, a silicon-modified acrylic resin applied to a soft vinyl chloride sheet at a solid content of 1 g / m 2 or less, preferably 0.8 g / m 2 or less and dried, By applying and drying a solution containing a hydrogenated ethylene resin to a solid content of 0.5 g / m2 or less, it has excellent antifouling properties even indoors without damaging the outer casing and flexibility. A soft vinyl chloride sheet for partitions can be realized.
この発明の防汚性アコーデオンドア用軟質塩化ビニルシートは、所定の厚さの軟質塩化ビにルシートの表面に接着層を形成し、その表面に上塗り層を形成することにより製造した。この上塗り層の付着量が多くなると光触媒効果が減少することを見出した。
以下に実験例を示す。
The antifouling accordion door soft vinyl chloride sheet of the present invention was produced by forming an adhesive layer on the surface of a sheet of soft vinyl chloride having a predetermined thickness and forming an overcoat layer on the surface. It has been found that the photocatalytic effect decreases as the amount of the overcoat layer deposited increases.
Experimental examples are shown below.
軟質塩化ビニルシートにシリコン変性アクリル樹脂（樹脂固形分中におけるシリコン変性量２０％）のエマルジョンを固形分で０．６ｇ／ｍ2となるようにローラーにて塗布後、自然乾燥させて接着層を形成した。
次に、下記組成の上塗り水溶液を固形分で０．３ｇ／ｍ2となるように前記接着層の上に塗布ローラーにて塗布し、自然乾燥させサンプルを作成した。
After applying an emulsion of silicon-modified acrylic resin (silicon modification amount 20% in the resin solid content) to a soft vinyl chloride sheet with a roller so that the solid content is 0.6 g / m 2 , it is naturally dried to form an adhesive layer. Formed.
Next, an overcoating aqueous solution having the following composition was applied onto the adhesive layer with a coating roller so as to have a solid content of 0.3 g / m 2, and naturally dried to prepare a sample.
（上塗り水溶液の組成）
・光触媒酸化チタン …５重量％、
・四フツ化エチレン樹脂 …５重量％
・二酸化ケイ素 …４重量％
・精製水 …９０重量％
上記サンプルの純水の接触角を測定したところ約８５〜９０度で、光触媒酸化チタンを含有しているにもかかわらず表面自由エネルギーは小さく汚れが付着しにくいことが判かった。
また、水性染料系赤インキ（シヤチハタ工業株式会社製）を上記上塗りの防汚層の表面上に塗布し、表面を赤く染めた後、直射日光下に放置して光触媒の効果を把握した。その結果、約６時間で染色された表面の色素の著しい脱色が確認され光触媒作用の発現が認められた。
(Composition of topcoat aqueous solution)
・ Photocatalytic titanium oxide: 5% by weight,
・ Tetrafluoroethylene resin: 5% by weight
・ Silicon dioxide: 4% by weight
・ Purified water: 90% by weight
When the contact angle of pure water of the above sample was measured, it was about 85 to 90 degrees, and it was found that the surface free energy was small and dirt was hardly attached despite containing photocatalytic titanium oxide.
Further, aqueous dye-based red ink (manufactured by Shiachihata Kogyo Co., Ltd.) was applied on the surface of the above-mentioned top antifouling layer, dyed the surface red, and then left in direct sunlight to grasp the effect of the photocatalyst. As a result, remarkable decolorization of the dye on the surface dyed in about 6 hours was confirmed, and the expression of photocatalysis was recognized.
さらに耐候性（耐紫外線）に関して、本発明を処理していない軟質塩化ビニルシートにおいてその印刷面が著しく退色するメタルウエザー・８０時間の試験を実施した。
その結果、未処理品よりも悪化することなく、むしろ色あせは軽度であった。すなわち光触媒による劣化はなく、逆に光触媒による紫外線吸収が耐候性に良い影響を与えたものと考えられる。
Furthermore, regarding weather resistance (ultraviolet light resistance), a test of a metal weather and an 80-hour test in which the printed surface of the soft vinyl chloride sheet not treated according to the present invention is significantly discolored was performed.
As a result, the fading was milder without deterioration than the untreated product. That is, there is no deterioration due to the photocatalyst, and conversely, it is considered that the ultraviolet absorption by the photocatalyst has a good influence on the weather resistance.
〔比較例1〕
前記実施例において、接着層のシリコン変性アクリル樹脂の付着量を固形分で２ｇ／ｍ2となるようにした以外は全く同様の試験サンプルを作製して、その表面を水性染料系赤インキ（シヤチハタ工業株式会社製）を表面上に塗布し赤く染めた後、直射日光下に放置し光触媒の効果を把握した。その結果、色素の著しい脱色が確認されるのに約２日を要した。
(Comparative Example 1)
In the above examples, exactly the same test sample was prepared except that the adhesion amount of the silicon-modified acrylic resin in the adhesive layer was 2 g / m 2 in solid content, and the surface was coated with aqueous dye-based red ink (Shiyahata). Kogyo Co., Ltd.) was applied on the surface and dyed red, and then left under direct sunlight to grasp the effect of the photocatalyst. As a result, it took about 2 days for the significant decolorization of the pigment to be confirmed.
〔比較例２〕
実施例において、上塗り層の付着量を固形分換算で１ｇ／ｍ2となるようにした以外は全く同様の試験サンプルを作製したところ、上塗り層が粉状に脱落し密着性のないことが分かった。
[Comparative Example 2]
In the examples, when the same test sample was prepared except that the amount of the overcoat layer deposited was 1 g / m 2 in terms of solid content, it was found that the overcoat layer fell off in powder form and there was no adhesion. It was.
この発明の防汚性アコーデオンドア用軟質塩化ビニルシートは、室内の間仕切り用のシートとして安価に使用することができる。例えば、開閉自在の窓側の内側に使用するアコーデオンカーテンともいわれるものにも使用することができる。 The soft vinyl chloride sheet for an antifouling accordion door of the present invention can be used at a low cost as a room partition sheet. For example, it can be used for what is also called an accordion curtain used inside the openable window side.
Claims (4)
4. The antifouling accordion door soft according to claim 1, wherein the silicon-modified acrylic resin is modified with silane having a silicon structure. Vinyl chloride sea bream.
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