JP6343637B2 - Membrane structure - Google Patents
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- JP6343637B2 JP6343637B2 JP2016137402A JP2016137402A JP6343637B2 JP 6343637 B2 JP6343637 B2 JP 6343637B2 JP 2016137402 A JP2016137402 A JP 2016137402A JP 2016137402 A JP2016137402 A JP 2016137402A JP 6343637 B2 JP6343637 B2 JP 6343637B2
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- 239000012528 membrane Substances 0.000 title claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 114
- 239000010410 layer Substances 0.000 claims description 110
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- 239000002131 composite material Substances 0.000 claims description 46
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 35
- 239000011241 protective layer Substances 0.000 claims description 33
- 229920006026 co-polymeric resin Polymers 0.000 claims description 22
- 239000002759 woven fabric Substances 0.000 claims description 19
- 239000000835 fiber Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 9
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 claims description 7
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- 230000009969 flowable effect Effects 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 32
- 239000010419 fine particle Substances 0.000 description 27
- 239000006185 dispersion Substances 0.000 description 22
- 238000001035 drying Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 7
- HRPWYKJYMAGADJ-UHFFFAOYSA-N C=C.FC(C(F)=C(F)F)(F)F.F.F.F.F Chemical group C=C.FC(C(F)=C(F)F)(F)F.F.F.F.F HRPWYKJYMAGADJ-UHFFFAOYSA-N 0.000 description 6
- 239000005084 Strontium aluminate Substances 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910052692 Dysprosium Inorganic materials 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 229910003668 SrAl Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- WQNTXSXCXGWOBT-UHFFFAOYSA-N C=C.C=C.F.F.F.F Chemical group C=C.C=C.F.F.F.F WQNTXSXCXGWOBT-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- OFHQVNFSKOBBGG-UHFFFAOYSA-N 1,2-difluoropropane Chemical compound CC(F)CF OFHQVNFSKOBBGG-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Laminated Bodies (AREA)
- Luminescent Compositions (AREA)
Description
本発明は、蛍光複合体に関する。 The present invention relates to a fluorescent complex.
中大型テント等の膜構造物において、消灯時及び突発的な停電時に、電力を必要とすることなく、膜材自体が発光して、一時的に照明の代わりになり、混乱を避けると共に、大衆の目印、道標となることが可能な光天井用膜材の開発が行われている。 In membrane structures such as medium- and large-sized tents, the film material itself emits light without requiring power when the lights are turned off or during a sudden power failure, temporarily replacing lighting, avoiding confusion, Development of membrane materials for optical ceilings that can serve as landmarks and signposts.
例えば特許文献１は、繊維材料より形成された芯体と、その少なくとも１面に形成された白色樹脂層と、白色樹脂層の上に形成された蓄光性蛍光樹脂層と、蓄光性蛍光樹脂層の上に形成された光触媒層とを有する蓄光性蛍光膜材料を開示している。特許文献１の蓄光性蛍光膜材料のＪＩＳ Ｋ７１０５に規定される全光線透過率は５０％以上である。また、蓄光性蛍光樹脂層には、塩化ビニル樹脂のような熱可塑性樹脂が用いられている。 For example, Patent Document 1 discloses a core formed of a fiber material, a white resin layer formed on at least one surface thereof, a phosphorescent fluorescent resin layer formed on the white resin layer, and a phosphorescent fluorescent resin layer. A phosphorescent phosphor film material having a photocatalyst layer formed thereon is disclosed. The total light transmittance defined in JIS K7105 of the phosphorescent phosphor film material of Patent Document 1 is 50% or more. In addition, a thermoplastic resin such as vinyl chloride resin is used for the phosphorescent fluorescent resin layer.
一方、特許文献２は、ガラス繊維糸条、シリカ繊維糸条及びこれらの混用繊維糸条からなる繊維織物の表片面上に、蓄光性蛍光体物質を２０〜６０質量％含有する蓄光蛍光性樹脂層を設け、可視光透過率（ＪＩＳ Ｚ８７２２）が２０〜６０％である積層体とすることで、特に、コーンカロリーメーター試験（ＡＳＴＭ−Ｅ１３５４）に適合する不燃性の光天井用膜材を得ることを開示している。また、特許文献２の蓄光蛍光性樹脂層には、塩化ビニル樹脂のような熱可塑性樹脂が用いられている。 On the other hand, Patent Document 2 discloses a phosphorescent fluorescent resin containing 20 to 60% by mass of a phosphorescent phosphor substance on the surface of a fiber fabric composed of glass fiber yarns, silica fiber yarns, and mixed fiber yarns thereof. By providing a layer and providing a laminate having a visible light transmittance (JIS Z8722) of 20 to 60%, in particular, a nonflammable optical ceiling film material suitable for the cone calorimeter test (ASTM-E1354) is obtained. It is disclosed. Further, a thermoplastic resin such as vinyl chloride resin is used for the phosphorescent fluorescent resin layer of Patent Document 2.
光天井用膜材には、耐候性をさらに改善することが要望されている。 Optical ceiling membrane materials are required to further improve the weather resistance.
実施形態の目的は、耐候性に優れた蛍光複合体を提供することである。 An object of the embodiment is to provide a fluorescent composite having excellent weather resistance.
実施形態によれば、耐熱性織布と、前記耐熱性織布の両面に形成されたフッ素樹脂層とを含む芯体と、
蛍光体及び四ふっ化エチレン樹脂を含む蛍光体層とを含むことを特徴とする蛍光複合体を含んだ膜構造物が提供される。
According to the embodiment, a core including a heat resistant woven fabric and a fluororesin layer formed on both surfaces of the heat resistant woven fabric,
There is provided a film structure including a fluorescent composite comprising a fluorescent material and a fluorescent material layer containing a tetrafluoroethylene resin.
実施形態によれば、耐候性に優れた蛍光複合体を提供することができる。 According to the embodiment, a fluorescent composite having excellent weather resistance can be provided.
以下、本発明の実施の形態について、詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
実施形態によれば、芯体と、蛍光体層とを含む蛍光複合体が提供される。芯体は、耐熱性織布と、耐熱性織布の両面に形成されたフッ素樹脂層とを含む。蛍光体層は、蛍光体粒子及び四ふっ化エチレン樹脂（ＰＴＦＥ）を含む。本発明者らは、蛍光体粒子に塩化ビニル樹脂を混合させると、優れた透明性が得られるものの、水分により蛍光体粒子が劣化しやすく、一方、塩化ビニル樹脂の代りにＰＴＦＥを蛍光体粒子に混合させると、ＰＴＦＥが蛍光体粒子を被覆し、蛍光体粒子と水との接触を防止するため、蛍光体層の耐水性が高められ、蛍光体粒子の加水分解が抑制されることを究明したのである。また、この蛍光体層は、芯体のフッ素樹脂層との相溶融性に優れるため、蛍光複合体の一体化強度を高めることができる。以上のことから、実施形態によれば、蛍光複合体の耐候性を向上することができる。 According to the embodiment, a fluorescent composite including a core and a phosphor layer is provided. The core includes a heat resistant woven fabric and a fluororesin layer formed on both surfaces of the heat resistant woven fabric. The phosphor layer includes phosphor particles and tetrafluoroethylene resin (PTFE). When the present inventors have mixed vinyl chloride resin with phosphor particles, although excellent transparency is obtained, phosphor particles are easily deteriorated by moisture, while PTFE is used instead of vinyl chloride resin as phosphor particles. When mixed with PTFE, the PTFE coats the phosphor particles and prevents contact between the phosphor particles and water, so that the water resistance of the phosphor layer is increased and the hydrolysis of the phosphor particles is suppressed. It was. Moreover, since this fluorescent substance layer is excellent in a phase meltability with the fluororesin layer of a core, the integrated intensity | strength of a fluorescent composite can be raised. From the above, according to the embodiment, the weather resistance of the fluorescent composite can be improved.
実施形態の蛍光複合体を図面を参照して説明する。図１に示すように、実施形態の蛍光複合体は、芯体１と、芯体１の一方の面に形成された蛍光体層２と、芯体１の他方の面に形成された第１の保護層３1と、蛍光体層２上に形成された第２の保護層３2とを有する。芯体１は、耐熱性織布１ａと、耐熱性織布１ａの両面に形成されたフッ素樹脂層１ｂとを含む。また、蛍光体層２は、蛍光体及び四ふっ化エチレン樹脂を含む。蛍光複合体を構成するこれらの部材について説明する。 The fluorescent complex of the embodiment will be described with reference to the drawings. As shown in FIG. 1, the fluorescent composite according to the embodiment includes a core 1, a phosphor layer 2 formed on one surface of the core 1, and a first formed on the other surface of the core 1. Protective layer 3 1, and second protective layer 3 2 formed on phosphor layer 2. The core 1 includes a heat resistant woven fabric 1a and a fluororesin layer 1b formed on both surfaces of the heat resistant woven fabric 1a. Moreover, the fluorescent substance layer 2 contains fluorescent substance and tetrafluoroethylene resin. These members constituting the fluorescent composite will be described.
１）芯体
耐熱性織布の例には、ガラス繊維、炭素繊維、セラミックス繊維、アラミド繊維及び金属繊維よりなる群から選択される少なくとも一種類を含むものが挙げられる。これらの繊維は長繊維であることが望ましい。ここで、長繊維は、紡績せずに糸として利用可能なものである。耐熱性織布として好ましいのは、ガラス繊維を含むものである。
1) Core body Examples of the heat-resistant woven fabric include those containing at least one selected from the group consisting of glass fiber, carbon fiber, ceramic fiber, aramid fiber and metal fiber. These fibers are preferably long fibers. Here, the long fiber can be used as a yarn without spinning. Preferred as the heat resistant woven fabric is one containing glass fibers.
耐熱性織布の織組織は、朱子織、平織、バスケット織、綾織または変形綾織にすることができる。 The woven structure of the heat-resistant woven fabric can be satin weave, plain weave, basket weave, twill or modified twill.
フッ素樹脂層に含まれるフッ素樹脂の例には、溶融時に流動性を示さない四ふっ化エチレン樹脂（ＰＴＦＥ）、並びに、溶融流動性ふっ素樹脂（例えば、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂（ＦＥＰ））が含まれる。使用するふっ素樹脂の種類は、１種または２種以上にすることができる。ＰＴＦＥを含むフッ素樹脂層は、撥水性を有するため、蛍光体粒子への水分の浸入を抑制することができると共に、蛍光体層との相溶融性を向上させることができる。 Examples of the fluororesin contained in the fluororesin layer include a tetrafluoroethylene resin (PTFE) that does not exhibit fluidity when melted, and a melt flowable fluororesin (for example, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin). (PFA), ethylene tetrafluoride-hexafluoropropylene copolymer resin (FEP)). The kind of fluororesin to be used can be 1 type or 2 types or more. Since the fluororesin layer containing PTFE has water repellency, it can suppress the intrusion of moisture into the phosphor particles, and can improve the phase meltability with the phosphor layer.
フッ素樹脂層は、例えば、以下の方法で形成される。まず、水を溶媒とし、粒子径０．１〜０．４μｍのフッ素樹脂粒子及び懸濁安定剤（例えば、陰イオン界面活性剤または非イオン界面活性剤）を含む水系懸濁液を耐熱性織布の両面に含浸によって塗布し、雰囲気温度が１００℃以上２００℃以下で乾燥させた後、雰囲気温度が３３０℃以上４００℃以下で焼成する。この塗布、乾燥及び焼成を複数回繰り返すことにより、フッ素樹脂層を得る。 For example, the fluororesin layer is formed by the following method. First, an aqueous suspension containing fluororesin particles having a particle size of 0.1 to 0.4 μm and a suspension stabilizer (for example, an anionic surfactant or a nonionic surfactant) is used as a solvent. After being applied to both sides of the cloth by impregnation and drying at an ambient temperature of 100 ° C. or higher and 200 ° C. or lower, firing is performed at an ambient temperature of 330 ° C. or higher and 400 ° C. or lower. By repeating this coating, drying and baking a plurality of times, a fluororesin layer is obtained.
２）蛍光体層
蛍光体は、特に限定されるものではないが、例えば、蓄光性蛍光体（長残光性蛍光体）等を挙げることができる。蓄光性蛍光体の種類は、例えば、硫化物、酸硫化物、酸化物（例えば、アルミン酸塩）等を挙げることができる。硫化物の例には、ＣａＳｒＳ：Ｂｉ（発光色は青）、ＺｎＳ：Ｃｕ（発光色は黄緑）、ＺｎＳ：Ｃｕ，Ｃｏ（発光色は黄緑）、ＣａＳ：Ｅｕ，Ｔｍ（発光色は赤）等が含まれる。酸硫化物の例には、Ｙ2Ｏ2Ｓ：Ｅｕ，Ｍｇ，Ｔｉ（発光色は黄褐又は赤）等が含まれる。アルミン酸塩の例には、ＣａＡｌ2Ｏ4：Ｅｕ，Ｎｄ（発光色は紫青）、Ｓｒ4Ａｌ14Ｏ25：Ｅｕ，Ｄｙ（発光色は青緑）、ＳｒＡｌ2Ｏ4：Ｅｕ，Ｄｙ（発光色は黄緑）、ＳｒＡｌ2Ｏ4：Ｅｕ（発光色は黄緑）、Ｍ1-XＡｌ2Ｏ4-X（Ｍは、Ｃａ、Ｓｒ及びＢａからなる群から選ばれる少なくとも１つ以上の金属元素からなる化合物を母結晶にしたものが用いられ、Ｘが−０．３３≦Ｘ≦０．６０の範囲にあり、賦活剤としてＥｕを、Ｍで表す金属元素に対するモル％で０．００１％以上１０％以下添加し、共賦活剤としてＮｄ、Ｓｍ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ及びＬｕからなる群の少なくとも１つ以上の元素を、Ｍで表わす金属元素に対するモル％で０．００１％以上１０％以下添加したもの）で表わされる組成の化合物（発光色は緑）等が含まれる。使用する蛍光体の種類は、１種類または２種類以上にすることができる。Ｍ1-XＡｌ2Ｏ4-Xのような酸化物蛍光体の粒子は、ＰＴＦＥ水系懸濁液に対する分散性に優れるため、蛍光体層中に均一分散することが可能である。
2) Phosphor layer The phosphor is not particularly limited, and examples thereof include a phosphorescent phosphor (long afterglow phosphor). Examples of the phosphorescent phosphor include a sulfide, an oxysulfide, and an oxide (for example, aluminate). Examples of sulfides include CaSrS: Bi (light emission color is blue), ZnS: Cu (light emission color is yellow-green), ZnS: Cu, Co (light emission color is yellow-green), CaS: Eu, Tm (light emission color is Red) etc. are included. Examples of oxysulfides include Y 2 O 2 S: Eu, Mg, Ti (the emission color is yellow brown or red). Examples of aluminates include CaAl 2 O 4 : Eu, Nd (the emission color is purple-blue), Sr 4 Al 14 O 25 : Eu, Dy (the emission color is blue-green), SrAl 2 O 4 : Eu, Dy (The emission color is yellow-green), SrAl 2 O 4 : Eu (the emission color is yellow-green), M 1-X Al 2 O 4-X (M is at least one selected from the group consisting of Ca, Sr and Ba) A compound composed of the above metal element as a mother crystal is used, X is in the range of −0.33 ≦ X ≦ 0.60, Eu as an activator is 0% by mol% with respect to the metal element represented by M. 0.001% or more and 10% or less, and at least one element selected from the group consisting of Nd, Sm, Dy, Ho, Er, Tm, Yb and Lu as a co-activator in mol% with respect to the metal element represented by M Compound having a composition represented by 0.001% or more and 10% or less added (light emission) It is included in green), and the like. The kind of fluorescent substance to be used can be made into one type or two types or more. Oxide phosphor particles such as M 1-X Al 2 O 4-X are excellent in dispersibility with respect to the PTFE aqueous suspension, and therefore can be uniformly dispersed in the phosphor layer.
蛍光体層中の蛍光体粒子の含有量は１０重量％以上２５重量％以下の範囲にすることが望ましい。蛍光体粒子の含有量を１０重量％以上にすることによって、十分な輝度を得ることができる。また、蛍光体粒子の含有量を２５重量％以下にすることによって、屈曲による蛍光体粒子近傍における応力集中を低減させることができ、屈曲強度の低下を抑制することができるため、蛍光複合体に折り曲げ等の変形を加えた際に蛍光複合体にクラック等が生じるのを回避することができる。 The content of the phosphor particles in the phosphor layer is desirably in the range of 10 wt% to 25 wt%. Sufficient luminance can be obtained by setting the content of the phosphor particles to 10% by weight or more. In addition, by making the content of the phosphor particles 25% by weight or less, stress concentration in the vicinity of the phosphor particles due to bending can be reduced, and a decrease in bending strength can be suppressed. It is possible to avoid the occurrence of cracks or the like in the fluorescent composite when deformation such as bending is applied.
蛍光体層は、蛍光体粒子及び四ふっ化エチレン樹脂以外の成分を含んでいても良い。蛍光体層が蛍光体粒子及び四ふっ化エチレン樹脂からなる場合、蛍光体層中の四ふっ化エチレン樹脂の含有量は７５重量％以上９０重量％以下の範囲であることが望ましい。 The phosphor layer may contain components other than the phosphor particles and the tetrafluoroethylene resin. When the phosphor layer is composed of phosphor particles and ethylene tetrafluoride resin, the content of the ethylene tetrafluoride resin in the phosphor layer is preferably in the range of 75 wt% to 90 wt%.
蛍光体層は、例えば、以下の方法で形成される。まず、水を分散液とし、ＰＴＦＥ粒子及び懸濁安定剤（例えば、陰イオン界面活性剤または非イオン界面活性剤）を含む水系懸濁液に蛍光体の粒子を分散させる。得られた分散液を基材（例えば、芯体のフッ素樹脂層、保護層）の少なくとも片面に含浸によって塗布し、雰囲気温度が１００℃以上２００℃以下で乾燥させた後、雰囲気温度が３３０℃以上４００℃以下で焼成する。この塗布、乾燥及び焼成を複数回繰り返すことにより、蛍光体層を得る。この方法によると、蛍光体粒子が均一に分散された懸濁液を基材に塗布し、乾燥し、焼成する工程を繰り返すことにより蛍光体層が得られるため、懸濁液中の蛍光体粒子の分散性をほぼそのまま維持した蛍光体層を実現することができ、蛍光体層中の蛍光体粒子含有量が少量でも十分な輝度を得ることができる。その結果、屈曲による蛍光体粒子近傍における応力集中を低減させることができ、屈曲強度の低下を抑制することができるため、蛍光複合体に折り曲げ等の変形を加えた際に蛍光複合体にクラック等が生じるのを避けることができる。特に、Ｍ1-XＡｌ2Ｏ4-Xのような酸化物蛍光体の粒子は、ＰＴＦＥ水系懸濁液に対する分散性に優れるため、懸濁液の塗布・乾燥・焼成により、酸化物蛍光体粒子が均一分散された蛍光体層を実現することができる。 The phosphor layer is formed by the following method, for example. First, water is used as a dispersion liquid, and phosphor particles are dispersed in an aqueous suspension containing PTFE particles and a suspension stabilizer (for example, an anionic surfactant or a nonionic surfactant). The obtained dispersion is applied by impregnation on at least one surface of a substrate (for example, a fluororesin layer or a protective layer of a core), dried at an ambient temperature of 100 ° C. or higher and 200 ° C. or lower, and then the ambient temperature is 330 ° C. Firing is performed at 400 ° C. or lower. A phosphor layer is obtained by repeating this coating, drying, and baking a plurality of times. According to this method, a phosphor layer is obtained by repeating the steps of applying a suspension in which phosphor particles are uniformly dispersed to a substrate, drying, and firing. Thus, a phosphor layer in which the dispersibility of the phosphor layer is maintained as it is can be realized, and sufficient luminance can be obtained even if the phosphor particle content in the phosphor layer is small. As a result, stress concentration in the vicinity of the phosphor particles due to bending can be reduced, and a decrease in bending strength can be suppressed. Therefore, when the fluorescent composite is subjected to deformation such as bending, cracks etc. Can be avoided. In particular, particles of oxide phosphors such as M 1-X Al 2 O 4-X have excellent dispersibility in PTFE aqueous suspensions. A phosphor layer in which particles are uniformly dispersed can be realized.
蛍光体粒子の平均粒径は、大きい方が残光輝度が高くなるものの、懸濁液中での蛍光体粒子の沈降が起き易く、蛍光体層の機械的強度が低くなる傾向がある。一方、蛍光体粒子の平均粒径は、小さい方が、懸濁液中での分散性及び蛍光体層の機械的強度に優れるものの、残光輝度が低くなる傾向がある。 The larger the average particle diameter of the phosphor particles, the higher the afterglow luminance. However, the phosphor particles tend to settle in the suspension, and the mechanical strength of the phosphor layer tends to decrease. On the other hand, the smaller the average particle diameter of the phosphor particles, the better the dispersibility in the suspension and the mechanical strength of the phosphor layer, but the afterglow brightness tends to be low.
３）保護層
保護層は、溶融流動性フッ素樹脂を含有する。蛍光体層は、後述する通り、ＰＴＦＥ水系懸濁液を基材に塗布し、乾燥し、焼成する工程を繰り返すことにより得られるため、焼結体の一種である。このため、焼結体のピンホールを通して内部に水が浸入し、蛍光体粒子が加水分解する恐れがある。保護層は、溶融流動性フッ素樹脂を含むため、緻密性の高い成型体であることから、蛍光体層への水分の浸入を抑制することが可能である。保護層の配置は、特に限定されるものではないが、蛍光体層の少なくとも一方の面に配置するか、最外層に位置させることが望ましい。これにより、蛍光複合体の耐候性をより改善することができる。
3) Protective layer The protective layer contains a melt-flowable fluororesin. As will be described later, the phosphor layer is a kind of sintered body because it is obtained by repeating the steps of applying a PTFE aqueous suspension to a substrate, drying, and firing. For this reason, water may enter the inside through the pinhole of the sintered body, and the phosphor particles may be hydrolyzed. Since the protective layer contains a melt-flowable fluororesin, it is a highly dense molded body, and therefore it is possible to suppress the intrusion of moisture into the phosphor layer. The arrangement of the protective layer is not particularly limited, but it is desirable that the protective layer is arranged on at least one surface of the phosphor layer or positioned on the outermost layer. Thereby, the weather resistance of the fluorescent composite can be further improved.
溶融流動性フッ素樹脂には、四ふっ化エチレン樹脂（ＰＴＦＥ）以外のフッ素樹脂を使用することができる。好ましい例には、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂（ＦＥＰ）、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）、ポリふっ化ビニリデン（ＰＶＤＦ）及びエチレン四ふっ化エチレン共重合樹脂（ＥＴＦＥ）が含まれる。ＦＥＰ及びＰＦＡは、ＰＴＦＥとの相溶融性に優れており、また、ＦＥＰは蛍光複合体の製造コストを低く抑えることができる。使用する溶融流動性フッ素樹脂の種類は、１種類又は２種類以上にすることができる。 As the melt-flowable fluororesin, a fluororesin other than tetrafluoroethylene resin (PTFE) can be used. Preferred examples include ethylene tetrafluoride-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA), polyvinylidene fluoride (PVDF), and ethylene tetrafluoride ethylene copolymer. Polymerized resin (ETFE) is included. FEP and PFA are excellent in phase meltability with PTFE, and FEP can keep the production cost of the fluorescent composite low. The type of the melt flowable fluororesin used can be one type or two or more types.
保護層は、例えば、以下の方法で形成される。まず、溶融流動性フッ素樹脂及び懸濁安定剤（例えば、陰イオン界面活性剤または非イオン界面活性剤）を含む水系懸濁液を基材（例えば、芯体、蛍光体層）の少なくとも片面に含浸によって塗布し、雰囲気温度が１００℃以上２００℃以下で乾燥させた後、雰囲気温度が３００℃以上４００℃以下で焼成する。この塗布、乾燥及び焼成を複数回繰り返すことにより、保護層を得る。 The protective layer is formed by the following method, for example. First, an aqueous suspension containing a melt-flowable fluororesin and a suspension stabilizer (for example, an anionic surfactant or a nonionic surfactant) is provided on at least one surface of a substrate (for example, a core or a phosphor layer). After applying by impregnation and drying at an ambient temperature of 100 ° C. to 200 ° C., firing is performed at an ambient temperature of 300 ° C. to 400 ° C. A protective layer is obtained by repeating this coating, drying and baking a plurality of times.
蛍光複合体の積層構造は、図１に示すものに限られず、蛍光体層と芯体とを備えるものであれば良い。具体例を図２〜図６に示す。 The laminated structure of the fluorescent composite is not limited to that shown in FIG. 1, and any structure including a fluorescent layer and a core may be used. Specific examples are shown in FIGS.
図２に例示されるように、第１の保護層３1を最外層に配置する代りに、蛍光体層２と芯体１のフッ素樹脂層１ｂの間に配置しても良い。また、図３に例示されるように、保護層を三層設け、蛍光複合体の両方の最外層に第１，第２の保護層３1，３2を配置し、かつ蛍光体層２と芯体１のフッ素樹脂層１ｂの間に第３の保護層３3を配置しても良い。 As illustrated in FIG. 2, instead of arranging the first protective layer 3 1 to the outermost layer may be disposed between the fluororesin layer 1b of the phosphor layer 2 and the core 1. Further, as illustrated in FIG. 3, three protective layers are provided, the first and second protective layers 3 1 and 3 2 are disposed on the outermost layers of both of the fluorescent composites, and the phosphor layer 2 and between the fluororesin layer 1b of the core body 1 may be a third protective layer 3 3 is arranged.
蛍光体層の層数は一層に限られず、例えば二層以上にすることができる。この例を図４〜図６に示す。図４に示すように、芯体１の両方のフッ素樹脂層１ｂに第１，第２の蛍光体層２1，２2を積層し、さらにその外側に第１，第２の保護層３1，３2を配置しても良い。また、図５に示すように、第１の蛍光体層２1と芯体１のフッ素樹脂層１ｂの間に第３の保護層３3を配置するか、図６に示すように、第２の蛍光体層２2と芯体１のフッ素樹脂層１ｂの間に第３の保護層３3を配置しても良い。 The number of phosphor layers is not limited to one, and can be two or more, for example. Examples of this are shown in FIGS. As shown in FIG. 4, first and second phosphor layers 2 1 and 2 2 are laminated on both fluororesin layers 1b of the core body 1 , and the first and second protective layers 3 1 are further formed on the outer sides thereof. , 3 2 may be arranged. Further, as shown in FIG. 5, third or placing a protective layer 3 3 between the first phosphor layer 2 1 and the core 1 of the fluororesin layer 1b, as shown in FIG. 6, the second the third protective layer 3 3 may be disposed between the phosphor layer 2 2 and core 1 of the fluororesin layer 1b.
蛍光複合体には、芯体、蛍光体層、保護層以外の層（例えば、光拡散層、防汚層）を含むことを許容する。 The fluorescent composite is allowed to include layers other than the core, the phosphor layer, and the protective layer (for example, a light diffusion layer and an antifouling layer).
蛍光複合体は、ＪＩＳ Ｚ８７２２に規定される可視光透過率が２０％未満である。 The fluorescent composite has a visible light transmittance of less than 20% as defined in JIS Z8722.
蛍光複合体の用途には、中大型テント等の膜構造物があり、例えば、ドーム型競技場における防災時の避難誘導等の光天井用膜材が挙げられる。装飾等のデザイン性を重視するコンサートホール、多目的ホール等で蛍光複合体を使用する場合、デザイン性を考慮し、蓄光性蛍光体（長残光性蛍光体）以外の蛍光体（例えば、ブラックライトを照射することによって発光するもの）を蛍光複合体に設けることができる。また、蓄光性蛍光体（長残光性蛍光体）を使用する場合、残光時間を調節する機能を蛍光複合体に設けることができる。 Applications of the fluorescent composite include membrane structures such as medium and large tents, and examples thereof include optical ceiling membrane materials for evacuation guidance during disaster prevention in a dome-type stadium. When using fluorescent composites in concert halls and multipurpose halls that place emphasis on design such as decoration, phosphors other than phosphorescent phosphors (long-afterglow phosphors) (for example, black light) Can be provided in the fluorescent composite. In addition, when a phosphorescent phosphor (long afterglow phosphor) is used, a function for adjusting the afterglow time can be provided in the fluorescent composite.
以下、実施例を図面を参照して説明する。 Hereinafter, embodiments will be described with reference to the drawings.
（実施例１）
耐熱性織布として厚さが４５０μｍで、織組織が平織のガラス繊維織物（日東紡績製）を用い、ガラス繊維織物の両面に、四ふっ化エチレン樹脂微粒子分が６０重量％、非イオン界面活性剤が６重量％及び水が３４重量％からなる四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）を含浸することによって塗布し、雰囲気温度を１００℃に調整した密封炉で５分乾燥させ、水分を飛ばしたのち、雰囲気温度を３６０℃に調整した密封炉にて５分焼成した。この工程を複数回繰り返すことによって、両面の厚さの合計が１３０μｍの四ふっ化エチレン樹脂層を得ることにより、芯体を得た。
Example 1
A glass fiber woven fabric (manufactured by Nitto Boseki) with a thickness of 450 μm as a heat-resistant woven fabric and a woven structure made by Nitto Boseki. It was applied by impregnating with a tetrafluoroethylene resin fine particle aqueous dispersion (made by Daikin Industries) consisting of 6% by weight of the agent and 34% by weight of water, and dried for 5 minutes in a sealed oven with the atmospheric temperature adjusted to 100 ° C. After the moisture was blown off, the substrate was baked for 5 minutes in a sealed furnace whose atmospheric temperature was adjusted to 360 ° C. By repeating this step a plurality of times, a core body was obtained by obtaining an ethylene tetrafluoride ethylene resin layer having a total thickness of both surfaces of 130 μm.
次に、四ふっ化エチレン樹脂微粒子分が６０重量％、非イオン界面活性剤が６重量％及び水が３４重量％からなる四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）１．５８ｋｇに対して、ＳｒＡｌ2Ｏ4：Ｅｕ，Ｄｙで表されるアルミン酸ストロンチウム系蓄光性蛍光体（根本特殊化学製）粉末を５０ｇ混合攪拌して蓄光蛍光体粉末が混合された四ふっ化エチレン樹脂微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、四ふっ化エチレン樹脂微粒子分９５重量％に対して５重量％となる。次に、上記四ふっ化エチレン樹脂層と同じ製造条件の塗布、乾燥及び焼成によって、芯体の一方の四ふっ化エチレン樹脂層上に厚さ２００μｍの蛍光体層を作製した。 Next, 1.58 kg of a tetrafluoroethylene resin fine particle aqueous dispersion (made by Daikin Industries) consisting of 60% by weight of the tetrafluoroethylene resin fine particle, 6% by weight of the nonionic surfactant and 34% by weight of water. On the other hand, 50 g of strontium aluminate phosphorescent phosphor (manufactured by Nemoto Special Chemical) represented by SrAl 2 O 4 : Eu, Dy is mixed and stirred, and the tetrafluoroethylene resin fine particles are mixed with phosphorescent phosphor powder. An aqueous dispersion was prepared. The mixing ratio of the phosphorescent phosphor powder at this time is 5% by weight with respect to 95% by weight of the tetrafluoroethylene resin fine particles. Next, a phosphor layer having a thickness of 200 μm was formed on one of the tetrafluoroethylene resin layers of the core by applying, drying and firing under the same production conditions as the above-described tetrafluoroethylene resin layer.
さらに、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子分５４重量％、非イオン界面活性剤が１５．５重量％及び水が４０．５重量％からなる四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造条件の塗布、乾燥及び焼成によって、蛍光体層及び芯体の他方の四ふっ化エチレン樹脂層上に厚さ２０μｍの保護層（最外層）を形成した。得られた蛍光複合体は、図１に示す積層構造を有するものであった。得られた蛍光複合体のＪＩＳ Ｚ８７２２に規定される可視光透過率は２０％未満であった。 Furthermore, ethylene tetrafluoride-hexafluoropropylene copolymer resin 54% by weight fine particle, nonionic surfactant 15.5% by weight and water 40.5% by weight ethylene tetrafluoride-hexafluoropropylene A protective layer having a thickness of 20 μm is formed on the phosphor layer and the other tetrafluoroethylene resin layer of the core body by coating, drying and firing under the same production conditions as above using a copolymer resin fine particle aqueous dispersion (manufactured by Dupont). (Outermost layer) was formed. The obtained fluorescent composite had the laminated structure shown in FIG. The visible light transmittance defined in JIS Z8722 of the obtained fluorescent composite was less than 20%.
（実施例２）
実施例１と同様な方法で芯体を作製した。
(Example 2)
A core body was produced in the same manner as in Example 1.
次に、実施例１と同様な組成の四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）１．５ｋｇに対して、実施例１と同様な組成のアルミン酸ストロンチウム系蓄光性蛍光体粉末を１００ｇ混合攪拌して蓄光蛍光体粉末が混合された四ふっ化エチレン樹脂微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、四ふっ化エチレン樹脂微粒子分９０重量％に対して１０重量％となる。次に、実施例１と同じ製造条件の塗布、乾燥及び焼成によって、芯体の一方の四ふっ化エチレン樹脂層上に厚さ２００μｍの蛍光体層を得た。 Next, strontium aluminate-based phosphorescent phosphor powder having the same composition as that of Example 1 was applied to 1.5 kg of an ethylene tetrafluoride resin fine particle aqueous dispersion (manufactured by Daikin Industries) having the same composition as that of Example 1. 100 g of the mixture was mixed and stirred to prepare an aqueous dispersion of ethylene tetrafluoride resin fine particles mixed with phosphorescent phosphor powder. The mixing ratio of the phosphorescent phosphor powder at this time is 10% by weight with respect to 90% by weight of the tetrafluoroethylene resin fine particles. Next, a phosphor layer having a thickness of 200 μm was obtained on one of the tetrafluoroethylene resin layers of the core by application, drying and firing under the same production conditions as in Example 1.
さらに、実施例１と同様な組成の四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造条件の塗布、乾燥及び焼成によって、蛍光体層及び芯体の他方の四ふっ化エチレン樹脂層上に厚さ２０μｍの保護層（最外層）を得た。得られた蛍光複合体は、図１に示す積層構造を有するものであった。得られた蛍光複合体のＪＩＳ Ｚ８７２２に規定される可視光透過率は２０％未満であった。 Further, by using a tetrafluoroethylene-hexafluoropropylene copolymer resin fine particle aqueous dispersion (manufactured by Dupont) having the same composition as in Example 1, the phosphor layer and A protective layer (outermost layer) having a thickness of 20 μm was obtained on the other tetrafluoroethylene resin layer of the core. The obtained fluorescent composite had the laminated structure shown in FIG. The visible light transmittance defined in JIS Z8722 of the obtained fluorescent composite was less than 20%.
（実施例３）
実施例１と同様な方法で芯体を作製した。
(Example 3)
A core body was produced in the same manner as in Example 1.
次に、実施例１と同様な組成の四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）１．３３ｋｇに対して、実施例１と同様な組成のアルミン酸ストロンチウム系蓄光性蛍光体粉末を２００ｇ混合攪拌して蓄光蛍光体粉末が混合された四ふっ化エチレン樹脂微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、四ふっ化エチレン樹脂微粒子分８０重量％に対して２０重量％となる。次に、実施例１と同じ製造条件の塗布、乾燥及び焼成によって、芯体の一方の四ふっ化エチレン樹脂層上に厚さ２００μｍの蛍光体層を作製した。 Next, a strontium aluminate-based phosphorescent phosphor powder having the same composition as that of Example 1 was applied to 1.33 kg of an ethylene tetrafluoride resin fine particle aqueous dispersion (made by Daikin Industries) having the same composition as that of Example 1. An aqueous dispersion of fine tetrafluoroethylene resin particles mixed with 200 g of phosphorescent phosphor powder was prepared by mixing and stirring. The mixing ratio of the phosphorescent phosphor powder at this time is 20% by weight with respect to 80% by weight of the tetrafluoroethylene resin fine particles. Next, a phosphor layer having a thickness of 200 μm was produced on one of the tetrafluoroethylene resin layers of the core by application, drying and firing under the same production conditions as in Example 1.
さらに実施例１と同様な組成の四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造条件の塗布、乾燥及び焼成によって、蛍光体層及び芯体の他方の四ふっ化エチレン樹脂層上に厚さ２０μｍの保護層（最外層）を得た。得られた蛍光複合体は、図１に示す積層構造を有するものであった。得られた蛍光複合体のＪＩＳ Ｚ８７２２に規定される可視光透過率は２０％未満であった。 Further, the phosphor layer and the core were formed by coating, drying and firing under the same production conditions as described above using an ethylene tetrafluoride-hexafluoropropylene copolymer resin fine particle aqueous dispersion (manufactured by Dupont) having the same composition as in Example 1. A protective layer (outermost layer) having a thickness of 20 μm was obtained on the other tetrafluoroethylene resin layer of the body. The obtained fluorescent composite had the laminated structure shown in FIG. The visible light transmittance defined in JIS Z8722 of the obtained fluorescent composite was less than 20%.
（実施例４）
実施例１と同様な方法で芯体を作製した。
Example 4
A core body was produced in the same manner as in Example 1.
次に、実施例１と同様な組成の四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）１．２５ｋｇに対して、実施例１と同様な組成のアルミン酸ストロンチウム系蓄光性蛍光体粉末を２５０ｇ混合撹拌して蓄光蛍光体粉末が混合された四ふっ化エチレン樹脂微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、四ふっ化エチレン樹脂微粒子分７５重量％に対して２５重量％となる。次に、実施例１と同じ製造条件の塗布、乾燥及び焼成によって、芯体の一方の四ふっ化エチレン樹脂層上に厚さ２００μｍの蛍光体層を得た。 Next, strontium aluminate-based phosphorescent phosphor powder having the same composition as that of Example 1 was applied to 1.25 kg of an ethylene tetrafluoride resin fine particle aqueous dispersion (made by Daikin Industries) having the same composition as that of Example 1. An aqueous dispersion of ethylene tetrafluoride resin fine particles mixed with 250 g of phosphorescent phosphor powder was prepared by mixing and stirring. The mixing ratio of the phosphorescent phosphor powder at this time is 25% by weight with respect to 75% by weight of the tetrafluoroethylene resin fine particles. Next, a phosphor layer having a thickness of 200 μm was obtained on one of the tetrafluoroethylene resin layers of the core by application, drying and firing under the same production conditions as in Example 1.
さらに、実施例１と同様な組成の四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造条件の塗布、乾燥及び焼成によって、蛍光体層及び芯体の他方の四ふっ化エチレン樹脂層上に厚さ２０μｍの保護層（最外層）を得た。得られた蛍光複合体は、図１に示す積層構造を有するものであった。得られた蛍光複合体のＪＩＳ Ｚ８７２２に規定される可視光透過率は２０％未満であった。 Further, by using a tetrafluoroethylene-hexafluoropropylene copolymer resin fine particle aqueous dispersion (manufactured by Dupont) having the same composition as in Example 1, the phosphor layer and A protective layer (outermost layer) having a thickness of 20 μm was obtained on the other tetrafluoroethylene resin layer of the core. The obtained fluorescent composite had the laminated structure shown in FIG. The visible light transmittance defined in JIS Z8722 of the obtained fluorescent composite was less than 20%.
（比較例１）
実施例１と同様な種類のガラス繊維織物（日東紡績製）に対して、実施例１と同様な組成の四ふっ化エチレン樹脂微粒子水系分散液（ダイキン工業製）を含浸することによって塗布し、雰囲気温度を１００℃に調整した密封炉で５分乾燥させ、水分を飛ばしたのち、雰囲気温度を３６０℃に調整した密封炉にて５分焼成した。この工程を複数回繰り返すことによって両面の厚さ合計が３３０μｍの四ふっ化エチレン樹脂層を得ることにより、芯体を得た。さらに実施例１と同様な組成の四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造方法によって、芯体の両面に厚さ２０μｍの保護層を形成した。得られた複合体は、蛍光体層を含まないものである。
(Comparative Example 1)
The same kind of glass fiber fabric as in Example 1 (manufactured by Nitto Boseki) was applied by impregnating with a tetrafluoroethylene resin fine particle aqueous dispersion (manufactured by Daikin Industries) having the same composition as in Example 1. After drying for 5 minutes in a sealed furnace with the atmospheric temperature adjusted to 100 ° C. and removing the moisture, it was fired for 5 minutes in a sealed furnace with the atmospheric temperature adjusted to 360 ° C. By repeating this process a plurality of times, a core body was obtained by obtaining a tetrafluoroethylene resin layer having a total thickness of 330 μm on both sides. Further, a protective layer having a thickness of 20 μm is formed on both surfaces of the core by the same production method as described above using a tetrafluoroethylene-hexafluoropropylene copolymer resin fine particle aqueous dispersion (manufactured by Dupont) having the same composition as in Example 1. Formed. The obtained composite does not include a phosphor layer.
（比較例２）
図７に示す積層構造を有する蛍光複合体を以下の方法で作製した。
(Comparative Example 2)
A fluorescent composite having the laminated structure shown in FIG. 7 was produced by the following method.
まず、実施例１と同様な方法で芯体１を作製した。 First, the core body 1 was produced by the same method as in Example 1.
次に、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）が６０重量％、非イオン界面活性剤が６重量％及び水が３４重量％からなるＰＦＡ微粒子水系分散液（三井デュポンフロロケミカル製）１．３３ｋｇに対して、実施例１と同様な組成のアルミン酸ストロンチウム系蓄光性蛍光体粉末を２００ｇ混合攪拌して蓄光蛍光体粉末が混合されたＰＦＡ微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、ＰＦＡ微粒子分８０重量％に対して２０重量％となる。次に、実施例１と同じ製造条件の塗布、乾燥及び焼成によって、芯体１の両方のＰＦＡ１ｂ層上に厚さ２００μｍの第１，第２の蛍光体層１１1，１１2を作製した。 Next, a PFA fine particle aqueous dispersion (made by Mitsui DuPont Fluorochemical Co., Ltd.) comprising 60% by weight of a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA), 6% by weight of a nonionic surfactant and 34% by weight of water. ) With respect to 1.33 kg, 200 g of strontium aluminate phosphorescent phosphor powder having the same composition as in Example 1 was mixed and stirred to prepare a PFA fine particle aqueous dispersion in which phosphorescent phosphor powder was mixed. The mixing ratio of the phosphorescent phosphor powder at this time is 20% by weight with respect to 80% by weight of the PFA fine particles. Next, the first and second phosphor layers 11 1 and 11 2 having a thickness of 200 μm were formed on both PFA 1b layers of the core 1 by coating, drying and firing under the same manufacturing conditions as in Example 1.
さらに実施例１と同様な組成の四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）を用いて上記と同じ製造条件の塗布、乾燥及び焼成によって、両方の蛍光体層上に厚さ２０μｍの保護層（最外層）３1，３2を得た。 Further, both phosphor layers were obtained by coating, drying and firing under the same production conditions as described above using an ethylene tetrafluoride-hexafluoropropylene copolymer resin fine particle aqueous dispersion (manufactured by Dupont) having the same composition as in Example 1. On top, protective layers (outermost layers) 3 1 and 3 2 having a thickness of 20 μm were obtained.
（比較例３）
図８に示す積層構造を有する蛍光複合体を以下の方法で作製した。
(Comparative Example 3)
A fluorescent composite having the laminated structure shown in FIG. 8 was produced by the following method.
実施例１と同様な方法で芯体１を作製した。 A core body 1 was produced in the same manner as in Example 1.
次に、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂（ＦＥＰ）が５４重量％、非イオン界面活性剤が５．５重量％及び水が４０．５重量％からなる四ふっ化エチレン−六ふっ化プロピレン共重合樹脂微粒子水系分散体（Ｄｕｐｏｎｔ製）１．３３ｋｇに対して、実施例１と同様な組成のアルミン酸ストロンチウム系蓄光性蛍光体（根本特殊化学製）粉末を２００ｇ混合攪拌して蓄光蛍光体粉末が混合されたＦＥＰ微粒子水系分散液を調整した。この時の蓄光性蛍光体粉末の混合率は、ＦＥＰ微粒子分８０重量％に対して２０重量％となる。次に、実施例１と同じ製造条件の塗布、乾燥及び焼成によって、芯体１の両方のＦＥＰ層１ｂ上に厚さ２００μｍの第１，第２の蛍光体層１２1，１２2を作製した。 Next, ethylene tetrafluoride-6 hexapropylene-hexafluoropropylene copolymer resin (FEP) comprising 54% by weight, nonionic surfactant 5.5% by weight and water 40.5% by weight. 200 g of strontium aluminate phosphorescent phosphor (manufactured by Nemoto Special Chemical Co., Ltd.) having the same composition as in Example 1 was mixed and stirred with respect to 1.33 kg of propylene fluoride copolymer resin fine particle aqueous dispersion (manufactured by Dupont). An FEP fine particle aqueous dispersion mixed with phosphorescent phosphor powder was prepared. The mixing ratio of the phosphorescent phosphor powder at this time is 20% by weight with respect to 80% by weight of the FEP fine particle content. Next, first and second phosphor layers 12 1 and 12 2 having a thickness of 200 μm were produced on both FEP layers 1b of the core 1 by coating, drying and firing under the same production conditions as in Example 1. .
（比較例４）
最外層に保護層３1，３2を設けないこと以外は、比較例２と同様な方法で、図９に示す積層構造の蛍光複合体を作製した。
(Comparative Example 4)
A fluorescent composite having a multilayer structure shown in FIG. 9 was produced in the same manner as in Comparative Example 2 except that the protective layers 3 1 and 3 2 were not provided on the outermost layer.
実施例１〜４の蛍光複合体を、２４時間光を遮断した環境で保管した。保管後の蛍光複合体に、照度５０００Ｌｘの光を１時間照射した。照射後、暗室に移し、１分後、ＬＳ−１００輝度計（コニカミノルタ製）を使用し、９０°の角度で０．２ｍの距離から残光輝度を測定した。測定時間を、暗室移動後、１０分、３０分及び６０分に変更し、残光輝度を測定した。
表１から、蛍光体層中の蛍光体粒子の含有量が多い方が残光輝度が高いことがわかる。
以下に、原出願の当初の特許請求の範囲に記載された発明を付記する。
［１］
耐熱性織布と、前記耐熱性織布の両面に形成されたフッ素樹脂層とを含む芯体と、
蛍光体及び四ふっ化エチレン樹脂を含む蛍光体層とを含むことを特徴とする蛍光複合体。
［２］
前記蛍光体層中の前記蛍光体の含有量は１０重量％以上２５重量％以下の範囲であることを特徴とする［１］記載の蛍光複合体。
［３］
前記フッ素樹脂層は、四ふっ化エチレン樹脂、四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂、及び、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂よりなる群から選択される少なくとも一種類を含むことを特徴とする［１］〜［２］いずれか１記載の蛍光複合体。
［４］
溶融流動性フッ素樹脂を含有する保護層をさらに含み、前記保護層が少なくとも前記蛍光体層の片面に配置されることを特徴とする［１］〜［３］いずれか１記載の蛍光複合体。
［５］
溶融流動性フッ素樹脂を含有する保護層をさらに含み、前記保護層が少なくとも最外層に配置されることを特徴とする［１］〜［３］いずれか１記載の蛍光複合体。
［６］
前記耐熱性織布は、ガラス繊維、炭素繊維、セラミックス繊維、アラミド繊維及び金属繊維よりなる群から選択される少なくとも一種類を含むことを特徴とする［１］〜［５］いずれか１記載の蛍光複合体。
［７］
前記耐熱性織布の織組織は、バスケット織、綾織、変形綾織、朱子織または平織であることを特徴とする［１］〜［６］いずれか１記載の蛍光複合体。
［８］
前記蛍光体は、蓄光性蛍光体であることを特徴とする［１］〜［７］いずれか１記載の蛍光複合体。
［９］
ＪＩＳ Ｚ８７２２に規定される可視光透過率が２０％未満である［１］〜［８］いずれか１記載の蛍光複合体。
From Table 1, it can be seen that the afterglow luminance is higher when the content of the phosphor particles in the phosphor layer is larger.
The invention described in the scope of the claims of the original application is appended below.
[1]
A core including a heat-resistant woven fabric and a fluororesin layer formed on both surfaces of the heat-resistant woven fabric;
A phosphor composite comprising a phosphor and a phosphor layer containing an ethylene tetrafluoride resin.
[2]
The phosphor composite according to [1], wherein the content of the phosphor in the phosphor layer is in the range of 10 wt% to 25 wt%.
[3]
The fluororesin layer includes at least one selected from the group consisting of a tetrafluoroethylene resin, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin, and a tetrafluoroethylene-hexafluoropropylene copolymer resin. The fluorescent complex according to any one of [1] to [2], wherein
[4]
The fluorescent composite according to any one of [1] to [3], further comprising a protective layer containing a melt-flowable fluororesin, wherein the protective layer is disposed on at least one surface of the phosphor layer.
[5]
The fluorescent composite according to any one of [1] to [3], further comprising a protective layer containing a melt-flowable fluororesin, wherein the protective layer is disposed at least in the outermost layer.
[6]
The heat-resistant woven fabric includes at least one selected from the group consisting of glass fiber, carbon fiber, ceramic fiber, aramid fiber, and metal fiber, [1] to [5] Fluorescent complex.
[7]
The fluorescent composite according to any one of [1] to [6], wherein the woven structure of the heat-resistant woven fabric is basket weave, twill weave, deformed twill weave, satin weave or plain weave.
[8]
The phosphor composite according to any one of [1] to [7], wherein the phosphor is a phosphorescent phosphor.
[9]
The fluorescent composite according to any one of [1] to [8], wherein the visible light transmittance defined in JIS Z8722 is less than 20%.
１…芯体、１ａ…耐熱性織布、１ｂ…フッ素樹脂層、２1〜２2，１１1〜１１2，１２1〜１２2…蛍光体層。 1 ... core, 1a ... heat resistant woven textile, 1b ... fluororesin layer, 2 1 to 2 2, 11 1 to 11 2, 12 1 to 12 2 ... phosphor layer.
Claims (11)
蛍光体及び四ふっ化エチレン樹脂を含む蛍光体層とを含む蛍光複合体を含んだ膜構造物。 A core including a heat-resistant woven fabric and a fluororesin layer formed on both surfaces of the heat-resistant woven fabric;
A film structure including a fluorescent composite including a phosphor and a phosphor layer containing an ethylene tetrafluoride resin.
前記溶融流動性フッ素樹脂は、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂（ＦＥＰ）及び四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）からなる群より選択される少なくとも１つを含むことを特徴とする請求項１〜３いずれか１項記載の膜構造物。 It further includes a protective layer containing a melt-flowable fluororesin, and the protective layer is disposed on at least one side of the phosphor layer ,
The melt flowable fluororesin includes at least one selected from the group consisting of a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP) and a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA). The membrane structure according to any one of claims 1 to 3, wherein:
前記溶融流動性フッ素樹脂は、四ふっ化エチレン−六ふっ化プロピレン共重合樹脂（ＦＥＰ）及び四ふっ化エチレンパーフルオロアルキルビニルエーテル共重合樹脂（ＰＦＡ）からなる群より選択される少なくとも１つを含むことを特徴とする請求項１〜３いずれか１項記載の膜構造物。 It further includes a protective layer containing a melt-flowable fluororesin, and the protective layer is disposed at least in the outermost layer ,
The melt flowable fluororesin includes at least one selected from the group consisting of a tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP) and a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin (PFA). The membrane structure according to any one of claims 1 to 3, wherein:
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