JP2007051171A - Flame-retardant light-accumulating resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To impart flame retardancy to a resin containing a light-accumulating pigment that comprises the resin used as a matrix for applying the light-accumulating pigment on walls or floors and the light-accumulating pigment used as a display for guiding evacuation routes at the time of disaster so that it can be applied also at the time of a fire disaster, as well as transparency, friction resistance or other properties. <P>SOLUTION: An ordinary temperature-curable organosiloxane composition is used as a resin satisfying the properties above. The resin is admixed with the light-accumulating pigment and cured to give the flame-retardant light-accumulating resin. The flame-retardant light-accumulating resin may further comprise glass fibers, silica and silicone spheres. These substances are used for enhancing friction resistance, viscosity and vibration resistance of the flame-retardant light-accumulating resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a phosphorescent resin mainly composed of a flame retardant resin.

  A property that emits light for a long time without receiving energy supply even in the dark after receiving light from sunlight or an electric lamp is called luminous property, and a substance having luminous property is called luminous pigment. The characteristics of the phosphorescent pigment are characterized by the emission color, the emission luminance, the afterglow time (the time for which light continues to be emitted after the light irradiation is stopped), and the like. There are two types of phosphorescent pigments whose main crystal is zinc sulfide and those whose main crystal is strontium aluminate salt. The former phosphorescent pigment emits yellowish green light, and the afterglow time is about 0.5 hours. The latter phosphorescent pigment emits green light and has an afterglow time of 5 hours or longer.

  There are various usage forms of phosphorescent pigments having long persistence such as evacuation route guidance display in case of darkness in the event of a disaster, ornaments, clocks, stationery, and fishing gear. In particular, the evacuation route guidance display is indispensable from the viewpoint of ensuring safety because it emits light even when power is stopped and can evacuate people to a safe place.

  Since the phosphorescent pigment is usually in a powder form, it is generally mixed with a resin when applied to a building wall or floor for evacuation route guidance display. That is, in powder form, even if it is applied to walls, floors, etc., it will scatter, but by mixing with resin and curing after application, the phosphorescent pigment can be stably fixed to walls, floors, etc. it can. The resin to be mixed with the phosphorescent pigment is required to have high transparency in order to exhibit the light emission performance of the phosphorescent pigment. In addition, since the evacuation route guidance display is assumed to be used in the event of a fire such as a simultaneous terrorist attack in the United States or a Korean subway fire, it is preferable that the resin mixed with the phosphorescent pigment is flame retardant. Further, since the resin wears when a person walks on the resin mixed with the phosphorescent pigment, the resin for mixing with the phosphorescent pigment preferably has wear resistance.

（式中：Ｒ^１は水素原子もしくはＣ_１からＣ_５のアルキル基あるいはアシル基；Ｒ^２ないしＲ^６はそれぞれが水素原子、ＯＲ^１基もしくは一価の炭化水素基より選ばれた同一もしくは異なる基、ｎは１ないし１５の数）で表される化合物の１種または２種以上からなり、且つその中のケイ素成分をＳｉＯ_２酸化物基準で表して５０重量％以上含有している液状オルガノポリシロキサン（Ａ）、
下記化学式５もしくは６

（式中：Ｍはアルミニウムまたはホウ素元素；Ｑはケイ素、チタンまたはジルコニウム元素；Ｒ^８は水素原子もしくはＣ_１ないしＣ_５のアルキル基、アシル基あるいはオキシム基；Ｒ^７は水素原子、ＯＲ^８基もしくは一価の炭化水素基より選ばれた基；ｐは１または２；ｍは１ないし３の整数）で表される有機金属化合物の１種または２種以上からなる架橋剤（Ｂ）、および、亜鉛、コバルト、アルミニウムまたは錫元素の１または２種以上の含金属有機化合物であり、触媒反応ブロッキング剤が配合された硬化触媒（Ｃ）、からなり、且つ該三成分混合液組成物が含有する全金属元素成分をＭＯ_ｙ／２酸化物基準（Ｍはアルミニウム、ホウ素、ケイ素、チタン、ジルコニウム元素、ｙは金属元素の価数）で表わして４０重量％以上含有している常温硬化型オルガノシロキサン組成物である請求項１に記載の難燃性蓄光樹脂を提供する。第三の発明は、第一または第二の発明に基づいて、前記難燃性樹脂に対する蓄光顔料の割合が重量比率で５％以上３０％以下である難燃性蓄光樹脂を提供する。第四の発明は、第一から第三の発明に基づいて前記蓄光顔料が、アルミン酸ストロンチウム系蓄光顔料である難燃性蓄光樹脂を提供する。第五の発明は、第四の発明に基づいて、前記アルミン酸ストロンチウム系蓄光顔料が、Ｓｒ_{１−ｎ−ｍ}Ｅｕ_ｎＤｙ_ｍＡｌ_２−ｋＢ_ｋＯ_４（０．０００１<ｎ<０．２、０．０００１<ｍ<０．２、０．０００１<ｋ<０．２）で表される難燃性蓄光樹脂を提供する。第六の発明は、第一から第五の発明に基づいて、補強剤、増粘剤、および耐振動剤のうちいずれか一以上をさらに含む難燃性蓄光樹脂を提供する。第七の発明は、第六の発明に基づいて、前記補強剤がガラス繊維および／またはガラスフラックスである難燃性蓄光樹脂を提供する。第八の発明は、第六または第七の発明に基づいて、前記増粘剤が微粉末シリカである難燃性蓄光樹脂を提供する。第九の発明は、第六から第八の発明に基づいて、前記耐振動剤がシリコーン球および／またはシリコーン系可撓剤である難燃性蓄光樹脂を提供する。 In order to solve the above problems, the present invention provides a phosphorescent resin obtained by mixing a flame-retardant and transparent resin with a phosphorescent pigment. That is, the first invention provides a flame retardant phosphorescent resin comprising a flame retardant resin and a phosphorescent pigment. A second invention is based on the first invention, wherein the flame retardant resin is represented by the following chemical formula 4:

(Wherein R ¹ is a hydrogen atom, a C ₁ to C ₅ alkyl group or an acyl group; R ² to R ⁶ are the same or different each selected from a hydrogen atom, an OR ¹ group or a monovalent hydrocarbon group) Group, wherein n is a number of 1 to 15), and a liquid organocontaining 50% by weight or more of a silicon component in terms of SiO ₂ oxide Polysiloxane (A),
The following chemical formula 5 or 6

(Wherein M is an aluminum or boron element; Q is a silicon, titanium or zirconium element; R ⁸ is a hydrogen atom or a C ₁ to C ₅ alkyl group, acyl group or oxime group; R ⁷ is a hydrogen atom, OR ⁸ group Or a group selected from monovalent hydrocarbon groups; p is 1 or 2; m is an integer of 1 to 3), and a crosslinking agent (B) comprising one or more organometallic compounds represented by: , One or more metal-containing organic compounds of zinc, cobalt, aluminum, or tin element, comprising a curing catalyst (C) blended with a catalytic reaction blocking agent, and containing the three-component mixed liquid composition the total metal element component MO y _{/ 2} oxide basis (M is aluminum, boron, silicon, titanium, zirconium element, y is the valence of the metal element) or 40 wt% expressed in containing the And which provides a flame-retardant phosphorescent resin according to claim 1 which is cold-setting organosiloxane composition. A third invention provides a flame retardant phosphorescent resin in which the ratio of the phosphorescent pigment to the flame retardant resin is 5% or more and 30% or less based on the first or second invention. A fourth invention provides a flame retardant phosphorescent resin in which the phosphorescent pigment is a strontium aluminate phosphorescent pigment based on the first to third inventions. Fifth invention, based on the fourth invention, the strontium phosphorescent pigment _{aluminate, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0. 2, 0.0001 <m <0.2, 0.0001 <k <0.2). 6th invention provides the flame retardant luminous resin which further contains any one or more among a reinforcing agent, a thickener, and a vibration-proof agent based on 1st-5th invention. A seventh invention provides a flame retardant phosphorescent resin in which the reinforcing agent is glass fiber and / or glass flux based on the sixth invention. 8th invention provides the flame retardant luminous resin whose said thickener is a fine powder silica based on 6th or 7th invention. A ninth invention provides a flame retardant phosphorescent resin according to the sixth to eighth inventions, wherein the vibration-proofing agent is a silicone ball and / or a silicone-based flexible agent.

A tenth aspect of the invention is a mixing step in which a flame retardant resin and a phosphorescent pigment are mixed to form a coating agent, and a floor step and / or a wall surface to be coated with the coating agent, and a cleaning step. A flame retardant phosphorescent resin coating method comprising: a coating step of coating the coating agent on the floor and / or wall surface; and a curing step of curing until the coating agent is cured after the coating is completed I will provide a. An eleventh invention provides a flame retardant phosphorescent resin coating method, based on the tenth invention, wherein the flame retardant resin is the room temperature curable organosiloxane composition. A twelfth invention provides a flame retardant phosphorescent resin coating method according to the tenth or eleventh invention, wherein the ratio of the phosphorescent pigment to the flame retardant resin is 5% to 30% by weight. To do. A thirteenth invention provides a flame retardant phosphorescent resin coating method in which the phosphorescent pigment is a strontium aluminate phosphorescent pigment based on the tenth to twelfth inventions. Fourteenth invention, the strontium aluminate phosphorescent _{pigment, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0.2,0.0001 <m <0.2, 0.0001 <k <0.2) Provided is a flame retardant phosphorescent resin coating method. According to a fifteenth invention, on the basis of the tenth to fourteenth inventions, the mixing step further comprises mixing one or more of a reinforcing agent, a thickener, and a vibration proofing agent with a coating agent. A flame retardant phosphorescent resin coating method is provided. A sixteenth aspect of the invention provides a flame retardant phosphorescent resin coating method in which the reinforcing agent is glass fiber and / or glass flux based on the fifteenth aspect of the invention. A seventeenth invention provides a flame retardant phosphorescent resin coating method, wherein the thickener is fine powder silica based on the fifteenth or sixteenth invention. According to an eighteenth aspect of the present invention, there is provided a flame retardant phosphorescent resin coating method according to the fifteenth to seventeenth aspects, wherein the vibration proofing agent is a silicone ball and / or a silicone-based flexible agent.

Nineteenth _{invention, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0.2,0.0001 <m <0.2,0.0001 < A phosphorescent pigment represented by k <0.2) is provided. According to a twentieth aspect of the invention, there is provided a firing step of firing SrO, Al ₂ O ₃ , Eu ₂ O ₃ , Dy ₂ O ₃ , and B ₂ O ₃ in a reducing atmosphere to obtain a fired mixture, and cooling the fired mixture And a washing step of washing with acetic acid and glycerin, and a phosphorescent pigment production method comprising:

  The twenty-first aspect of the present invention is the flame retardant phosphorescent according to any one of claims 1 to 9, wherein the illuminating unit, a road surface portion provided with joints illuminated by the illuminating unit, and the road surface portion are disposed. And a passage structure made of resin. According to a twenty-second invention, based on the twenty-first invention, the width of the flame-retardant phosphorescent resin filled in the joint is 3 mm or more and 3 cm or less, and the flame-retardant phosphorescent resin filled in the joint is A passage structure having a depth of 1 mm or more and 1 cm or less is provided. The twenty-third invention is based on the twenty-first or twenty-second invention, wherein the joint provided on the road surface portion is made of an inorganic tile, an organic tile, a mortar block, a concrete block used for road pavement. Provided is a passage structure which is a gap generated by combining any one or more. According to the twenty-fourth invention, based on the twenty-first to twenty-third invention, the joint where the flame-retardant phosphorescent resin provided on the road surface portion is arranged becomes a figure for guiding evacuation. A passage structure is provided. According to a twenty-fifth aspect of the invention, based on the twenty-first to twenty-fourth aspects, the wear resistance of the flame retardant phosphorescent resin disposed on the joint provided on the road surface portion is JISK5600-5. In the test by No. 8, when the load of the wear wheel is 1 kg, the type of abrasive paper is CS-17, and the rotation speed is 1000 times, a passage structure having a wear loss of 500 mg or less is provided.

  According to a twenty-sixth aspect of the present invention, there is provided a mixing step in which the flame retardant resin according to any one of claims 1 to 9 and a phosphorescent pigment are mixed to form a coating agent, and the coating agent should be applied. A cleaning step for cleaning the floor surface and / or wall surface, a coating step for coating the coating agent on the joints of the passage illuminated by the illumination unit, and the coating agent is cured after the coating is completed. A path structure manufacturing method comprising a curing step for curing up to is provided.

  According to the present invention, even when a power failure occurs due to a fire, the evacuation route display does not burn, so the function as the evacuation route display is not lost. Therefore, the safety as an evacuation route display at the time of a disaster in a building or an underground shopping area is further improved. Moreover, since the resin used for displaying the evacuation route does not burn, it is safe without generating toxic gas.

  The best mode for carrying out the present invention will be described below. Note that the present invention is not limited to these embodiments, and can be implemented in various modes without departing from the scope of the invention.

  The first embodiment will mainly describe claims 1 and 10. The second embodiment will mainly describe claims 2, 3, 11 and 12. The third embodiment will mainly describe claims 4, 5, 13, 14, 19 and 20. The fourth embodiment will mainly describe claims 6, 7, 8, 9, 15, 16, 17 and 18. The fifth embodiment will mainly describe claims 21, 22 and 26. The sixth embodiment will mainly describe Claim 23. The seventh embodiment will mainly describe Claim 24. The eighth embodiment will mainly describe Claim 25.

<Embodiment 1>
<Embodiment 1: Concept>
FIG. 1 shows a conceptual diagram of this embodiment. The flame retardant phosphorescent resin of this embodiment is disposed in a tile groove or the like attached to a station platform. Even if a disaster occurs at night and the light is turned off, the flammable phosphorescent resin that has received the energy of light until then emits light, so that a pedestrian can be guided to the evacuation route.

<Embodiment 1: Material composition>
The “flame retardant phosphorescent resin” of the present embodiment is composed of “flame retardant resin” and “phosphorescent pigment”.

  “Flame retardant resin” is a resin that has the property of being difficult to burn even at high temperatures and under aerobic conditions. Specifically, it is preferable that the flame retardant resin satisfies UL standard 94V-0. The UL standard is a safety standard established by Underwriters Laboratories. Inc., a testing laboratory in the United States. Moreover, in order to exhibit the light emission characteristic as a phosphorescent resin, it is necessary for transparency to be high. Since the flame retardant resin is worn by contact with a pedestrian, the wear resistance is preferably high in order to facilitate maintenance.

  “Luminescent pigment” is a substance having the property of emitting light for a long time after being stimulated by light and then stopping the stimulation of light. The crystal structure constituting the phosphorescent pigment is mainly zinc sulfide, strontium aluminate or the like. In order to exhibit luminous properties, it is necessary to add an activator or a coactivator to these crystals. Examples of the activator or coactivator include Cu, Eu, Dy, and B.

The “flame retardant phosphorescent resin” preferably has a luminescent property that satisfies JIS standard Z9107. Conditions of emission characteristics that are defined in the JIS standard Z9107, after stopping the irradiation was irradiated for 20 minutes at an illuminance of 200 lux fluorescent lamp D ₆₅ in phosphorescent plate, luminance phosphorescent plate emitted after 5 minutes, after 10 minutes 20 minutes and 60 minutes later. The main usage mode of the flame-retardant phosphorescent resin is when it is applied to a floor or wall of a building or underground mall and used as an evacuation route display at the time of disaster. In this case, in order to avoid wear due to contact with a pedestrian, it is preferable to apply a flame-retardant phosphorescent resin in a recess such as a joint. In addition, the flame-retardant phosphorescent resin is not conspicuous under illumination, but when it is turned off at night, only the portion to which the flame-retardant phosphorescent resin is applied appears, so that it can also be used as a work of art.

<Embodiment 1: Application method>
FIG. 2 shows an example of a method for applying the flame retardant phosphorescent resin of this embodiment. The application method of the flame retardant phosphorescent resin of the present embodiment includes a mixing step (S0201), a cleaning step (S0202), an application step (S0203), and a curing step (S0204).

  In the mixing step (S0201), the flame retardant resin and the phosphorescent pigment are mixed to form a coating agent. In the mixing step, in order for the flame retardant phosphorescent resin to exhibit sufficient light emission characteristics, mixing is performed so that the phosphorescent pigment is uniformly dispersed in the flame retardant resin.

  In the cleaning step (S0202), the floor surface and / or the wall surface to which the coating agent is to be applied is cleaned. This is to prevent the transparency of the resin from deteriorating due to dust, dust, etc. accumulated on the floor surface being mixed into the coating agent. The transparency of the resin can be increased by the cleaning step, and the light emission luminance and the afterglow time of the flame retardant phosphorescent resin can be improved.

  In the applying step (S0203), the coating agent is applied to the floor surface and / or the wall surface. Prior to application, the luminous efficiency of the flame retardant phosphorescent resin may be improved by applying a white paint to the portion to be applied. Moreover, you may stick a curing tape around the location which should be applied so that a coating agent may not adhere other than the target location.

  The curing step (S0204) is performed until the coating agent is cured after the application is completed. In this step, the coating agent may wait until it naturally cures by reaction with moisture contained in the air, or may be forcibly cured by spraying a curing spray containing moisture.

<Embodiment 1: Effect>
With the flame-retardant phosphorescent resin of this embodiment, even when a power failure occurs due to a fire, the evacuation route display does not burn, so the function as the evacuation route display is not lost. Therefore, the safety as an evacuation route display at the time of a disaster in a building or an underground shopping area is further improved.

<Embodiment 2>
<Embodiment 2: Concept>
In this embodiment, a room temperature curable organosiloxane composition having characteristics such as flame retardancy and wear resistance is used for the flame retardant resin.

<Embodiment 2: Material composition>
The “flame retardant phosphorescent resin” of the present embodiment is composed of “flame retardant resin” and “phosphorescent pigment”.

The “flame retardant resin” is composed of the liquid organopolysiloxane (A), the crosslinking agent (B), and the curing catalyst (C), and is an all-metal element component contained in the three-component mixed liquid composition Is a room-temperature-curable organosiloxane composition containing 40% by weight or more in terms of MO _{y / 2} oxide standard (M is aluminum, boron, silicon, titanium, zirconium element, y is a valence of a metal element) . The room-temperature curable organosiloxane composition is the same as the composition shown in Patent Document 1, and is currently manufactured and sold by Suzuki Sangyo Co., Ltd. under the trade name Ceraton NP.
JP 7-72250

  The room temperature effect organosiloxane composition contains Si—O bonds and is not oxidized any more, and thus has flame retardancy. Moreover, since it is solvent-free, there is no smell of a solvent and it does not give an unpleasant feeling to an operator when applying. Moreover, since it is inorganic, it is excellent in chemical resistance, acid resistance and anti-staining properties, and maintenance is easy.

  The ratio of the “phosphorescent pigment” is preferably 5% to 30% by weight with respect to the “flame retardant phosphorescent resin”. When the ratio of the phosphorescent pigment is 5% or less, the light emission luminance of the flame-retardant phosphorescent resin is weak, and the function as an evacuation route display cannot be sufficiently performed. Moreover, when the ratio of the phosphorescent pigment is 30% or more, the performance of the flame retardant phosphorescent resin such as flame retardancy and wear resistance is weakened. The ratio of the phosphorescent pigment is more preferably about 15% by weight with respect to the flame retardant phosphorescent resin. The type and properties of the phosphorescent pigment are the same as in the first embodiment.

<Embodiment 2: Application method>
Since the application method of the flame-retardant phosphorescent resin of this embodiment is the same as that of Embodiment 1, it is omitted.

<Embodiment 2: Effect>
By using the flame retardant phosphorescent resin of the present embodiment, the flame retardancy becomes even stronger and the safety as an evacuation route display is further improved.

<Embodiment 3>
<Embodiment 3: Concept>
The present embodiment relates to a flame-retardant phosphorescent resin in which emission luminance and afterglow time are further improved by using strontium aluminate as a phosphorescent pigment.

<Embodiment 3: Material composition>
The “flame retardant phosphorescent resin” of the present embodiment is composed of “flame retardant resin” and “phosphorescent pigment”. The “flame retardant resin” is the same as in the first embodiment.

  The “phosphorescent pigment” is a strontium aluminate-based phosphorescent pigment. The strontium aluminate phosphorescent pigment is a phosphorescent pigment containing Sr, Al, and O as main constituent elements. The strontium aluminate phosphorescent pigment contains trace amounts of elements such as Eu, Dy, and B in addition to the above elements. The strontium aluminate phosphorescent pigment has dramatically improved emission luminance and afterglow time compared to the conventionally used zinc sulfide type crystals, and is harmless to the human body.

Strontium phosphorescent pigment _{aluminate, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0.2,0.0001 <m <0.2,0.0001 <k <0.2) is more preferable. Here, Eu has a function as a light emission center that emits light even after light stimulation is stopped. That is, it is considered that the light emission of the strontium aluminate-based phosphorescent pigment is due to electronic transition between Eu's 4f orbit and 5d orbitals. It is considered that Dy and B have a role of assisting light emission by forming a defect complex, and holes supplied by the defect complex are combined with the electrons.

_{Sr 1-n-m Eu n} Dy m Al 2-k B k O 4 in (0.0001 <n <0.2,0.0001 <m <0.2,0.0001 <k <0.2) The luminous pigment represented is obtained by firing SrO, Al ₂ O ₃ , Eu ₂ O ₃ , Dy ₂ O ₃ , and B ₂ O ₃ at about 1300 ° C. Boron (B) taken into the crystal is a substance that exhibits a long afterglow, but boron that has not been taken into the crystal is considered to be a factor that decreases the emission luminance. Therefore, the phosphorescent pigment may be washed with acetic acid after baking to remove excess boron.

<Embodiment 3: Application method>
Since the application method of the flame-retardant phosphorescent resin of this embodiment is the same as that of Embodiment 1, it is omitted.

<Embodiment 3: Effect>
In the present embodiment, by using strontium aluminate as the phosphorescent pigment, it is possible to improve the light emission luminance and the afterglow time of the flame-retardant phosphorescent resin.

<Embodiment 4>
<Embodiment 4: Concept>
The present embodiment relates to a flame retardant phosphorescent resin in which the abrasion resistance and impact resistance of the flame retardant phosphorescent resin are improved by adding a reinforcing agent, a thickener, and a vibration proofing agent.

<Embodiment 4: Material composition>
FIG. 3 shows the material configuration of this embodiment. The “flame retardant phosphorescent resin” (0300) of the present embodiment includes “reinforcing agent” (0303) and “thickener” (0304) in addition to “flame retardant resin” (0301) and “phosphorescent pigment” (0302). ), And “Vibration Resistant” (0305).

  “Flame-retardant resin” (0301) and “phosphorescent pigment” (0302) are the same as those in the first to third embodiments.

  “Reinforcing agent” (0303) is a substance added to improve the wear resistance of the flame retardant phosphorescent resin (0300). As the reinforcing agent (0303), for example, glass fiber and / or glass flux may be used. The glass fiber includes a long fiber and a short fiber. Here, the long fiber is mainly used. When glass fiber is used as the reinforcing agent (0303), the length is preferably 1 mm or more and 1 cm or less in order to sufficiently exhibit the effect as the reinforcing agent. The reinforcing agent is preferably added in an amount of 5 to 30% by weight with respect to the flame retardant resin (0301).

  The “thickening agent” (0304) is added to increase the viscosity of the flame-retardant resin (0301) before curing so that it does not spread to the surroundings when applied. For example, fine powder silica may be used as the thickener (0304). Silica is another name for silicon dioxide and has a network structure composed of siloxane bonds (bonds of Si and O). The thickener (0304) is preferably added in an amount of 1 to 10% by weight with respect to the flame retardant resin (0301).

  “Vibration-proofing agent” (0305) is added to increase the strength against the impact of the flame-retardant phosphorescent resin (0301). As the vibration-resistant agent (0305), for example, a silicone ball and / or a silicone-based flexible agent may be used. The silicone resin has a size of 5 to 50 μm. The silicone-based flexible agent is a liquid material having a methoxy functional group. It is preferable to add 3-20% by weight ratio of the vibration-resistant agent (0305) with respect to the flame-retardant resin (0301).

<Embodiment 4: Application method>
FIG. 4 shows an example of a method for applying the flame retardant phosphorescent resin of this embodiment. The application method of the flame retardant phosphorescent resin of the present embodiment includes a mixing step (S0401), a cleaning step (S0402), a coating step (S0403), and a curing step (S0404).

  In the mixing step (S0401), the flame retardant resin and the phosphorescent pigment are mixed, and one or more of a reinforcing agent, a thickener, and a vibration proofing agent are added. When adding a thickener, it is preferable to add it at the end. This is because if the thickener is added first, the viscosity becomes high and the materials cannot be sufficiently mixed. For other materials, the order of mixing is not particularly limited.

  The cleaning step (S0402), the applying step (S0403), and the curing step (S0404) are the same as in the first embodiment.

<Embodiment 4: Effect>
The flame retardant phosphorescent resin of the present embodiment has the characteristics that the wear resistance and vibration resistance are improved, and that it is difficult to spread around when applied. Therefore, the maintenance becomes easy and the work becomes easier when applying.

<Embodiment 5>
<Embodiment 5: Concept>
FIG. 5 shows a conceptual diagram of this embodiment. The present embodiment relates to a passage structure in which a flame-retardant phosphorescent resin containing a phosphorescent pigment and a resin is embedded in a joint such as a tile of the passage. When the passage structure becomes dark during a disaster or the like, the energy stored by the light received from the illumination unit during normal times is emitted as light. A pedestrian can follow the fire retardant phosphorescent resin that emits light to reach the evacuation exit.

<Embodiment 5: Configuration>
FIG. 6 shows a schematic view of the passage structure in the present embodiment. The “passage structure” (0600) shown in FIG. 6 includes an “illuminating part” (0601), a “road surface part” (0602), and a “flame retardant phosphorescent resin” (0603).

  The “illumination unit” (0601) is a device that artificially emits light. Examples of the illumination unit (0601) include a fluorescent lamp and an LED. The light emitted from the illumination unit (0601) is not limited to visible light (wavelength is about 400 to 700 nm), and some or all of its components are ultraviolet light (wavelength is about 400 nm or less) or infrared light (wavelength is about 400 nm or less). About 700 nm or more).

  The “road surface portion” (0602) is a road surface provided with joints that are illuminated by the illumination portion (0601). A road surface is a passage where people walk, whether indoors or outdoors. Examples of the road surface portion (0602) include a pedestrian road, an underpass, and a passage inside a building. The joint is an elongated concave portion provided on the road surface. It is not necessary for all of the joints provided on the road surface to receive light by the illumination unit (0601), and a part of the joints may be in a position where the illumination unit (0601) does not receive light. Since the joint reflects light emitted from the flame-retardant phosphorescent resin, the base is preferably white.

  The “flame retardant phosphorescent resin” (0603) is the flame retardant phosphorescent resin according to any one of claims 1 to 9, which is disposed at the joint of the road surface portion (0602). The flame retardant phosphorescent resin (0603) need not be disposed on all joints of the road surface portion (0602), and may be disposed only on a part of the joints. In particular, the flame-retardant phosphorescent resin (0603) does not have to be disposed at the joint where the light is not received from the illumination unit (0601). Other configurations of the flame-retardant phosphorescent resin (0603) are the same as those in the first to fourth embodiments.

  The width of the flame retardant phosphorescent resin filled in the joint is preferably 3 mm or more and 3 cm or less, and the depth of the flame retardant phosphorescent resin filled in the joint is preferably 1 mm or more and 1 cm or less. The reason why such a value is preferable is that when the width of the flame retardant phosphorescent resin is 3 mm or less, it is difficult for a person with low vision to visually recognize the flame retardant phosphorescent resin in the dark, thus indicating an evacuation route. If the width of the flame retardant phosphorescent resin is 3 cm or more or the depth is 1 cm or more, the amount of the flame retardant phosphorescent resin is increased and the cost is increased. This is because when the thickness is 1 mm or less, the flame-retardant phosphorescent resin easily peels from the joint.

<Embodiment 5: Application method>
FIG. 7 shows the flow of the passage structure manufacturing method of the present embodiment. The passage structure manufacturing method of the present embodiment includes a flame-retardant phosphorescent resin generation step (S0701), a cleaning step, (S0702), a coating step (S0703), and a curing step (S0704).

  In the flame retardant phosphorescent resin generation step (S0701), the flame retardant resin according to any one of claims 1 to 9 and a phosphorescent pigment are mixed to form a coating agent. The phosphorescent pigment, resin, and curing agent are the same as those described in the first embodiment.

  In the cleaning step (S0702), the floor surface and / or the wall surface to which the coating agent is to be applied is cleaned. If the joint is cleaned before applying the flame retardant phosphorescent resin, the foreign matter is not mixed with the flame retardant phosphorescent resin, the transparency of the resin is improved, and higher light emission characteristics are realized.

  In the applying step (S0703), the coating agent is applied to the joints of the passage illuminated by the illumination unit. Since the flame retardant phosphorescent resin cures over time, it is quickly placed on the joint before curing. If the joint is not white, a white paint may be applied to the joint before the arrangement of the flame retardant phosphorescent resin. Moreover, you may put a masking tape and a curing tape on parts other than a joint so that a flame-retardant phosphorescent resin may not disperse | distribute to the surrounding road surface.

  In the curing step (S0704), curing is performed until the flame-retardant phosphorescent resin is cured. In the coating step (S0703), when a masking tape or a curing tape is stretched, it is preferable to remove these tapes before the flame-retardant phosphorescent resin is cured. This is because after the flame retardant phosphorescent resin is cured, the flame retardant phosphorescent resin is fixed to the tape and it is difficult to remove it.

<Embodiment 5: Effect>
By using the passage structure of the present embodiment, the evacuation route can be displayed in an easy-to-understand manner for pedestrians even when darkness occurs during a disaster or power failure. In addition, the passage structure according to the present embodiment has the flame-retardant phosphorescent resin embedded in the joint, so that it does not become an obstacle for the pedestrian and can reduce the chance of wear due to contact with the pedestrian. .

<Embodiment 6>
<Sixth Embodiment: Concept>
The present embodiment relates to a passage structure in which a joint where a flame-retardant phosphorescent resin is disposed is a tile and a gap between the tiles.

<Embodiment 6: Configuration>
In this embodiment, the joint provided in the road surface portion (0602) is a gap generated by combining one or more of inorganic tiles, organic tiles, mortar blocks, and concrete blocks used for road surface paving. The road surface portion (0602) may be a combination of different tiles or blocks. For example, a structure in which square organic tiles and inorganic tiles are combined in a checkered pattern may be used. Even if the tiles can be arranged without a gap, if a certain amount of gap is provided, the phosphorescent filler is easily arranged.

  The shape of the tile is not limited to a square, but may be a rectangle, a triangle, a hexagon, or the like. In addition to combining tiles having the same shape, tiles having different shapes such as a square and a rectangle, and a triangle and a hexagon may be combined.

  Other configurations are the same as those in the fifth embodiment.

<Embodiment 6: Effect>
Since the road surface is usually made of a hard material, it is often difficult to dig a groove for placing the flame-retardant phosphorescent resin. In this embodiment, the joint where the flame-retardant phosphorescent resin is disposed is a gap such as a tile or a block, so that it is not necessary to dig a new groove. In addition, the flame retardant phosphorescent resin also has a role as an adhesive for bonding the tiles together, and the stability of the tiles laid on the road surface is increased. In addition, by filling the joint with the flame retardant phosphorescent resin, it is possible to prevent the heel of the stiletto pinch from being caught in the joint by the joint of the tile or the block.

<Embodiment 7>
<Embodiment 7: Concept>
In this embodiment, the flame retardant phosphorescent resin disposed in the joint indicates the path and direction of the evacuation route, so that the pedestrian can easily reach the evacuation exit. About.

<Embodiment 7: Configuration>
In the present embodiment, the flame-retardant phosphorescent resin (0603) is arranged so as to be a figure for guiding escape. The figure for evacuation guidance is, for example, an arrow shape indicating the evacuation direction, a simple figure such as ◯, ×, a sign indicating the evacuation route, and the like.

  FIG. 8 shows an example of the passage structure of the present embodiment. The passage structure shown in FIG. 8 is a combination of triangular tiles and a flame-retardant phosphorescent resin placed on part of the tile joints. If the flame retardant phosphorescent resin is disposed only in the portion indicated by the bold line in the joint, an arrow shape emerges when it becomes dark.

  FIG. 9 shows a state in which an evacuation route is shown in the dark by a passage structure in which flame-retardant phosphorescent resin is arranged in an arrow shape. When the flame-retardant phosphorescent resin (0901) is simply placed on the line, the pedestrian does not know which direction to escape and may escape in the opposite direction. If flame-retardant phosphorescent resin (0901) is arrange | positioned in the arrow shape like FIG. 9, a pedestrian does not mistake the direction of an evacuation exit, and safety improves more.

  Other configurations are the same as those of the fifth embodiment.

<Embodiment 7: Effect>
The passage structure of the present embodiment is a figure for the flame-retardant phosphorescent resin to indicate the evacuation route, so that the pedestrian can reach the evacuation route more easily, leading to an improvement in safety.

<Embodiment 8>
<Eighth embodiment: concept>
The present embodiment relates to a passage structure in which a flame retardant phosphorescent resin has high wear resistance.

<Eighth embodiment: configuration>
In this embodiment, the abrasion resistance of the flame retardant phosphorescent resin (0603) is determined by the test according to JISK5600-5-8, where the load of the wear wheel is 1 kg, the type of abrasive paper is CS-17, and the rotation speed is 1000 times. In this case, the wear loss is 500 mg or less. JISK5600-5-8 is a standard for wear resistance determined by the Japan Industrial Standards Committee. The rotating shaft with abrasive paper is rotated at a constant load and speed, and the wear weight is measured. This is a standard for quantifying the wear resistance. That is, under a predetermined test condition, the smaller the wear weight, the higher the wear resistance. Detailed conditions such as the shape of the wear wheel and the test method are described in JISK5600-5-8. When the wear resistance is below the above level, the flame retardant phosphorescent resin (0603) is easily consumed due to abrasion, and it is necessary to apply the flame retardant phosphorescent resin again, which is not preferable.

  Other configurations are the same as those of the first embodiment.

<Embodiment 8: Effect>
The passage structure according to the present embodiment uses a flame-resistant phosphorescent resin having high wear resistance, so that it is not necessary to reapply the flame-retardant phosphorescent resin many times, leading to cost reduction.

FIG. 3 is a conceptual diagram for explaining the first embodiment. The figure which shows an example of the coating method of Embodiment 1. FIG. The figure which shows the material structure of Embodiment 4. FIG. The figure which shows an example of the coating method of Embodiment 4. FIG. FIG. 6 is a conceptual diagram for explaining a fifth embodiment. FIG. 6 is a schematic view of a passage structure according to a fifth embodiment. The figure explaining the coating method of Embodiment 5. FIG. An example of the channel | path structure of Embodiment 7. FIG. A state in which an evacuation route is guided by the passage structure according to the seventh embodiment.

Claims (26)

  A flame retardant phosphorescent resin comprising a flame retardant resin and a phosphorescent pigment. The flame retardant resin has the following chemical formula 1

(Wherein R ¹ is a hydrogen atom, a C ₁ to C ₅ alkyl group or an acyl group; R ² to R ⁶ are the same or different each selected from a hydrogen atom, an OR ¹ group or a monovalent hydrocarbon group) Group, n is a number of 0 to 15), and a liquid organocontaining 50% by weight or more of a silicon component in terms of SiO ₂ oxide Polysiloxane (A),
The following chemical formula 2 or 3

(Wherein M is an aluminum or boron element; Q is a silicon, titanium or zirconium element; R ⁸ is a hydrogen atom or a C ₁ to C ₅ alkyl group, acyl group or oxime group; R ⁷ is a hydrogen atom, OR ⁸ group Or a group selected from monovalent hydrocarbon groups; p is 1 or 2; m is an integer of 1 to 3), and a crosslinking agent (B) comprising one or more organometallic compounds represented by: , Zinc, cobalt, aluminum, titanium, phosphoric acid, or a metal-containing organic compound of two or more elements of phosphoric acid or tin, and a curing catalyst (C) in which a catalytic reaction blocking agent is blended. (M is aluminum, boron, silicon, titanium, zirconium element, y is the valence of the metal element) the total metal element component to the liquid composition contains MO y _{/ 2} oxide basis expressed by 4 Is a room temperature curing organosiloxane compositions containing wt% or more, the flame retardant phosphorescent resin according to claim 1.   The flame retardant phosphorescent resin according to claim 1 or 2, wherein a ratio of the phosphorescent pigment to the flame retardant resin is 5% or more and 30% or less by weight.   The flame retardant phosphorescent resin according to any one of claims 1 to 3, wherein the phosphorescent pigment is a strontium aluminate phosphorescent pigment. The strontium phosphorescent pigment _{aluminate, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0.2,0.0001 <m <0.2,0. The flame-retardant phosphorescent resin according to claim 4, represented by 0001 <k <0.2).   The flame retardant phosphorescent resin according to any one of claims 1 to 5, further comprising any one or more of a reinforcing agent, a thickener, and a vibration proofing agent.   The flame retardant phosphorescent resin according to claim 6, wherein the reinforcing agent is glass fiber and / or glass flux.   The flame retardant phosphorescent resin according to claim 6 or 7, wherein the thickener is fine powder silica.   The flame retardant phosphorescent resin according to any one of claims 6 to 8, wherein the vibration-resistant agent is a silicone ball and / or a silicone-based flexible agent. A mixing step in which a flame retardant resin and a phosphorescent pigment are mixed to form a coating agent;
A cleaning step of cleaning the floor and / or wall to which the coating agent is to be applied;
An application step of applying the coating agent to the floor and / or wall surface;
After the application is completed, a curing step for curing until the coating agent is cured,
A flame retardant phosphorescent resin coating method comprising: The flame retardant phosphorescent resin coating method according to claim 10, wherein the flame retardant resin is the room temperature curable organosiloxane composition.   The flame retardant phosphorescent resin coating method according to claim 10 or 11, wherein a ratio of the phosphorescent pigment to the flame retardant resin is 5% or more and 30% or less by weight.   The flame retardant phosphorescent resin coating method according to any one of claims 10 to 12, wherein the phosphorescent pigment is a strontium aluminate phosphorescent pigment. The strontium phosphorescent pigment _{aluminate, Sr 1-n-m Eu} n Dy m Al 2-k B k O 4 (0.0001 <n <0.2,0.0001 <m <0.2,0. The flame-retardant phosphorescent resin coating method according to claim 13, represented by 0001 <k <0.2).   The flame-retardant phosphorescent resin according to any one of claims 10 to 14, wherein the mixing step further mixes at least one of a reinforcing agent, a thickener, and a vibration-resistant agent to form a coating agent. Application method.   The flame retardant phosphorescent resin coating method according to claim 15, wherein the reinforcing agent is glass fiber and / or glass flux.   The flame retardant phosphorescent resin coating method according to claim 15 or 16, wherein the thickener is fine powder silica.   The flame retardant phosphorescent resin coating method according to any one of claims 15 to 17, wherein the vibration-resistant agent is a silicone ball and / or a silicone-based flexible agent. _{Sr 1-n-m Eu n} Dy m Al 2-k B k O 4 in (0.0001 <n <0.2,0.0001 <m <0.2,0.0001 <k <0.2) Luminescent pigment represented. A firing step of firing SrO, Al ₂ O ₃ , Eu ₂ O ₃ , Dy ₂ O ₃ , and B ₂ O ₃ in a reducing atmosphere to form a fired mixture;
A cooling step of cooling the fired mixture and then washing with acetic acid and glycerin;
A phosphorescent pigment manufacturing method comprising: A lighting section;
A road surface portion provided with joints illuminated by the illumination unit;
A passage structure comprising the flame retardant phosphorescent resin according to any one of claims 1 to 9 disposed on the road surface portion.   The passage according to claim 21, wherein a width of the flame retardant phosphorescent resin filled in the joint is 3 mm or more and 3 cm or less, and a depth of the flame retardant phosphorescent resin filled in the joint is 1 mm or more and 1 cm or less. Structure.   23. The passage structure according to claim 21, wherein the joint provided in the road surface portion is a gap generated by combining any one or more of an inorganic tile, an organic tile, a mortar block, and a concrete block used for road pavement. .   The passage structure according to any one of claims 21 to 23, wherein the joint where the flame-retardant phosphorescent resin provided on the road surface portion is arranged is a figure for evacuation guidance.   In the test according to JISK5600-5-8, the wear resistance of the flame retardant phosphorescent resin disposed on the joint provided on the road surface is 1 kg of wear wheel load, the type of abrasive paper is CS-17, and the rotational speed. 25 is a passage structure according to any one of claims 21 to 24, wherein the wear loss is 500 mg or less in the case of 1000 times. A mixing step in which the flame retardant resin according to any one of claims 1 to 9 and a phosphorescent pigment are mixed to form a coating agent;
A cleaning step of cleaning the floor and / or wall to which the coating agent is to be applied;
An application step of applying the coating agent to a joint of a passage illuminated by an illumination unit;
After the application is completed, a curing step for curing until the coating agent is cured,
A method for manufacturing a passage structure.

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