JPS6077158A - Luminescent resin concrete - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to resin concrete having luminescent properties.

Luminescent pigments are commercially available and have the property of accumulating light when they receive it from sunlight, fluorescent lights, etc. and continuing to glow in the dark even after the light source has disappeared, and are used for a variety of purposes. . For example, it is mixed with glass to make a sheet or plate-like product, which is then cut into the desired shape or character and pasted onto concrete or the like.

It is also in liquid form. However, these luminescent products have various problems such as reduced luminescence due to wear, combustibility, insufficient adhesion and easy to fall off, and are expensive and dull, so their uses are extremely limited. ing.

The present inventors completed this invention as a result of studies to compensate for the above-mentioned drawbacks.

This invention is a luminescent resin concrete that is composed of three components: an inorganic filler, a luminescent pigment, and a synthetic resin, and in which the inorganic filler accounts for about 40% by weight or more of the total amount thereof.

Luminous pigments are substances that emit phosphorescence, and their main components are, for example, artificial alkaline earth metal sulfides (calculum sulfide, strontium sulfide, barium sulfide) and zinc sulfide, with trace amounts of heavy metals (manganese). , copper, lead, zinc, etc.). When a trace amount of a radioactive element such as radium is added to these phosphorescent pigments, they retain their phosphorescence for a longer period of time than their emission IK and continue to emit light in the dark.

If a small amount of copper is added as an activator and an alkali metal flux is mixed and fired, it will be a sulfide of alkali metal. Compared to other materials, it is more stable than other materials, such as blackening due to sunlight, etc. The luminescent pigment is preferably used in an amount of about 0.2 to 50% by weight, or preferably about 1 to 35% by weight, based on the total amount of the inorganic filler, synthetic resin, and luminescent pigment. If it is below the above range, the luminescence will be reduced to such an extent that it cannot be put to practical use, and if it is above the above range, the advantages of the resin concrete of the present invention, such as flame retardancy and abrasion resistance, are likely to be impaired.

One of the other components used in the present invention is a synthetic resin with excellent transparency. Specifically, they include furan resin, epoxy resin, unsaturated polyester resin, urethane resin, polystyrene resin, methacrylic resin, and the like. If the transparency of the synthetic resin is high, the luminance of the resin concrete will be high. The resin concrete of the present invention is produced by mixing a polymerizable synthetic resin that is liquid at room temperature (10 to 35 ° C.) with other components used in the present invention, and then subjecting the resin to a polymerization reaction using a curing catalyst. , it is easy to contain a large amount of inorganic filler. Particularly preferred synthetic resins are unsaturated polyester resins and methacrylic resins. Unsaturated polyester resin is a resin that can be cured by mixing a vinyl compound such as styrene with an unsaturated polyester obtained by a polycondensation reaction of a glycol compound and an unsaturated dicarboxylic acid, and causing crosslinking by a polymerization reaction using a catalyst. It is.

When using unsaturated polyester resin, the surface hardness of resin concrete is a dog. A polymerizable mixed solution of a methyl methacrylate polymer and a monomer mainly composed of methyl methacrylate (hereinafter referred to as "acrylic syrup") is subjected to a polymerization reaction using a catalyst to yield a methacrylic resin. By using methacrylic resin, resin concrete with excellent properties such as water resistance, weather resistance, and luminance can be easily obtained. The content of methyl methacrylate units in the methacrylic resin is preferably about 50% by weight or more.

As the acrylic syrup, it is preferable to use one containing about 5 to 40% by weight of methyl methacrylate polymer and having a solution viscosity of about 0.5 to 30 poise at 25°C. Examples of the catalyst include radical polymerization catalysts such as benzoyl peroxide, lauroyl peroxide, and azobisisobutyronitrile. Radical polymerization catalysts can be used alone or in combination with other substances. When a redox catalyst, for example a combination of a peroxide such as benzoyl peroxide and a tertiary amine such as N,N-dimethylaniline, is used, unsaturated polyester resin liquid and acrylic syrup can be produced not only under heating but also at room temperature of 10 to 35°C. Can be cured in a short time. Of the total amount of the inorganic filler, synthetic resin, and luminescent pigment, the synthetic resin is used in an amount of about 5 to 40% by weight, preferably about 10 to 30% by weight.

Other ingredients used in the present invention are inorganic fillers.

Specific examples of inorganic fillers other than luminescent pigments include calcium carbonate, barium sulfate, talc, and kaori, and these can be used alone or in combination of two or more. The inorganic filler is used in an amount of about 40% by weight, preferably about 50% by weight or more, of the total amount of the inorganic filler, synthetic resin, and luminescent pigment. When used in such a large amount, properties such as wear resistance and flame retardance are imparted to the resin concrete of the present invention. When using an inorganic filler with an average particle size of approximately 0.2 mm or more,
Since the emitted light is blocked, the luminance of the emitted light increases.

The average particle size of highly transparent silica sand, limestone, etc. containing about 50% by weight or more of silicon dioxide and calcium carbonate is about 0.2
When inorganic aggregate with a diameter of mm or more is used, luminescence brightness increases. Another preferred inorganic filler for use is hydrated fine-grained inorganic powder. Specifically, calcium sulfate dihydrate, basic magnesium carbonate dihydrate, alumina trihydrate, etc., and mixtures of these hydrated fine inorganic powders with unsaturated polyester resin, methacrylic resin, etc. Compared to calcium carbonate, etc., the luminance of light tends to be higher, and the flame propagation resistance (flame retardance) of the resin concrete of the present invention is also highly improved.

The resin concrete of the present invention can also be produced by a molding method such as a hot press method or an extrusion method, but a mixture consisting of a polymerizable liquid resin, an inorganic filler, and a luminescent pigment is poured onto the casting surface, and It may be produced by curing the mixture at room temperature or under heating.

As shown in FIG. 1, a luminescent layer (1) with higher luminescence properties consisting of an inorganic filler, a synthetic resin, and a luminescent pigment can be provided to a desired thickness on the surface layer of resin concrete. The thickness is about 1. On or above, preferably between 3 and 10, not only is there no practical problem in abrasion resistance, but the amount of expensive phosphorescent pigment used is small, making it economical as well as flame retardant.
Resin concrete with excellent dimensional stability etc. can be manufactured. The light-emitting layer (1) and layer (2) can be easily integrated with fRR by pouring the mixture forming the layer (2) on the mixture forming the light-emitting layer (1) and curing it, without using an adhesive. can.

Although containing a large amount of inorganic filler, the luminescent resin concrete of the present invention surprisingly exhibits extremely good luminescence and emits a large amount of luminescent light even in the dark even after the external light source has disappeared. In addition, it has excellent abrasion resistance and flame retardancy, so it is suitable for emergency evacuation signboards and signage tiles for underground passages, tunnels, movie theaters where the masses gather, high-rise buildings, basements, etc. Moreover, it has a display effect as it emits light constantly or for a certain period of time in the darkness even after the external light source such as an electric light is extinguished, making it suitable as a member of furniture and building materials.

Other additives such as fillers such as metal powder and fibers, colorants such as dyes and pigments, light and heat stabilizers, other synthetic resins, viscosity modifiers, etc. can be added to the resin concrete of the present invention to achieve the intended use. can be made to match.

Furthermore, if the surface of the resin concrete of the present invention is coated with a transparent resin by painting or the like, the durability of the luminescent layer can be improved.

The present invention will be explained in more detail below using examples. Parts and percentages are by weight.

Example 1 15 parts of a thermosetting unsaturated polyester resin liquid having a solution viscosity of 8 voids at 25°C, and a luminescent pigment.

(Zinc sulfide phosphor containing traces of copper, specific gravity 4.11 all passes through an 80 mesh sieve.) 15 parts, 70 parts silica sand
1 part, and then 0.2 part of benzoyl peroxide. Pour the mixture into a mold and heat press at 100°C for 20 minutes until the thickness is 20! +1 resin concrete was obtained.

When used as paving stones for an underground passage, it glowed even in the dark for about two hours after a power outage, helping guide passersby to evacuate. Luminescence was not lost even when the surface layer was abraded by passersby, and the resin concrete of this example was self-extinguishing, so it was highly safe against underground fires.

Example 2 An acrylic syrup consisting of 25% methyl methacrylate polymer and 75% methyl methacrylate and having a solution viscosity of 1 void at 25°C was prepared. A mixture of 12 parts of the acrylic syrup, 15 parts of the luminescent pigment of Example 1, 73 parts of crushed limestone (average particle size of about 1 inch), a small amount of benzoyl peroxide, and N,N-dimethylaniline was molded. I poured it.

The cast material was exothermically cured in about 30 minutes in an atmosphere of 25°C. 1
After a period of time, the mold was demolded to obtain luminescent resin concrete with a thickness of 20 mm. Acrylic resin paint was applied to the surface of the resulting resin concrete, and the names of the people were engraved and inked to create nameplates. This was glued to the concrete gatepost. Even after the gate lights were turned off, they continued to glow for about two hours in the darkness, letting visitors know their names. After being exposed to sunlight, wind and rain for three months, no changes in appearance (such as yellowing, minute laces, or whitening due to rainwater) were observed, indicating excellent weather resistance.

Example 3 The same mixture as in Example 2 was cast into a mold to a thickness of about 2 mm, and then 10 parts of the same thermosetting unsaturated polyester resin liquid as in Example] and calcium carbonate powder (average A mixture containing no phosphorescent pigment, consisting of 10 parts (particle size: 5 microns), 80 parts river sand, 0.1 part methyl ethyl ketone peroxide and 0.05 part cobalt naphthenate solution, was further mixed to a thickness of about 15 mm. I poured it. Casting is at 25℃
It heat-cures in about 1 hour in an atmosphere and is demolded after 24 hours to create a 17 m thick, non-warping, luminescent layer with a luminescent layer (1) about 2 thick thick and a layer (2) that does not contain luminescent pigment. Obtained resin concrete. Next, after displaying the words "exit direction" on the surface of the luminescent resin concrete obtained,
It was attached to the concrete wall inside the tunnel with cement mortar.

After the tunnel's lights went out, it glowed for several hours in the darkness, helping to evacuate passersby. The resin concrete of this example was self-extinguishing and safe against tunnel fires, and no decrease in luminescence was observed due to equal pressure of water. The resin concrete of this example contained only a small amount of expensive phosphorescent pigment, so it was excellent in terms of economy.

Example 4 30 parts of unsaturated polyester resin liquid of Example 1, Example 1
A mixture of 10 parts of phosphorescent pigment, 60 parts of alumina trihydrate, 0.3 parts of methyl ethyl ketone peroxide, and 1 part of cobalt naphthenate solution was cast into a mold about 3 cm thick, and then The same mixture as in Example 3, but not containing a luminescent pigment, was poured on top to a thickness of about 7 cm. The cast material hardens exothermically in about 1 hour in an atmosphere of 25°C, and
After a period of time, the mold was demolded to obtain a luminescent resin concrete with a thickness of 10I11+ having a luminescent layer (1) with a thickness of about 3 layers and a shoulder (2) containing no luminescent pigment. After coating the luminescent layer (11) with transparent urethane paint, the resulting resin concrete was used as a washstand, and it emitted light in the dark even after the fire was extinguished.

When I placed a lit cigarette on the sink, the cigarette went out immediately and did not ignite the sink.

Example 5 A composition consisting of 17 parts of the acrylic syrup of Example 2, 3 parts of the luminescent pigment of Example 1, 12 parts of alumina trihydrate, 68 parts of crushed sand, and a small amount of N,N-dimethylaniline was A mixture containing 0.02 part of benzoyl oxide was linearly cast onto a cement mortar bed to a thickness of 2 mm. The cast material was cured in 30 minutes in an atmosphere of 20° C., and a luminescent resin concrete was obtained as marked lines on the cement mortar bed.

Even though the amount of phosphorescent pigment used was small, the luminance in the dark after smoke extinguishing was high, and the luminescence lasted for about 2 hours in the dark.

[Brief explanation of drawings]

Figure 1g1 is a sectional view of resin concrete according to the present invention. Patent applicant: Showa Gas Chemical Industry Co., Ltd. Shimizu Laboratory Co., Ltd. Figure 1

Claims (1)

[Claims] l) Consists of three components: inorganic filler, synthetic resin, and luminescent pigment, and out of the total amount of these, inorganic filler accounts for approximately 40%
Luminescent resin concrete that is more than % by weight.