KR100280232B1 - Fluorescent and luminous urethane manufacturing method and composition - Google Patents

Abstract

The present invention is to detect the object in a dark place during the power outage in the daytime emergency and a blackout to recognize the surrounding situation in more detail, for example, personal items of workers working in construction and industrial sites Fluorescent and luminous urethane manufacturing method for securing driver's visibility during daytime as well as in dark night to prevent safety accidents by applying to bags, sneakers, etc. It relates to a composition.

One embodiment of the technical means for solving the above object is [in a melted prepolymer, 100 parts by weight of a plasticizer, 10 to 12 parts by weight of a fluorescent pigment and 20 to a photoluminescent pigment in the molten prepolymer. Adding a mixed pigment to 25 parts by weight; Vacuum defoaming the prepolymer in which the mixed pigment is added; It is composed of a step of forming a fluorescent and luminous thermosetting urethane material by mixing and stirring the curing agent in the prepolymer in which the mixed pigment is added, the plasticizer is DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used Preferably, 100 parts by weight of the prepolymer is mixed with 5 to 6 parts by weight of the mixed pigment, while in the conventional polyol compound that is molten, the molten polyol mixture is added to the molten polyol mixture. A mixture of 100 parts by weight of plasticizer, 10-12 parts by weight of fluorescent pigment and 20-25 parts by weight of photoluminescent pigment; The mixed pigment is added to the polyol mixture in which the polyisocyanate (polyisocyante) is mixed and stirred to form a fluorescent and luminous foamed urethane material, and the plasticizer is DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used, preferably a method for producing a fluorescent and luminous urethane, characterized in that 5 to 6 parts by weight of a mixed pigment is mixed with 100 parts by weight of the polyol mixture, a conventional prepolymer or Fluorine and luminous urethane composition, characterized in that a mixed pigment comprising 100 parts by weight of a DOP solution, 10-12 parts by weight of a fluorescent pigment and 20-25 parts by weight of a photoluminescent pigment is added.

As described above, the present invention configured to provide a more durable effect when used in industrial sites, traffic signs, etc. by forming a urethane to have a fluorescent and luminous properties, in particular, the present invention is a light emitting urethane luminous by adding a fluorescent pigment, etc. By emitting light with more beautiful colors than the city, it provides the effect of increasing the recognition of objects in the dark at daytime as well as at night.

Description

Fluorescent and luminous urethane manufacturing method and composition

The present invention relates to a method of manufacturing a fluorescent and luminous urethane (urethane), and a composition thereof, which is fluorescent in daylight and detects an object in a dark place during a power outage at night, so that the surrounding situation can be recognized. Workers' personal belongings in construction and industrial sites, such as bags and sneakers, for example, to prevent safety accidents, or especially for traffic guidance signs or centerline signs on motor roads The present invention relates to a fluorescent and luminous urethane manufacturing method and a composition for securing visibility of a city driver.

In general, industrial or construction sites or automobile roads or facilities installed or installed, for example, traffic guidance signs and center line lights are manufactured and attached or installed with materials that emit light in order to prevent safety accidents. The use of materials can enhance the ability of workers to work in dark places, especially at night. Furthermore, on automobile roads, it is an essential facility or sign for the driver to recognize the road situation at night and drive safely.

As described above, the fluorescent material or the luminous material emits by reflecting or accumulating light incident from the outside. In order to increase the reflection efficiency of light incident from the outside, a reflector is used, and is installed in a hazardous area. It is used for guide signs of construction, industrial sites, roads, etc. so that the surrounding environment can be recognized in the dark place by using the luminous substance or the isomer of reflector.

Fluorescent or luminous materials and reflectors are used in a variety of construction and industrial applications. Coated on personal items such as bags and sneakers, for example, to identify them in a dark place so that the wearer can be recognized. In construction sites, it is applied to non-slip floor sheets and stairs sheets, and in industrial sites, it is installed in places that require special recognition for the prevention of safety accidents, and it is used for traffic guide signs so that drivers can be aware of road conditions.

Fluorescent or luminous materials and reflectors used in construction and industrial or traffic sites require durability. In an industrial or traffic site, shocks caused by strong objects are frequently generated and must be durable to withstand them. The object of the conventional reflective plate or synthetic resin or plastic product for guiding is formed in a state in which the fluorescent or luminous material is applied, so that it is damaged or discolored due to a strong impact, which is weak in durability.

The present invention has a fluorescent and luminous urethane manufacturing method having fluorescence and luminous properties, strong durability against shock and shock absorption to recognize the surrounding conditions in a dark place in the daytime, nighttime, as well as emergency power outages, and its It is an object to provide a composition.

1 is a process chart showing a fluorescent and luminous thermosetting urethane manufacturing method according to the present invention.

2 is a table showing the mixing ratio of the mixed pigments shown in FIG.

3 is a table showing the mixing ratio with the mixed pigment, prepolymer and curing agent shown in FIG.

Figure 4 is a process chart showing a fluorescent and luminous foam urethane manufacturing method of an embodiment of the present invention.

FIG. 5 is a table showing the mixing ratio of the polyol compound, polyisocyanate and mixed pigment shown in FIG.

FIG. 6 is a table showing examples of the blending ratios of the polyol compound, polyisocyanate and mixed pigments shown in FIG.

7 is a real picture showing the luminous properties of the existing product and the present invention at night.

8 is a real picture showing the fluorescence of the existing product and the present invention during the day.

In order to achieve the above object, the present invention is [in a conventional prepolymer melted; Into the molten prepolymer, a mixed pigment mixed with 100 parts by weight of plasticizer, 10 to 12 parts by weight of fluorescent pigment and 20 to 25 parts by weight of photoluminescent pigment; Vacuum defoaming the prepolymer in which the mixed pigment is added; It is composed of a step of forming a fluorescent and luminous thermosetting urethane material by mixing and stirring the curing agent in the prepolymer in which the mixed pigment is added, the plasticizer is DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used Preferably, 5 to 6 parts by weight of the mixed pigment is mixed to 100 parts by weight of the prepolymer, while in the conventional polyol compound (melt),

Adding a mixed pigment mixed with 100 parts by weight of a plasticizer, 10-12 parts by weight of a fluorescent pigment and 20-25 parts by weight of a photoluminescent pigment to the molten polyol mixture; It is characterized by another step consisting of forming a fluorescent and luminous foamed urethane material by mixing and stirring the polyisocyanate to the polyol mixture into which the mixed pigment is added,

The plasticizer is a DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used, preferably 100 parts by weight of the polyol mixture, 5 to 6 parts by weight of a mixed pigment is characterized in that And a luminous urethane manufacturing method and a mixed pigment containing 100 parts by weight of a DOP solution, 10 to 12 parts by weight of a fluorescent pigment and 20 to 25 parts by weight of a photoluminescent pigment into a conventional prepolymer or polyol mixture. And a luminous urethane composition] can achieve the above object.

The present invention will be described in more detail with reference to the accompanying drawings as follows.

1 is a process chart showing a fluorescence and luminous thermosetting urethane manufacturing method according to the present invention. As shown, the step (S1) of melting the prepolymer to a predetermined temperature, mixed with 100 parts by weight of a plasticizer, 10 to 12 parts by weight of a fluorescent pigment and 20 to 25 parts by weight of a photoluminescent pigment in the molten prepolymer Injecting the pigment (S2), Vacuum degassing the prepolymer in which the mixed pigment is added (S3), Maintaining the prepolymer in which the defoaming mixed pigment is added at a predetermined temperature state (S4) and the curing agent in a predetermined temperature state Maintaining in step (S5), and mixing and stirring the prepolymer and the curing agent to which the mixed pigment is maintained at a predetermined temperature state to produce a fluorescent and luminous thermosetting urethane material (S6), and forming a fluorescent and luminous urethane material It consists of S7.

Before describing the preparation method of the present invention in more detail, a general scheme for the prepolymer and polyol mixtures employed in the present invention will be described and the preparation method of the present invention will be described in detail.

General Scheme

The structural formula of the curing agent (MOCA)

(3,3'-Dichoro-4.4-diamino diphenyl methane) and the general scheme for producing polyurethane is

That is, the prepolymer is a liquid polyurethane of terminal isocyanate type obtained by reaction of terminal isocyanate obtained by reaction of polyester, polyester and aromatic diisocyanate. The curing agent (MOCA) is added to the prepolymer and reacted to form various necessary elastomeric products having excellent wear resistance, oil resistance, and aging resistance.

The present invention dissolves the aromatic pigments, ie fluorescent and photoluminescent pigments, which are bright in color in a pre-melted conventional prepolymer before reacting the prepolymer and the curing agent, and then adds and mixes them to react at a predetermined temperature. It is possible to obtain a variety of elastomeric products of excellent fluorescence and luminous color.

In other words, in the manufacture of fluorescent and luminous thermosetting urethane, the fluorescence and luminous pigments are fixed at a predetermined ratio in the state of preparing a prepolymer by reacting diisocyanate (OCN-R'-NCO) with a conventional polyol (HO-R-OH). After mixing, vacuum degassing and then curing agent is mixed. Fluorescent and luminous foaming urethane react with diisocyanate (OCN-R'-NCO) to a conventional polyol (HO-R-OH), After producing a polyol mixture in which glycols are mixed, fluorescence, luminous pigment and polydiisocyanate are mixed.

In the present invention as described above, in the manufacture of a fluorescent and luminous thermosetting urethane and a fluorescent and luminous foam urethane, it can be said that there is a significant difference depending on the timing of the fluorescent and luminous pigments.

Such a prepolymer or polyol mixture will be described in detail with respect to the time and amount of the fluorescence and luminous pigments and other preparation methods for the present invention.

The prepolymer is heated to a predetermined temperature and melted (S1). After heating at 80 degreeC for 90 hours at 90 degreeC, a prepolymer is melted and mixed pigment is mix | blended in a ratio of predetermined ratio in this state. A D.O.P (DiOctyl Phthalate) (futal acid dioxyl) solution, a fluorescent pigment and a photoluminescent pigment are blended in a ratio of a predetermined ratio. D.O.P solutions are used to facilitate the processing of products and to control their elasticity and strength. DOP solution, fluorescent pigment and photoluminescent pigment are mixed by adding powdered fluorescent pigment to DOP solution, and then adding mixed photoluminescent pigment to prepare mixed pigment and adding it to the pre-melted prepolymer. By dispersing and dissolving evenly, the product can be produced in many different colors.

Mixed pigments are HBr, NaBr, TiO ₂ , CoO, FeO ₃ , NaHSO ₃ , ZnO ₂ , KMnO ₄ , 2H ₂ O, MnCl ₂ 4H ₂ O, Sb ₂ O ₃ , TiCl ₄ , (NH ₄ ) Mo ₇ O ₄ Inorganic materials such as 4H ₂ O may be used by mixing the above inorganic materials to show a desired color. Fluorescent pigments are composed of diazomethane (C ₆ H ₅ N = NC ₆ H ₅ ) containing mixed inorganic materials and azo groups. Fluorescent pigments include anthraquinone (C ₁₄ H ₈ O ₃ ), which is a slight aromatic compound in diazomethane, and photoluminescent pigments are composed of some diazomethane in anthraquinone. A mixed pigment is prepared by mixing the DOP solution in the order of a fluorescent pigment having such a component and a photoluminescent pigment.

The mixing ratio of the prepared mixed pigment is measured and added so that the fluorescent pigment is 10 to 12 parts by weight if the weight part of the D.O.P solution is 100 as in FIG. For example, if the D.O.P solution is 100 g, the fluorescent pigment is added so that about 10 g to 12 g. 10 to 12 parts by weight of the fluorescent pigment is added to the D.O.P solution and mixed, and then 20 to 25 parts by weight of the photoluminescent pigment is added and mixed. The D.O.P solution, the fluorescent pigment, and the photoluminescent pigment are mixed in a predetermined weight ratio, and then allowed to stir and dissolve sufficiently.

Fluorescent pigments mixed in DOP solutions give their own color characteristics during the re-reflection of light incident by ultraviolet rays or sunlight during the day, and the phosphorescent pigments emit light in dark places during power outages at night or during emergencies. do. The photoluminescent pigment, which emits light in a dark place, accumulates incident light and emits light for a predetermined time according to the amount of incident light. That is, it is used as a material for emitting light in proportion to the amount of incident light.

After reflecting or accumulating the incident light, fluorescent pigments and photoluminescent pigments diverging according to the amount of accumulated light should be added to the D.O.P solution to remove moisture contained in the mixed pigment. A hot air oven (not shown) is used to remove water contained in the mixed pigment. Conditions for removing the water contained in the mixed pigment using a hot air oven is stored for about 1 hour between 100 ℃ to 110 ℃ to remove the moisture sufficiently.

The mixed pigment from which the moisture is sufficiently removed is added to the molten prepolymer while being kept at 80 ° C to 90 ° C. As a mixed pigment added to the prepolymer, diazomethane including azo groups and an anthraquinone, an aromatic compound, are highly mixed with the prepolymer, thereby producing fluorescent and luminous urethanes having various colors.

The mixed pigment added to 100 parts by weight of the melted prepolymer should not exceed 8 parts by weight. That is, when 8 parts by weight or more of the mixed pigment is added to the molten prepolymer, an excessively added mixed pigment breaks the binding ring between molecules of the polymer prepolymer. As a result, the intermolecular ring of the prepolymer is weakened and the physical properties of the polymer are lowered, so that the mixed pigment is added to 8 parts by weight or less in order to prevent this.

When the mixed pigment is added to the molten prepolymer, the molten prepolymer into which the mixed pigment is added is degassed in vacuum (S3). A vacuum degassing apparatus (not shown) is used to remove water, air, and the like contained in the molten prepolymer to which the mixed pigment is added. To remove moisture or air, remove water or air by heating from 90 ° C to 100 ° C for 40 to 60 minutes. The pressure in the vacuum defoaming apparatus is maintained at about 5 mmHg in order to remove moisture or air contained in the molten prepolymer to which the mixed pigment is added.

The molten prepolymer in which the mixed pigment is added by using the vacuum degassing apparatus is maintained at 80 ° C. to 90 ° C. (S4). The curing agent for curing the molten prepolymer in the state of the mixed pigment is maintained to be between 100 ℃ to 120 ℃ (S5). Fluorescent and luminous thermosetting urethane are prepared by mixing and stirring the curing agent and the molten prepolymer maintained at 100 ° C to 120 ° C (S6).

The molten prepolymer mixed with the mixed pigment and the curing agent in the liquid state are sufficiently mixed using an agitator (not shown) to prepare a fluorescent and luminous thermosetting urethane material. The prepolymer mixed with the curing agent with sufficient agitation adds isocyanate functional groups to both ends of each molecule. Isocyanate functional groups react with polyfunctional groups of amines or glycols contained in the curing agent to form urethanes having thermosetting properties. That is, the functional group of the isocyanate of the prepolymer containing the mixed pigment is bonded to the polyfunctional group of the amine or glycols contained in the curing agent to prepare a fluorescent and luminous thermosetting urethane material.

Prepolymers, curing agents, and mixed pigments for producing fluorescent and luminous thermosetting urethane materials have the same blending ratio as in FIG. That is, when the prepolymer is 100 parts by weight, the curing agent is mixed at 14.3 to 15.2 parts by weight, and the mixed pigment is mixed at 5 to 6 parts by weight. In this blending ratio, the fluorescent and luminous urethane materials formed of the prepolymer, the curing agent, and the mixed pigment are manufactured by forming a fluorescent and luminous thermosetting urethane having a predetermined form (S7).

Fluorescent and luminous foamed urethanes having elasticity to fluorescent and luminous urethanes are prepared by treatment at lower temperatures than fluorescent and luminous thermoset urethanes. Fluorescent and noctilucent foamed urethane production method will be described with reference to the accompanying drawings, omitting the same as the fluorescent and luminous thermosetting urethane manufacturing method as follows.

4 is a process chart showing a fluorescent and luminous foamed urethane manufacturing method according to an embodiment of the present invention. As shown, melting the polyol compound to a predetermined temperature (S11) and mixing the molten polyol mixture with 100 parts by weight of plasticizer, 10 to 12 parts by weight of fluorescent pigment and 20 to 25 parts by weight of photoluminescent pigment. Mixing the mixed pigment (S12), maintaining the polyol mixture to which the mixed pigment is added at a predetermined temperature state (S13), and mixing the polyol mixture and polyisocyanate to which the mixed pigment is maintained at the predetermined temperature state. It comprises a step (S15) of preparing a fluorescent and luminous foamed urethane material by stirring, and a step (S16) of forming a fluorescent and luminous foamed urethane material.

Referring to the fluorescent and luminous foam urethane manufacturing method of an embodiment of the present invention in more detail as follows.

The polyol mixture is melted at a predetermined temperature (S11). At this time, the melting temperature is heated by melting for about 1 hour from 70 ℃ to 80 ℃. The mixed pigment is added to the molten polyol mixture (S12). Mixed pigments are prepared by sequentially adding fluorescent pigments and photoluminescent pigments to a D.O.P solution. The preparation conditions of the mixed pigments are the same as in the manufacture of fluorescent and luminous thermosetting urethane, and the holding temperature before the addition to the polyol mixture is maintained at 35 ° C to 40 ° C.

When the polyol mixture is melted, a mixed pigment is added (S12). The polyol mixture into which the mixed pigment is added is maintained at 34 ° C to 40 ° C (S13). In the state where the polyol mixture is maintained at 35 ° C to 40 ° C, the polyisocyanate is also maintained at 35 ° C to 40 ° C in a liquid state (S14). The polyol mixture is maintained between 35 ° C. and 40 ° C. and polyisocyanate is used and maintained at 40 ° C.

The polyol mixture maintained at 35 ° C. to 40 ° C. and the polyisocyanate are mixed and stirred by a stirrer to form a fluorescent and luminous foamed urethane material (S15). The fluorescent and luminous foamed urethane materials are prepared by stirring for at least 8 to 11 seconds to sufficiently mix the polyol mixture and the polyisocyanate to which the mixed pigment is added. Fluorescent and luminous foamed urethane materials have hardness determined by the blending ratio of polyisocyanates.

The hardness of the fluorescent and luminous foamed urethane material is from 60 ° A to 70 ° A when the polyisocyanate is 120 parts by weight as shown in FIG. In this case, the blending ratio of the polyol mixture is 100 parts by weight, and the mixed pigment is included in the ratio of 5 to 6 parts by weight. When the hardness of the fluorescent and luminous foamed urethane material is 40 ° A to 45 ° A, the blending ratio of the polyol mixture, the polyisocyanate and the mixed pigment is 100 parts by weight, 75 parts by weight and 5 to 5, respectively, as shown in FIG. It is contained in the ratio of 6 weight part. That is, the hardness of the fluorescent and luminous foaming urethanes is determined by the kind of polyol, but also by the blending ratio of polyisocyanate.

On the other hand, Figure 7 shows a real picture showing the luminous properties of the existing product and the present invention at night, Figure 8 shows a real picture showing the fluorescent light of the existing product and the present invention at daytime.

As shown in the real picture, the present invention shows not only durability but also light emission of beautiful colors and high recognition of an object.

In the present invention, the mixed pigments included in the fluorescent and luminous thermosetting urethanes or the fluorescent and luminous foamed urethane materials are used by combining the fluorescent and luminous phosphorescent pigments, that is, by adding the fluorescent and luminous pigments to the urethane material to have the fluorescent and luminous properties. By having fluorescence and luminous properties at the same time urethane can be used in construction and industrial sites, traffic guide signs, disaster safety field, necessities, and the like by using fluorescence and luminous urethane.

As described above, the present invention is formed with urethane to have fluorescence and luminous properties. As a result of the use of a band or a material having existing luminous properties for a long time, the present invention solves problems such as fluorescence and luminous fading or disappearance of luminous properties due to damage. In other words, in the process of manufacturing urethane, urethane is prepared by mixing a mixture of fluorescent and luminous pigments at a constant ratio to produce fluorine and luminous properties up to the inside even if it is torn, broken, cut or otherwise damaged during long-term use. It is manufactured so that it can be used. Therefore, even if it is used for a long time, the effect does not disappear or fade. Furthermore, by using a mixed pigment in which fluorescent pigments are mixed with luminous pigments, the degree of reflection of light from products manufactured only with the luminous pigments, which are conventional luminous pigments, is used. The visibility of objects is seen in the above Figures 7 and 8 As you can see the effect is superior. Therefore, it provides a more durable effect when used in construction and industrial sites, traffic guide signs, etc. In particular, the present invention is characterized by the complex effect of the fluorescent pigment during the day, the phosphorescent pigment at night by adding a fluorescent pigment, etc. When the luminous urethane emits light with a more beautiful color, it provides an effect of increasing the recognition of objects in the dark day and night.

Claims (7)

In the conventional melted prepolymer (prepolymer), to the molten prepolymer, a mixed pigment mixed with 100 parts by weight of plasticizer, 10 to 12 parts by weight of fluorescent pigment and 20 to 25 parts by weight of photoluminescent pigment; Vacuum defoaming the prepolymer in which the mixed pigment is added; Fluorescent and luminous urethane manufacturing method comprising the step of forming a fluorescent and luminous thermosetting urethane material by mixing and stirring the curing agent in the prepolymer to the mixed pigment. According to claim 1, wherein the plasticizer is a fluorescent and luminous urethane manufacturing method, characterized in that DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used. The method of claim 1, wherein 5 to 6 parts by weight of the mixed pigment is mixed with 100 parts by weight of the prepolymer. In the melted conventional polyol compound (polyol compound), to the molten polyol mixture, adding a mixed pigment mixed with 100 parts by weight of plasticizer, 10 to 12 parts by weight of fluorescent pigment and 20 to 25 parts by weight of photoluminescent pigment; Fluorescent and luminous urethane manufacturing method comprising the step of mixing and stirring the polyisocyanate to the polyol mixture into which the mixed pigment is added to form a fluorescent and luminous foamed urethane material. The method of claim 4, wherein the plasticizer is a fluorescence and luminous urethane manufacturing method, characterized in that DOP [DiOctyl Phthalate, OC ₆ H ₄ (COOC ₈ H ₁₇ ) ₂ ] solution is used. The method of claim 4, wherein 5 to 6 parts by weight of the mixed pigment is mixed with 100 parts by weight of the polyol mixture. A fluorescent and luminous urethane composition comprising a mixture of 100 parts by weight of a D.O.P solution, 10-12 parts by weight of a fluorescent pigment, and 20-25 parts by weight of a photoluminescent pigment into a conventional prepolymer or polyol mixture.