KR20000060654A - Manufacturing method of textile having retroreflectivity - Google Patents

Abstract

PURPOSE: Provided is a process for producing a reflexive reflection fabric which has excellent water resistance and durability useful for a sports bag, a school bag and a knapsack. CONSTITUTION: The reflexive reflection fabric is obtained by a process containing the steps of: coating and drying 3-12g/m¬2 of an adhesive composition on a surface of a foundation cloth to form an adhesive layer; surface-treating diameter 20-90micron of a surface being a grassbead with silanes type surface treatment; coating and drying 25-85g/m¬2 of a reflexive reflection layer composition on the adhesive layer of the foundation cloth to form a reflexive reflection layer; and then heating the same at the temperature of 90-150°C to harden it.

Description

Manufacturing method of retroreflective fabric {Manufacturing method of textile having retroreflectivity}

The present invention relates to a method of manufacturing a retroreflective fabric that can be used for bags or for garments. More specifically, the present invention provides a beautiful retro-reflective fabric having a high durability by expressing a beautiful color at daytime, having good retroreflective properties under light at night, and preventing the fall of glass beads as a retroreflective material, especially with excellent waterproofness. It is about a method.

Recently, many researches have been conducted on the retroreflective fabric that retroreflects light in order to prevent lubrication caused by a vehicle running at night or to give a decorative effect at night.

Conventionally, a part of the work clothes is used by partially attaching a reflector that reflects light, but such a light reflector is expensive and has a problem in that it cannot exert sufficient recognition function because it is partially attached, and the work clothes themselves. Too heavy was the problem causing inconvenience to work.

Japanese Unexamined Utility Model Publication No. 59-79011 describes the application of various types of luminescent paints onto the bubble, but in this case, the luminescent part is partially applied, so that a blind spot can be visually formed. There was a problem that the recognition function can not be performed. In addition, the light-emitting paint used includes a fluorescent (phosphorescent) material or a photoluminescent material, and can exhibit a high luminous effect at a close distance to the light source, but in general, the luminous effect is extremely low at about 50 m or more, so that sufficient recognition function can be exhibited. There was a problem that can not.

Japanese Patent Application Laid-open No. 50-53661 describes the application of a mixture of glass beads to a coating material using a pigment mixed with a polymer resin and a reflective layer coating material for appearance color effect, but the inherent opacity of the pigment Due to this, there was a problem that the reflection performance of the glass bead (particulate glass beads) was remarkably reduced, thereby decreasing the recognition function.In order to increase the reflection effect, a large amount of expensive glass beads should be used, and accordingly, the fabric itself There is a problem that the physical properties of the deterioration, the production cost increases.

In particular, the textile fabrics for bags and the like are mostly nylon or polyester, which is a thermoplastic polymer. Since the warp and weft yarns generally use denier fibers much thicker than those for garments, they provide form stability or firmness. In particular, air texturing is given to both the warp yarn or the weft yarn or the theft yarn of the filament yarn, which is used to enhance the three-dimensional or robustness, so that the surface of the fabric appears in the form of fine hairs or uneven crimped yarns. Various problems have arisen in the resin coating process.

In general, the method of imparting retroreflective performance to a retroreflective fabric for a bag is performed by applying a retroreflective composition containing glass beads having retroreflective properties based on a water-soluble resin vehicle (Vehicle) through a screen print or a transfer print technique. However, because the printing process method of the vehicle is limited to the water-soluble resin, the glass beads cannot be sufficiently fixed, and the durability is poor. Therefore, the retroreflective performance is deteriorated because the glass beads are dropped during washing or in use. Compared with the direct coating method, the productivity was extremely low. Therefore, in the past, this limited method has been limited to producing small quantities of expensive products for limited consumers.

An object of the present invention is to provide a method for producing a retroreflective fabric that can mass-produce a durable retroreflective fabric.

1 is a side cross-sectional view schematically showing an enlarged cross section of a retroreflective fabric manufactured according to one specific embodiment of the present invention.

Figure 2 is a side cross-sectional view schematically showing an enlarged cross-section of the retroreflective fabric prepared in accordance with another specific embodiment of the present invention.

※ Explanation of code for main part of drawing

11: bubble 12: adhesive layer

12-1: First adhesive layer 12-2: Second adhesive layer

13: retroreflective layer 14: bead coating layer

15: Grass Bead

The method for producing a retroreflective fabric according to the present invention comprises (1) an isocyanate such as polyisocyanate in 100 parts by weight of a thermoplastic resin such as a polyacrylic acid ester having a solid content of 18 to 35% by weight or a polyurethane having a solid content of 33 to 37% by weight. 3 to 5 parts by weight of a crosslinking agent such as a compound, 0.1 to 2 parts by weight of a crosslinking accelerator such as an organotin such as alkyl tin halide (R ₂ SnX ₂ ), and methyl ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol or these The adhesive composition obtained by adding 10 to 30 parts by weight of an organic solvent selected from the group consisting of two or more mixtures thereof and mixing the mixture with natural fibers, chemical fibers, synthetic fibers, or fabrics of two or more of them mixed in a conventional manner. Applying an amount of 3 to 12 g / m ² on the surface of the adhesive layer composition step of drying; (2) a bead surface treatment step of surface treating a surface of glass beads having a diameter of 20 to 90 microns with a silane-based surface treatment agent; (3) 100 to 200 parts by weight of glass beads obtained in the bead surface treatment step to 100 parts by weight of a thermoplastic resin such as polyacrylic acid ester having a solid content of 18 to 35% by weight or polyurethane having a solid content of 33 to 37% by weight Bubbles obtained in the adhesive layer composition step of the retroreflective layer composition obtained by adding 30 to 60 parts by weight of an organic solvent selected from the group consisting of ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol or a mixture of two or more thereof A retroreflective layer forming step of applying and drying in an amount of 25 to 85 g / m ² on the adhesive layer of the; And (4) a curing step of heating and curing at a temperature of 90 to 150 ° C.

Hereinafter, specific embodiments of the present invention will be described in detail with reference to the drawings.

In the method of manufacturing a retroreflective fabric according to the present invention for producing a retroreflective fabric having a configuration as schematically shown in Figure 1, at least one or more adhesive compositions and retroreflective layer composition in order to sequentially wide, long bubbles ( 11) It can be made by applying and curing on.

The adhesive composition used in the adhesive layer composition step is an isocyanate compound such as polyisocyanate in 100 parts by weight of a thermoplastic resin such as polyacrylic acid ester having a solid content of 18 to 35% by weight or a polyurethane having a solid content of 33 to 37% by weight. 3 to 5 parts by weight of crosslinking agent, 0.1 to 2 parts by weight of crosslinking accelerator such as organotin such as alkyl tin halide (R ₂ SnX ₂ ) and methyl ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol or two or more of them It can be obtained by adding by mixing 10 to 30 parts by weight of the organic solvent selected from the group consisting of a mixture.

The thermoplastic resin is not particularly limited, but polyacrylic acid ester or polyurethane resin may be preferably used. Especially, the polyurethane resin may be suitably used as a reactive two-component polyurethane resin. Without being limited, it can be understood that a commercially available resin such as a silicone elastomer can also be used.

The crosslinking agent and the crosslinking accelerator may vary depending on the type of thermoplastic resin used. Examples of the polyurethane resin include a crosslinking agent made of a polyisocyanate compound and a halogenated alkyl tin used as a catalyst in the synthesis of polyurethane. According to the type of thermoplastic resin, the main chain constituting the thermoplastic resin or side chains continuous to the main chains can be cured by crosslinking and bonding with respect to each other. As these crosslinking agents and crosslinking accelerators, commercially available crosslinking agents (Fine CLA; Fine Chemicals, FINE-CLA, Korea) and crosslinking accelerators (HI-ACCEL; HI-ACCEL, Fine Chemicals, Korea) can be selected and used. It can be understood by those of ordinary knowledge in Esau.

The crosslinking agent may be used in an amount of 3 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin, and may vary depending on the type of the crosslinking agent, but when used in an amount less than 3 parts by weight, the crosslinking may not be sufficient and curing may not be completed. It may not be possible, thereby reducing the physical properties of the thermoplastic resin itself, if there is more than 5 parts by weight there may be a problem that the retroreflective fabric finally obtained by curing by excessive crosslinking is too rigid.

The crosslinking accelerator is also selected in an amount suitable to promote the crosslinking agent, and may vary depending on the type and amount of the crosslinking agent used, and may generally be used in the range of 0.1 to 2 parts by weight. The use of less than 0.1 parts by weight may have a problem that the crosslinking promoting effect is insufficient, and it may be understood that more than 2 parts by weight is not preferable in terms of efficiency.

The organic solvent serves to uniformly apply the adhesive composition obtained by dispersing the thermoplastic resin, the crosslinking agent and the crosslinking accelerator on the bubble 11, and is also used in the thermoplastic resin and the crosslinking agent or the crosslinking accelerator. Therefore, the present invention may vary, but is exemplified based on the case where polyurethane is used as the thermoplastic resin. The organic solvent is preferably used 10 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin, which can be easily understood by those skilled in the art as a range set to control the overall viscosity of the adhesive composition to have a proper workability. It is.

The adhesive composition thus obtained is applied to the surface of the bubble 11 in an amount of 3 to 12 g / m ² so that the retroreflective layer 13 formed by applying and curing the bubble 11 and the subsequent retroreflective layer composition closely to each other. It serves to bond. There is no particular limitation on the application of the adhesive composition, but it is preferable to apply at a speed of 4 to 25m / min. If the coating speed is less than 4m / min, the application time is too long to be efficient in productivity, if it exceeds 25m / min there may be a problem that the coating stain is generated and uniform coating is not made. Application of the adhesive composition may be repeated at least one or more times, preferably two to six times to form the adhesive layer 12 of a multi-layer structure. At this time, the first adhesive layer 12-1 formed by the initial application of the adhesive composition is preferably such that the adhesive composition sufficiently penetrates between the hairs and pores of the bubbles 11, and for this purpose, the viscosity of the adhesive composition is low. It is possible to reduce the coating speed or to lower the coating speed, and to control the viscosity by adjusting the amount of organic solvent and the like, and also to control the coating speed by mechanical operation during operation of the coating apparatus. It can be easily understood by those skilled in the art.

The second adhesive layer 12-2 formed on the first adhesive layer 12-1 may be formed by applying the adhesive composition without any other limitation. The application here can be accomplished by conventional coating devices and coating methods. As the coating device and the coating method, a commercially available knife-on-air, knife-over-roller, comma-over-roller, and the like can be used as it is. For example, it has been experimentally confirmed that when the comma-over-roll method is used, the comma spreading gap can be achieved by adjusting it within the range of 150 to 280 microns. When the adhesive composition is applied in an amount of less than 3g / m ² may have a problem that the adhesive layer 12 is formed too thin to expect a sufficient adhesive effect, on the contrary exceeding 12g / m ² There may be a problem in that the adhesive layer 12 is made too thick to lower the physical properties of the retroreflective fabric also obtained. It is also readily understood by one of ordinary skill in the art that it is also possible to adjust the coating weight to the thickness of the knife at the time of application. In the case of stacking two or more layers in a multilayer structure, the total coating amount of the adhesive composition may be 10 to 70 gr / m ² .

In the bead surface treatment step, the surface of the glass bead 15 having a diameter of 20 to 90 microns is surface treated with a silane-based surface treatment agent so that the glass bead 15 is well mixed with the thermoplastic resin as the vehicle and adhered thereto. As the silane-based surface treatment agent that can be used, commercially available silane compounds such as gamma-methacryloxypropyltriethoxysilane (γ-MPS; γ-Methacryloxy Propyl triethoxy Silane) or vinyltriethoxysilane (Vinyltriethoxysilane) are selected and used. Can be. The method of surface-treating the glass beads 15 with the silane compound may vary depending on the type of the silane compound. However, in the case of the alkoxysilane, water 10 to 70 to 90% by weight of lower alcohol having 1 to 3 carbon atoms such as methanol or ethanol 20 to 30% by weight of alkoxysilane is mixed with 70 to 80% by weight of the mixed solvent in which 70% by weight is mixed, and the pH of the mixture is adjusted to an acid of 3 to 6 using a weak organic acid such as acetic acid at 2 to 4 at room temperature. The bead dispersion obtained by dispersing the glass beads (15) in a lower alcohol having 1 to 3 carbon atoms was mixed with the reaction mixture obtained by stirring for a hydrolysis reaction and stirred for 3 to 5 hours, and then the glass beads (15) were mixed. Consisting of drying separately. At this time, the throughput of the alkoxysilane to the glass beads 15 is preferably 1 to 3% by weight, and the drying after the treatment is first dried at 40 to 80 ° C. for 1 to 4 hours, and then at 1 to 100 to 130 ° C. It is preferable to dry separately by secondary drying for 3 hours. In this manner, the bead coating layer 14 may be formed on the surface of the glass beads 15.

The retroreflective layer composition used in the retroreflective layer forming step is a silane system in the bead surface treatment step in 100 parts by weight of a thermoplastic resin such as a polyacrylic acid ester having a solid content of 18 to 35% by weight or a polyurethane having a solid content of 33 to 37% by weight. 30 to 60 parts by weight of an organic solvent selected from the group consisting of 100 to 200 parts by weight of grasbis surface-treated with a compound, methyl ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol, or a mixture of two or more thereof is obtained by mixing can do. The thermoplastic resin and the organic solvent may be understood to be the same as or similar to the thermoplastic resin and the organic solvent in the adhesive composition. The glass beads 15 surface-treated with the silane-based compound used in the retroreflective layer composition may be understood to be known to be able to purchase and use commercially available ones by atomizing glass with a particle diameter of 20 to 90 microns. . If the particle diameter of the glass beads 15 is greater than 90 microns, there is a high possibility of the occurrence of coating stains, and may have a disadvantage that the side brightness is bad. The glass beads 15 may have different refractive indices according to the composition and particle diameter of the glass, and the glass beads 15 may be substantially different by varying the viscosity of the retroreflective layer composition covering the upper portion of the glass beads 15 according to the refractive indices of the glass beads 15. It is preferable to adjust the thickness of the resin component of (15). For example, when using the glass bead 15 having a refractive index of about 1.9, it is preferable to make the thickness of the resin component on the glass bead 15 as thin as possible so that the reflection and reflection occur inside the glass bead 15. For this purpose, the viscosity of the retroreflective layer composition may be applied in an open type to increase the retroreflective effect by using a viscosity of 4,000 to 5,000 cps (centipoise). At this time, it is preferable to use a knife-on air coating apparatus and method. In addition, when using the glass bead 15 with a refractive index of about 2.2, the resin component on the glass bead 15 is thickened to some extent and refracted by the glass bead 15, and total reflection is performed in the adhesive layer 12 below. It is preferable to cause it to occur, and for this purpose, the viscosity of the retroreflective layer composition may be applied in a close type of 10,000 to 30,000 cps. In this case, a comma over roll apparatus and method may be preferably used. In addition, when the refractive index of the glass beads 15 is 2.2 or more, it is also possible to form a transparent polyurethane resin layer by apply | coating with the above-mentioned open type, and further apply | coating the transparent polyurethane resin which added no additive thereon. Therefore, it can be obvious to those skilled in the art that the retroreflective effect can be adjusted by adjusting the viscosity of the retroreflective layer composition according to the refractive index of the glass beads 15 as described above. The retroreflective layer composition thus obtained can be formed on the adhesive layer 12 of the bubbles 11 obtained in the adhesive layer forming step in an amount of 25 to 85 g / m ² and dried to form the retroreflective layer 13. This may be performed in the same or similar manner as in the adhesive layer forming step. If the retroreflective layer composition is applied in an amount of less than 25g / m ² , there is a problem that the content of the glass beads 15 is insufficient to expect a sufficient retroreflective effect, on the contrary more than 85g / m ² There is a problem such as dropping of the glass bead 15, and is also not preferable due to problems such as physical properties.

Subsequently, the bubble 11 in which the adhesive layer 12 and the retroreflective layer 13 are laminated as described above may be achieved by heating to a temperature of 90 to 150 ° C., where the curing is performed on the adhesive composition. By means of crosslinking agents and crosslinking accelerators included in the main chain constituting the thermoplastic resin or the side chains that are continuous to these main chains means that the cross-linking, to each other.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described.

The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.

Example 1

As shown in Table 1 below, an adhesive composition and a retroreflective layer composition were prepared and obtained, respectively. The glass beads used in the retroreflective layer composition were mixed with a mixture of methanol and water in a ratio of 9: 1 and gamma-methacryloxypropyltriethoxysilane in a ratio of 75:25, and the pH of the mixture was adjusted to 4.5 with acetic acid. After mixing for 3 hours at room temperature and proceeding the hydrolysis reaction, the bead dispersion in which glass beads were dispersed in methanol was mixed so that the throughput of alkoxysilane to glass beads was 2% by weight and stirred for 4 hours. After that, the glass beads were separated and firstly dried at 60 ° C. for 2 hours, and again obtained by being secondly dried at 110 ° C. for 2 hours. Air amount of Texture rings in the processing of synthetic fiber yarns of 600 denier nose knife air coater apparatus and method on a Giro Dura bag bubble knife thickness of 1mm, 3mm, and adjusted to 3mm total of 17g / m ² of an adhesive composition to 12m / The coating was applied three times at a speed of min so that the total amount was 51 g / m ² . The retroreflective layer composition was adjusted to a knife thickness of 1 mm and applied at a rate of 12 m / min in an amount of 30 g / m ² , and finally heated and cured at a temperature of 130 ° C. to obtain a desired retroreflective fabric.

Composition and Content of Composition Composition Classification Product Name Mixing amount (part by weight) Adhesive composition Thermoplastic Polyurethane resin (35% by weight of solid content) 100 Crosslinking agent FINE CLA (Fine Chemical Products) 4 Crosslinking accelerator Hi-Accel (Fine Chemicals) One Organic solvent Methyl ethyl ketone 10 toluene 10 Retroreflective Composition Thermoplastic Polyurethane resin (35% by weight of solid content) 100 Grasvid Glass Beads Surface-treated with γ-MPS 100 Organic solvent Methyl ethyl ketone 20 toluene 20

Example 2

The desired retroreflective fabric was obtained in the same manner as in Example 1, except that the adhesive composition was applied only once.

Comparative Example 1

A retroreflective fabric was obtained in the same manner as in Example 1, except that the glass beads used in the retroreflective layer were not pretreated with a silane compound.

Comparative Example 2

100 parts by weight of the retroreflective layer composition as a thickener commercially available as a thickener, 3 parts by weight of a thickener, Hyrex-BES (Bowang Chemical Co., Ltd., Korea) and glass beads 100 treated with gamma-methacryloxypropyltriethoxysilane. A retroreflective fabric was obtained in the same manner as in Example 1, except that weight parts were used as the prepared one.

Test results of retroreflective fabrics such as initial brightness, luminance after 10 washes, and consumption of glass beads after 10 washes for the retroreflective fabrics obtained from Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 2 below. Indicated.

The washing method was to wash 10 times in the washing mode for 30 minutes in hot water at 60 ℃ using a household washing machine. Consumption rate was calculated as {(weight after washing / weight before washing) * 100}.

Test result of retroreflective fabric division Initial luminance (cd / m ² ) 10 washing after luminance (cd / m ² ) % Consumption Example 1 435 421 3.2 Example 2 89 50 4.4 Comparative Example 1 433 390 10.0 Comparative Example 2 450 130 71.1

As a result of the synthesis of the above examples, the retroreflective fabrics of Example 1 and Example 2 showed less than 5% consumption rate, it was confirmed that the durability is extremely superior to the comparative examples. In addition, it was confirmed that a sufficiently high initial luminance could be obtained by using the adhesive layer 12 in a multilayer structure.

Therefore, according to the present invention, in addition to the retroreflective effect, not only has excellent durability, but also functionality such as waterproofness, and has a long and wide bubble by using an existing coating device and method such as a knife-on air coater and a comma over roller coater. ) Can be processed continuously, the productivity is very high, it is effective to lower the production price and mass production of retroreflective fabric.

In addition, the retroreflective fabric produced according to the present invention can effectively use the retroreflective layer composition against the bubble 11 having a rough surface or a high degree of fineness, such as a bag, and extremely durable, such as a sports bag, a student bag, a backpack It has the effect of providing a retroreflective fabric which is particularly suitable for the manufacture of articles that require firmness, endurance, shape stability and the like.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (4)

(1) 3 to 5 parts by weight of a crosslinking agent, such as an isocyanate compound such as polyisocyanate, in 100 parts by weight of a thermoplastic resin such as polyacrylic acid ester having a solid content of 18 to 35% by weight or a polyurethane having a solid content of 33 to 37% by weight Organic solvents selected from the group consisting of 0.1 to 2 parts by weight of crosslinking accelerators such as organic tin such as tin (R ₂ SnX ₂ ), and methyl ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol or a mixture of two or more thereof To 30 parts by weight of the adhesive composition obtained by mixing the natural fibers, chemical fibers, synthetic fibers, or two or more of them in the amount of 3 to 12 g / m ² on the surface of the bubble of the fabric interwoven with conventional methods Applying and drying the adhesive layer composition step; (2) a bead surface treatment step of surface treating a surface of glass beads having a diameter of 20 to 90 microns with a silane-based surface treatment agent; (3) 100 to 200 parts by weight of grasbis obtained in the bead surface treatment step to 100 parts by weight of a thermoplastic resin such as polyacrylic acid ester having a solid content of 18 to 35% by weight or polyurethane having a solid content of 33 to 37% by weight Bubbles obtained in the adhesive layer composition step of the retroreflective layer composition obtained by adding 30 to 60 parts by weight of an organic solvent selected from the group consisting of ethyl ketone, toluene, acetone, dimethylformamide, isopropyl alcohol or a mixture of two or more thereof A retroreflective layer forming step of applying and drying in an amount of 25 to 85 g / m ² on the adhesive layer of the; And (4) a curing step of heating and curing at a temperature of 90 to 150 ℃; Method for producing a retroreflective fabric, characterized in that comprises a. The method of claim 1, The method of manufacturing the retroreflective fabric, characterized in that to form the adhesive layer of a multi-layer structure by repeating the application of the adhesive composition 2 to 6 times. The method of claim 2, Method for producing a retroreflective fabric, characterized in that the total coating amount of the adhesive composition to 10 to 70gr / m ² . The method of claim 1, As a silane-based surface treatment agent, an alkoxysilane such as gamma-methacryloxypropyltriethoxysilane (γ-MPS; γ-Methacryloxy Propyl triethoxy Silane) or vinyltriethoxysilane (Cinyl) may be used. 70 to 80% by weight of the mixed solvent, in which 70 to 90% by weight of the lower alcohol of 3 to 3 is mixed, 20 to 30% by weight of the alkoxysilane, and the pH of the mixture using a weak organic acid such as acetic acid. To an acid of 3 to 6 and stirred at room temperature for 2 to 4 hours to proceed with a hydrolysis reaction so that the throughput of alkoxysilane to glass beads is 1 to 3% by weight to 1 to 3 carbon atoms. The bead dispersion in which the glass beads were dispersed in the lower alcohol was mixed and stirred for 3 to 5 hours. , To remove the glass beads, allowed to 1-4 during the time a primary drying at 40 to 80 ℃, method for producing the retroreflective fabric, characterized by yirueojim shown to 1-3 hours secondary drying at 100 to 130 ℃ again.