KR20190118105A - Reflecting composition comprising glassbead treated by plasma, fabrics having retroreflecting and manufacturing method of fabrics having reflectivity - Google Patents

Abstract

The present invention relates to a retro-reflective composition comprising glass bead surface-treated using a plasma and to a retro-reflective fabric using the same. By surface-modifying a glass bead with plasma, the retro-reflective fabric having increased adhesion between the fabric and the retro-reflective composition is provided. In addition, due to the increase in adhesion and dispersibility, the brightness of the retro-reflective fabric is improved, and the physical properties such as washing durability is improved.

Description

REFLECTING COMPOSITION COMPRISITION COMPRISING GLASSBEAD TREATED BY PLASMA, FABRICS HAVING RETROREFLECTING AND MANUFACTURING METHOD OF FABRICS HAVING REFLECTIVITY}

The present invention relates to a retroreflective composition comprising a glass bead treated with plasma and a retroreflective fabric using the same, and more particularly, adhesion and dispersion stability between fibers and glass beads, which are fabrics, to increase brightness and durability of washing. The present invention relates to an improved retroreflective fabric and a method of manufacturing the same.

Many researches related to low temperature (at room temperature ~ 150 ° C) and atmospheric pressure plasma are actively conducted worldwide. As a method of implementing the atmospheric pressure plasma, there are a dielectric barrier discharge, a corona discharge, a microwave discharge, a microwave discharge, an arc discharge, and the like.

Plasma process is characterized by dry process, continuous process and simple processing process. In general fiber processing, it uses a large amount of water and steam, and also requires a large amount of thermal energy. The plasma process is used for the improvement.

As a prior art, Korean Patent No. 10-1588210 discloses a water repellent processing method of fibers using atmospheric pressure plasma to improve water repellency and productivity.

Meanwhile, safety work clothes, firefighting clothes, safety articles, sports clothes, shoes, or other decorative items use various reflectors having a light reflection function for a part where visibility is required, such as marking of specific information or incidence of design.

Conventionally, a method of directly attaching a reflector reflecting light to clothes or applying a luminous paint has been proposed, and a method of using a retroreflective function of glass beads or microprism has recently been proposed. .

Retroreflective reflects light in the direction of the light source no matter which direction it is from which direction, so it has the advantage of excellent visibility even at night or in dark places. Accordingly, it was mainly used for signs of severe roads, night road work signs, night work clothes, safety clothes, and firefighting clothes. Glass beads are also used in a variety of ways because of their excellent workability with retroreflective properties.

As a prior art, US Patent Publication No. 2016-0199876 discloses a plasma treatment of thermosetting resin filler fine particles. The technique describes a method of crosslinking a thermosetting resin body and glass bead particles, which is a filler, by using glass beads as a filler of the thermosetting resin and exposing the glass beads together with the thermosetting resin in a plasma activation space. Also described is an apparatus for applying crosslinking in a fluidized bed reactor.

As a prior art, Korean Patent No. 10-1424912 discloses a high refractive index glass bead having excellent retroreflective property and a method of manufacturing the same. The technique is prepared by a process including upstream injection and descending of compressed air using high refractive index TiO2, BaO, La2O and Bi2O3 compositions, having a particle diameter of 1 to 1000 μm, a visible light transmittance of 65% or more, and a 2.0 to 2.5 It is described as showing the refractive index.

Further, as a prior art, Korean Patent No. 10-1406876 discloses a reflective layer forming composition in which a reflective layer using glass beads or microprism is attached to glass beads or microprism using a resin adhesive binder. In addition, the Republic of Korea Patent No. 10-1577008 discloses a laminating method of the fabric that can implement a variety of patterns to transfer the glass bead on the upper surface of the hot melt pattern layer and then the mesh fabric on the upper surface of the glass bead layer.

However, in the case of using the adhesive binder, in order to maximize the retroreflective property, the amount of glass beads added is increased compared to the amount of the binder. As a result, the bond strength between the fabric and the glass bead reflector is lowered, resulting in more than 50% of glass bead dropping when washing. There was a problem in that the retroreflective property is significantly reduced, and if the glass bead addition amount is reduced, the amount of adhesive addition becomes excessive, causing a problem in that luminance decreases due to discoloration of the adhesive itself.

In addition, the thermal transfer method is performed by heat treatment at a high temperature of 100 ° C. or higher. If the substrate on which the reflective layer is formed has a problem such as cotton, nylon, silk or miles, the fabric burns or discolors, and the reflective layer is formed of glass beads. In the case of the method, due to the low processability due to the high desorption rate of the glass beads or microprism, it is difficult to carry out the subsequent dyeing process or pattern forming process, and there is a problem in that washing durability is lowered.

In the art, there is a gravure method using a pattern roller and a knife coating method using a knife, but such a method can be molded only by partial painting. Some gravure method and knife coating ice type are used to apply the front coating method, but due to low luminance properties, they are currently applied to fashion clothes.

Therefore, it is possible to improve the physical properties such as brightness, washing durability, dry cleaning durability and friction durability by increasing the adhesion between fabric fibers and glass beads even with the minimum amount of adhesive binder. The demand is on.

Meanwhile, in the textile industry, prior art is known in which surface modification is performed using plasma on fabric fibers, and glass beads are also surface modified using plasma. However, both types of fabric fibers and glass beads are continuous by using plasma. Retroreflective surface modification with work is not known.

In addition, partial application of clothing makes it difficult to diversify the fashion of clothing and harden the texture of clothing, because the bead shape of the part that is partially coated even during the day seems to be distinguished from the fabric part that is not applied. There is little deformation, it is not distinguished from the part where the bead shape is not applied during the day, and the bead shape is visible only at night or when the light is shot.

Regarding the application method to the garment, there are gravure method using a patterned roll copper plate, direct coating method using a knife, and spray method. The gravure coating method is patterned as the pattern roller rotates and squeezes the surface of the fabric, so it is structurally limited to uniformly squeeze the front surface of the 1500 mm width moving at high speed, which is inappropriate for continuous mass production.

Retroreflective Some companies are using direct knife coating, but the glass bead loss rate is about 50% by weight after one time of washing.

The present invention provides a retroreflective composition in which the surface of the glass bead is modified with plasma, thereby increasing the adhesion to the fabric, thereby reducing the loss of the glass bead even after washing, thereby maintaining high luminance and improving washing durability of the fabric. For work purposes.

In addition, the present invention increases the surface tension of the modified glass beads and improves wettability due to the plasma treatment of the glass bead surface, thereby reducing the contact angle between components during the mixing process of the binder, glass bead, and solvent. Another object of the present invention is to provide a retroreflective composition which can be uniformly applied to a fabric as a result of the dispersibility of the glass beads being uniformly mixed in the retroreflective composition, and a fabric coated with the retroreflective composition.

In addition, another object of the present invention is to apply the retroreflective composition including the glass bead having improved dispersibility to the entire fabric so that the luminance is uniformly expressed not only in high luminance but also in the entire fabric.

In order to achieve the above object, an aspect of the present invention provides a retroreflective composition comprising glass beads surface-treated with plasma.

The glass beads may be treated using at least one activator selected from the group consisting of a silane coupling agent, a reactive discharge gas, compressed air, and a combination thereof as an activator in the plasma active space.

The glass beads may have a refractive index of 1.7 to 2.5 and a transparency of 98% or more, and may be aluminum coated or non-coated. The glass beads may be made of spherical particles having an average particle diameter of 30 to 90㎛.

The retroreflective composition may further include a binder, a thickener and a solvent, and the retroreflective composition may include a dispersant, a curing agent, a curing accelerator, an ultraviolet absorber, a yellowing agent, a light diffusing agent, a surfactant, an antistatic agent, an anti-precipitation agent and these At least one additive selected from the group consisting of a mixture may further include.

In addition, another aspect of the present invention; And it provides a retroreflective fabric comprising a retroreflective layer containing a glass bead surface-treated with a plasma applied on the fabric.

The fabric may be surface modified with plasma.

The glass beads may have a refractive index of 1.7 to 2.5 and a transparency of 98% or more, and may be coated with aluminum or not. The glass beads may include spherical particles having an average particle diameter of 30 to 90 μm. It may be.

In addition, another aspect of the present invention comprises the steps of modifying the surface of the glass bead with plasma; Mixing the modified glass beads with a binder to prepare a retroreflective composition; And forming a retroreflective layer by applying the retroreflective composition to the entire surface of the fabric to form a retroreflective layer.

The fabric may be a fabric whose surface is modified by plasma.

According to the present invention as described above, the glass bead surface-treated by plasma to increase the adhesion between the fabric and the retroreflective composition can provide a retroreflective fabric with improved laundry durability.

In addition, due to the improved dispersibility of the glass bead in the retroreflective composition, when the retroreflective composition is applied to the front surface of the fabric or the like, it exhibits not only high luminance but also uniform brightness across the entire fabric.

1 is a flow chart of a retroreflective composition and a retroreflective fabric manufacturing process applied thereto according to an embodiment of the present invention.
Figure 2 is an enlarged photograph showing the microstructure of the retroreflective fabric prepared by Example 1 and the retroreflective fabric prepared by Comparative Example 4 according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The retroreflective composition of one embodiment of the present invention includes glass beads surface-treated with plasma.

The glass beads may be surface treated with plasma after pretreatment using a coupling agent.

The method of coating the glass beads with a coupling agent may use a spray injection method that is commonly used, but is not particularly limited.

Specifically, the coupling agent is not particularly limited as long as it can improve the interfacial adhesion between the binder and the glass bead applied to the fabric, it is preferable to use selectively according to the fabric and the binder type.

The coupling agent may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the glass bead, but the amount of the coupling agent may be used for the price of the coupling agent, the material of the glass bead, the average particle size, the binder type, the reactive gas in the chamber, and the reactive functional group ( radicals) and the like may be appropriately changed and used, and are not limited to the above-described contents.

If the amount of the coupling agent is less than 0.1 part by weight, the adhesive force may be lowered. If the amount of the coupling agent is 10 parts by weight or more, the brightness may be reduced due to the decrease in transparency of the glass beads, which is not preferable.

As the coupling agent, any one selected from the group consisting of a silane coupling agent, a titanate coupling agent, a chromium coupling agent, an aluminate coupling agent, and a combination thereof may be used.

The glass beads preferably have a refractive index of 1.7 to 2.5. When the refractive index of the glass bead is in the range of 1.7 to 2.5, a focus is formed on the inner wall of the reflector, thereby exhibiting a higher focus reflectivity, thereby realizing high retroreflectivity. However, when the refractive index is less than 1.7, the focus reflectivity is lowered, and as a result, the retroreflectivity is lowered, which is not preferable.

The glass bead preferably has a light transmittance (transparency) of 98% or more, and the light reflectance is increased through the light transmittance as described above. However, when the light transmittance is less than 98%, the amount of light absorption is increased and the retroreflectivity may be lowered, which is not preferable.

The refractive index and the light transmittance of the glass beads are determined according to the composition, shape, or particle diameter of the glass beads, and the properties of the glass beads are spherical in consideration of the effect on the adhesion to the substrate and the durability of the glass beads themselves. It is preferable to have the form of.

The glass beads may be made of spherical particles having an average particle diameter of 30 to 90 ㎛. It is preferable to have an average particle diameter of 30 to 90 μm because it exhibits excellent refractive index, low loss to the substrate, and excellent durability against external physical and chemical stimuli. If the average particle diameter of the glass beads is less than 30 μm, the refractive index may be lowered. If the average particle diameter of the glass beads exceeds 70 μm, coating workability and adhesion to the substrate may be lowered, which is not preferable.

The glass beads may be used by mixing two or more kinds having different average particle diameters within the above average particle diameter range.

When the glass beads are surface treated with plasma, the glass beads may be treated with one or more activators selected from the group consisting of a coupling agent, a reactive discharge gas, compressed air, and a combination thereof as an activator in the plasma active space.

The glass beads may be coated with a coupling agent in a plasma chamber after being pretreated in a plasma chamber, or may be performed after being pretreated in a separate space.

The plasma surface treatment may be performed at room temperature and / or vacuum at atmospheric pressure, and may be performed using various types of plasma discharge devices.

The plasma active space refers to a plasma flow having a plasma jet or beam shape generated when an alternating voltage is applied between electrodes in a plasma apparatus. The plasma active space is a surface in an active space at atmospheric pressure and / or a vacuum chamber. It is preferred that the modification be made.

The reactive discharge gas may be nitrogen, argon, oxygen, hydrogen, helium, fluorine and the like, but is not particularly limited, and is preferably used in consideration of the quality and economical efficiency of the surface-treated glass beads.

The compressed air may use compressed air generated by a compressor, but is not particularly limited, and the compressed air may exhibit plasma discharge performance and cooling performance of the plasma active space.

The retroreflective composition may further include a binder, a dispersant, and a solvent.

The binder is a binder adhesive capable of bonding the modified glass beads on the surface of the fabric, and a binder of a series such as polyurethane or epoxy may be used, and is not particularly limited.

As an example, a one-component method in which a main agent and a curing agent are mixed, a two-component method used by separately mixing, a method of curing by applying heat, an ultraviolet or moisture curing method at room temperature, and a solvent-free method may be used. It is preferable to use the polyurethane resin series of alcohol and isocyanate which have a urethane bond (-NHCOO-), the general-purpose epoxy resin series of epoxy and amine which react with bisphenol A, a modified urethane resin series, etc. in the repeating unit of a chain.

The solvent and dispersant may be used without limitation, those conventionally used in the art.

The solvent is not particularly limited, but may help to mix the retroreflective composition and the additive, and may have an appropriate viscosity in the process of applying the retroreflective composition, and if the solvent does not interfere with the physical properties of the retroreflective composition, It may be applied, preferably may be used methyl ethyl ketone (MEK).

The dispersant may be silicone that can be used for a defoaming agent, a dispersant, a leveling agent, and the like.

In one embodiment, the retroreflective composition may include a polyurethane emulsion as a binder, methyl ethyl ketone (MEK) as an organic solvent, a crosslinking agent, and silicone as a dispersant to improve leveling properties.

The retroreflective composition may further include a thickener. The thickeners include cellulose thickeners, specifically hydroxypropylmethyl cellulos, hydroxyethylmethyl cellulose, ethyl hydroxyethyl cellulose and carboxymethyl cellulose. It may be, but is not limited to such. Moreover, these 1 type can be used individually or in mixture of 2 or more types.

The thickener may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of glass beads. If the thickener content of the glass beads is too high, the viscosity of the retroreflective composition becomes high and coating is poor. On the contrary, if the viscosity of the retroreflective composition is too low, the glass bead phase separation may occur.

The retroreflective composition may further include an additive selected from the group consisting of a crosslinking agent, a curing agent, a curing accelerator, an ultraviolet absorber, a yellowing agent, a light diffusing agent, a surfactant, an antistatic agent, a precipitation inhibitor, and a mixture thereof. .

Retroreflective fabric of one embodiment of the present invention is a fabric; And a retroreflective layer containing glass beads surface-treated with a plasma applied on the fabric, wherein the coating includes glass beads spread over the fabric. Conventionally, there is a knife coating (knife coating) and gravure (gravure) method using a pattern roller, it can be molded only by partial coating method in this way. In some cases, a roll coating method is used to apply the front coating method. However, the present invention is limited to fashion clothes due to low luminance properties due to high bead loss rate during washing.

The retroreflective layer may be composed of the retroreflective composition of one embodiment of the present invention described above.

The thickness of the retroreflective layer is greater than or equal to the maximum particle diameter of the glass bead and is preferably 3 times or less the average particle diameter of the glass bead. If it is smaller than the maximum particle diameter of the glass bead, the coating process is difficult. On the other hand, if it exceeds three times the glass bead average particle size, there is a fear of a decrease in the refractive index.

The fabric is not particularly limited, and may be fibers, paper, leather, natural fabrics or knitted fabrics such as cotton, hemp, silk, wool, synthetic fabrics or knitted fabrics such as nylon, polyurethane, polyester, rayon, or the like. Transfer, printing, UV printing, solvent printing, aqueous printing, offset printing, etc. may be one substrate. More preferably, it may be a cotton fabric (Denim) or a blended fabric ripstop (ripstop), the fabric may be a fabric treated with a softening agent.

The fabric may be surface modified with plasma. Plasma treatment of the fabric includes modifying, etching or stripping chemical materials such as softeners, water repellents, flame retardants, fluorine compounds or hydrocarbon-based treatment materials coated on the fabric at the time of fabric shipment.

The plasma treatment may be performed at room temperature at atmospheric pressure, may be performed using various types of discharge devices, and dielectric barrier corona discharge devices may be used.

The plasma apparatus may have a discharge output of 2 to 15 kW, a discharge width of up to 2000 mm, a discharge length of 6 to 15 mm, and a discharge head of 1 to 10, but is not limited thereto. In addition, the discharge width is dependent on the size of the fabric, the discharge length may be changed when the body output is changed and the discharge head may be preferably adjusted in accordance with the surface modification rate of the fabric very close to the productivity.

Plasma surface modification of the fabric is preferably surface treated at a treatment rate of 5 to 60 m per unit time (minutes) through an atmospheric plasma apparatus. If the discharge treatment time is too long, less than 5 m per unit time (minutes), the production speed is reduced and economical, and the etching effect of the surface of the fabric is partially concentrated, resulting in a hole in the surface, thereby deteriorating the inherent properties of the fabric fiber. And, there is a fear that the spark occurs in the space between the warp and weft of the fabric damage the fabric tissue. If the unit time (minutes) exceeds 60 m, that is, the discharge treatment time is too short, the surface modification effect of the original fabric does not appear.

By surface modifying the fabric with plasma, it is possible to generate reactive radicals that can be chemically bound strongly, thereby reducing the amount of binder applied. Reduction of the amount of binder not only can soften the feel of the fabric, but also can increase productivity by reducing the drying time.

In the retroreflective layer, the glass bead content may be appropriately adjusted according to the use of the retroreflective article. Specifically, considering the physical properties of the retroreflective glass bead and the adhesion to the substrate, it is preferable that the glass bead is 20 to 60 mg / m ² in the retroreflective layer, and the content of glass bead is 20 mg / m ^2. If less than the glass bead content is too low to obtain a sufficient reflection effect, while the glass bead content is more than 60 mg / m ^{2 It} is not preferable because the drop rate of the glass bead and the manufacturing cost is increased.

In addition, referring to Figure 1, the method of manufacturing a retroreflective fabric of one embodiment of the present invention (a) plasma surface treatment step of modifying the surface of the glass bead (S100); (b) mixing the modified glass beads with a binder to prepare a retroreflective composition (S200); And (c) applying the retroreflective composition to the surface of the fabric to form a retroreflective layer (S300), wherein the application includes a front coating.

Specifically, as shown in Figure 1, (a) step (S100) is to modify the surface of the glass bead using a coupling agent and / or discharge gas in the plasma jet (plasma jet) or the plasma active space of the beam shape It includes a step.

(a) In step S100, the glass beads may be pretreated with a silane coupling agent and then surface treated with plasma.

The glass beads preferably have a refractive index of 1.7 to 2.5. When the refractive index of the glass bead is in the range of 1.7 to 2.5, a focus is formed on the inner wall of the reflector, thereby exhibiting a higher focus reflectivity, thereby realizing high retroreflectivity. However, when the refractive index is less than 1.7, the focus reflectivity is lowered, and as a result, the retroreflectivity is lowered, which is not preferable.

The glass bead preferably has a light transmittance (transparency) of 98% or more, and the light reflectance is increased through the light transmittance as described above. However, when the light transmittance is less than 98%, the amount of light absorption is increased and the retroreflectivity may be lowered, which is not preferable.

The refractive index and the light transmittance of the glass beads are determined according to the composition, shape, or particle diameter of the glass beads, and the properties of the glass beads are considered in consideration of the effect on the adhesion to the substrate and the durability of the glass beads themselves. It is preferable to have a spherical form.

The glass beads may be made of spherical particles having an average particle diameter of 30 to 90 ㎛. It is preferable to have an average particle diameter of 30 to 90 μm because it exhibits excellent refractive index, low loss to the substrate, and excellent durability against external physical and chemical stimuli. If the average particle diameter of the glass bead is less than 30 μm, the refractive index may be lowered. If the average particle diameter of the glass bead is more than 90 μm, coating workability and adhesion to the substrate may be lowered, which is not preferable.

As the glass beads, a mixture of two or more kinds of glass beads having different average particle diameters within the above average particle diameter range may be used.

(a) Plasma surface treatment in the step (S100) is preferably a surface modification of the glass beads in the atmospheric pressure room temperature and / or active space in the vacuum chamber. That is, although the discharge characteristics of the plasma have a straightness, since the glass beads have a spherical shape, the area that can be irradiated with the plasma is relatively small compared to the fabric, and the irradiation amount is unevenly distributed. The method of irradiating the plasma may be preferable.

(a) Plasma treatment of the glass beads in step (S100), when the dispersant, surfactant, and the like to be described later adsorbed to the glass particles during the mixing process may change the contact angle made by the dispersion medium such as glass beads, binder, and solvent. Increasing the contact angle may cause glass beads to agglomerate from the dispersion medium or float on the surface of the medium, while decreasing the contact angle may increase dispersion stability.

(a) In step S100, the plasma irradiation time is preferably irradiated 1 to 10 minutes. If the treatment is less than 1 minute (min), the surface modification state of the glass bead may be insufficient, and if the treatment is more than 10 minutes (min) may be disadvantageous in terms of economics.

(a) In step (S100), when the surface of the glass bead, the glass bead is activated in any one or more selected from the group consisting of a coupling agent, a reactive discharge gas, compressed air and a combination thereof as an activator in the plasma active space It is preferable to process using an agent.

The plasma surface treatment may be performed at room temperature and / or vacuum at atmospheric pressure, and may be performed using various known plasma discharge apparatuses.

The plasma active space refers to a plasma flow having a plasma jet or beam shape generated when an alternating voltage is applied between electrodes in a plasma apparatus. The plasma active space is a surface in an active space at atmospheric pressure and / or a vacuum chamber. It is preferred that the modification be made.

The coupling agent is not particularly limited, and it is preferable to selectively use the coupling agent according to the material of the glass bead and the presence or absence of the coating. Specifically, the coupling agent may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the glass bead, but the amount of the coupling agent is used in consideration of the adhesion strength, the average particle diameter, the reactive gas and the reactive functional group in the chamber, and the like. It can be used as appropriate and can be changed, and is not limited to the contents disclosed above.

As the coupling agent, any one selected from the group consisting of a silane coupling agent, a titanate coupling agent, a chromium coupling agent, an aluminate coupling agent, and a combination thereof may be used.

The reactive discharge gas may be nitrogen, argon, oxygen, hydrogen, helium, fluorine and the like, but is not particularly limited, and is preferably used in consideration of the quality and economical efficiency of the surface-treated glass beads.

The compressed air may use compressed air generated by a compressor, but is not particularly limited, and the compressed air may be capable of exhibiting plasma discharge performance and cooling performance of a plasma active space.

(B) step (S200) comprises the step of mixing the modified glass beads with a binder to prepare a retroreflective composition.

In more detail, (b) step (S200) is a step of forming a retroreflective composition by moving the glass beads modified in (a) step (S100) to a retroreflective composition hopper is a binder, a thickener and a solvent is mixed, Dispersion stability can be further improved by utilizing the viscoelasticity of the retroreflective composition and the self alignment characteristics of the glass beads. For this purpose, stirrers, ultrasonic waves, vacuum deaerators, and dispensers are used. It may be desirable to use.

The retroreflective composition may further include a binder, a dispersant, and a solvent.

The binder is a binder adhesive capable of bonding the modified glass beads on the surface of the fabric, and a binder of a series such as polyurethane or epoxy may be used, and is not particularly limited.

As an example, a one-component method in which a main agent and a curing agent are mixed, a two-component method used by separately mixing, a method of curing by applying heat, an ultraviolet or moisture curing method at room temperature, and a solvent-free method may be used. It is preferable to use the polyurethane resin series of alcohol and isocyanate which have a urethane bond (-NHCOO-), the general-purpose epoxy resin series of epoxy and amine which react with bisphenol A, a modified urethane resin series, etc. in the repeating unit of a chain.

The solvent and dispersant may be used without limitation, those conventionally used in the art.

The solvent is not particularly limited, but may help to mix the retroreflective composition and the additive, and may have an appropriate viscosity in the process of applying the retroreflective composition, and if the solvent does not interfere with the physical properties of the retroreflective composition, It may be applied, preferably may be used methyl ethyl ketone (MEK).

The dispersant may be silicone that can be used for a defoaming agent, a dispersant, a leveling agent, and the like.

In one embodiment, the retroreflective composition may include a polyurethane emulsion as a binder, methyl ethyl ketone (MEK) as an organic solvent, a crosslinking agent, and silicone as a dispersant to improve leveling properties.

The retroreflective composition may further include a thickener. The thickeners include cellulose thickeners, specifically hydroxypropylmethyl cellulos, hydroxyethylmethyl cellulose, ethyl hydroxyethyl cellulose and carboxymethyl cellulose. It may be, but is not limited to such. Moreover, these 1 type can be used individually or in mixture of 2 or more types.

The thickener may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of glass beads. If the thickener content of the glass beads is too high, the viscosity of the retroreflective composition becomes high and coating is poor. On the contrary, if the viscosity of the retroreflective composition is too low, the glass bead phase separation may occur.

The retroreflective composition may further include an additive selected from the group consisting of a crosslinking agent, a curing agent, a curing accelerator, an ultraviolet absorber, a yellowing agent, a light diffusing agent, a surfactant, an antistatic agent, a precipitation inhibitor, and a mixture thereof. .

(c) step (S300) The retroreflective composition is a step of forming a retroreflective layer by coating the entire surface of the fabric and then drying.

(c) In the retroreflective layer formed in step (S300), the coating process of the retroreflective composition may be performed using a dispensing device or the like capable of automatically and uniformly dispensing the coating amount, specifically, a knife The coating may be applied by a coating method such as knife coating, roll coating, spray, reverse coating, gravure, comma coater, bar coating, or the like.

The fabric is not particularly limited, and may be fibers, paper, leather, natural fabrics or knitted fabrics such as cotton, hemp, silk, wool, synthetic fabrics or knitted fabrics such as nylon, polyurethane, polyester, rayon, or the like. Transfer, printing, UV printing, solvent printing, aqueous printing, offset printing, etc. may be one substrate. More preferably, it may be a cotton fabric (Denim) or a blended fabric ripstop (ripstop), the fabric may be a fabric treated with a softening agent.

The fabric may be surface modified with plasma. Plasma treatment of the fabric includes modifying, etching or stripping chemical materials such as softeners, water repellents, flame retardants, fluorine compounds or hydrocarbon-based treatment materials coated on the fabric at the time of fabric shipment.

The plasma treatment may be performed at room temperature at atmospheric pressure, may be performed using various types of discharge devices, and dielectric barrier corona discharge devices may be used.

The plasma apparatus may have a discharge output of 2 to 15 kW, a discharge width of up to 2000 mm, a discharge length of 6 to 15 mm, and a discharge head of 1 to 10, but is not limited thereto. In addition, the discharge width is dependent on the size of the fabric, the discharge length may be changed when the body output is changed and the discharge head may be preferably adjusted in accordance with the surface modification rate of the fabric very close to the productivity.

Plasma surface modification of the fabric is preferably surface treated at a treatment rate of 5 to 60 m per unit time (minutes) through an atmospheric plasma apparatus. If the discharge treatment time is too long, less than 5 m per unit time (minutes), the production speed is reduced and economical, and the etching effect of the surface of the fabric is partially concentrated, resulting in a hole in the surface, thereby deteriorating the inherent properties of the fabric fiber. And, there is a fear that the spark occurs in the space between the warp and weft of the fabric damage the fabric tissue. If the unit time (minutes) exceeds 60 m, that is, the discharge treatment time is too short, the surface modification effect of the original fabric does not appear.

By surface modifying the fabric with plasma, it is possible to generate reactive radicals that can be chemically bound strongly, thereby reducing the amount of binder applied. Reduction of the amount of binder not only can soften the feel of the fabric, but also can increase productivity by reducing the drying time.

The thickness of the retroreflective layer is greater than or equal to the maximum particle diameter of the glass bead and is preferably 3 times or less the average particle diameter of the glass bead. If it is smaller than the maximum particle diameter of the glass bead, the coating process is difficult. On the other hand, if it exceeds three times the glass bead average particle size, there is a fear of a decrease in the refractive index.

(c) In the retroreflective layer formed in step S300, the glass bead content in the retroreflective composition may be appropriately adjusted according to the use of the retroreflective article. Specifically, in consideration of the physical properties of the retroreflective glass beads and the adhesion to the substrate, the retroreflective composition is preferably a glass bead applied in an amount of 20 to 60 mg / m ^2, the content of glass beads If 20 mg / m ² , the glass bead content is too low to obtain a sufficient reflection effect, whereas if the glass bead content exceeds 60 mg / m ² , the drop rate of the glass bead is not preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.

Example 1.

Glass beads having an average diameter of 40 μm were prepared in a transparent spherical shape having a refractive index of 1.93 and specific gravity of 2.6.

After the prepared glass beads are pretreated with a silane coupling agent, the surface of the pretreated glass beads is modified with plasma. Thereafter, 35 kg of a thermosetting polyurethane binder, 0.35 kg of a silicone dispersant, 20 kg of MEK (methyl ethyl ketone) as a solvent, and 30 kg of the surface-modified glass beads were mixed to prepare a retroreflective composition.

The glass bead plasma reforming conditions are modified at a production rate of 30 kg per hour while using a compressor compressed air as the discharge gas and penetrating the interior of the discharge head (80 mm diameter) with a discharge output of 800 watts (W) and a discharge length of 10 mm. It was.

As a fabric to which the retroreflective composition is to be applied, a fabric having a width of 150 cm of a soft fabric treated with a softening agent was prepared, and the surface of the fabric was modified with plasma. Plasma treatment conditions on the fabric surface were modified at 160 mm / sec production rate using compressed air as discharge gas and two discharge heads having a discharge output of 400 watts (W), a discharge width of 1,500 mm, and a discharge length of 3 mm.

A retroreflective fabric was prepared by applying a retroreflective composition prepared in advance to a plasma-modified fabric at a rate of 20 m per minute to form a film, and then passing it through a hot air drying chamber maintained at 100 ° C.

Example 2.

In the same manner as in Example 1, as a fabric to which the retroreflective composition is to be applied, a cotton fabric (Denim) was not prepared, and the surface of the fabric was modified through plasma.

Example 3.

As in Example 1, but as a fabric to which the retroreflective composition is to be applied, a blended fabric ripstop without a softening agent (40% polyester as a C / P fabric is mixed with 40) Thus, the surface of the fabric was modified through the plasma.

Example 4.

The same process as in Example 1, except that the retroreflective composition was applied to the fabric, the surface of the softener-treated cotton fabric (Denim) was not modified.

Example 5.

In the same manner as in Example 1, as a fabric to which the retroreflective composition is to be applied, the surface of the cotton fabric (Denim) without the softener was not modified.

Example 6.

As in Example 1, but the fabric to be applied to the retroreflective composition, the surface of the blended fabric ripstop (lipstop 40% polyester blended to 60% cotton as a C / P fabric) without the softener treatment Did not reform.

Comparative Example 1.

In the same manner as in Example 1, as a fabric to which the retroreflective composition is to be applied, a cotton fabric treated with a softening agent (Denim) was prepared, the surface of the fabric was modified by plasma, and the surface of the glass bead was not modified.

Comparative Example 2.

In the same manner as in Example 1, as a fabric to which the retroreflective composition is to be applied, a soft fabric-treated cotton fabric (Denim) was prepared, the surface of the fabric was modified by plasma, and the surface of the glass bead was not modified.

Comparative Example 3.

As in Example 1, but as a fabric to which the retroreflective composition is to be applied, a blended fabric ripstop without a softening agent (40% polyester as a C / P fabric is mixed with 40) The surface of the fabric was modified with plasma, and the surface of the glass beads was not modified.

Comparative Example 4.

In the same manner as in Example 1, the prepared fabric and glass beads did not modify the surface.

Comparative Example 5.

In the same manner as in Example 2, the prepared fabric and glass beads did not modify the surface.

Comparative Example 6.

In the same manner as in Example 3, the prepared fabric and glass beads did not modify the surface.

The retroreflective fabrics prepared in Examples 1 to 6 and Comparative Examples 1 to 6 are summarized in Table 1 below.

Fabric type  Softener Use Fabric surface modification Glass Bead Surface Modification Example 1 Cotton Fabric (Denim) use Surface modification Surface modification Example 2 Cotton Fabric (Denim) unused Surface modification Surface modification Example 3 Blended fabric ripstops unused Surface modification Surface modification Example 4 Cotton Fabric (Denim) use No surface modification Surface modification Example 5 Cotton Fabric (Denim) unused No surface modification Surface modification Example 6 Blended fabric ripstops unused No surface modification Surface modification Comparative Example 1 Cotton Fabric (Denim) use Surface modification No surface modification Comparative Example 2 Cotton Fabric (Denim) unused Surface modification No surface modification Comparative Example 3 Blended fabric ripstops unused Surface modification No surface modification Comparative Example 4 Cotton Fabric (Denim) use No surface modification No surface modification Comparative Example 5 Cotton Fabric (Denim) unused No surface modification No surface modification Comparative Example 6 Blended fabric ripstops unused No surface modification No surface modification

Experimental Example 1.

Washing durability, ie, brightness before and after washing of the retroreflective fabrics, for the fabric specimens prepared by cutting the retroreflective fabrics prepared in Examples 1 to 6 and Comparative Examples 1 to 6 to 300 mm × 300 mm square size The change in value due to the loss of glass beads was tested.

Wash durability assessments were measured using a model No.920, serial No. RT1595 instrument from gamma scientific. In the past, there was no device for measuring the brightness of the fabric. Brightness was measured by good, normal, or poor visual observation simply by a flash light. However, in relation to luminance measurement, VF CORP and INNO 10 CORP in Korea introduced the luminance measurement method using the above instrument for the first time in the world and the luminance standard of industrial safety work clothes in the United States (6-8 cd / ㎡). / ix) has been established and is currently recognized as the luminance standard for industrial safety workwear. The brightness of the fabrics prepared in Examples and Comparative Examples and the change in brightness (washing durability) after three washes by the brightness measurement method were measured and displayed in numbers, and the results are summarized in Table 2 below.

Luminance value [cd / ㎡ / ix] Before washing After washing Example 1 7.6 7.0 Example 2 7.9 7.4 Example 3 11.1 10.3 Example 4 7.0 6.5 Example 5 7.6 6.7 Example 6 11.0 10.0 Comparative Example 1 6.6 5.9 Comparative Example 2 6.5 5.9 Comparative Example 3 8.7 8.2 Comparative Example 4 5.7 5.4 Comparative Example 5 6.3 5.6 Comparative Example 6 8.7 7.4

Referring to Table 2, in the case of the retroreflective fabric prepared in Examples 1 to 6, the surface of the glass bead according to the present invention, the retroreflective fabric prepared in Comparative Examples 1 to 6 without the surface treatment of glass beads Compared with the improved effect.

In contrast to Comparative Example 4 in which both the fabric and the glass beads were not surface-modified by using the fabric fabric treated with the softener, Example 1 in which the fabric and the glass beads were surface-modified by plasma showed a 32% increased luminance value.

In addition, in comparison with Comparative Example 5, in which both the fabric and the glass bead did not undergo surface modification, the fabric and the glass bead exhibited a 25% increase in luminance in the case of Example 2 in which the fabric and the glass bead were surface-modified by plasma.

In addition, in contrast to Comparative Example 6 in which both the blended fabric and glass beads not treated with the softener did not undergo surface modification treatment, Example 3 in which both the fabric and glass beads were surface-modified with plasma showed a 28% increased luminance value. It was.

Generally, in the art, fabric softeners are treated, and thus, the binding strength with the binder is weak and the compatibility is weak, so that an additive such as a separate compatibilizer or a coupling agent is used to prevent the binding force of the binder from being lowered. However, in the present invention, the bonding force between the original and the binder is increased by the plasma treatment on the fabric surface, and the bonding force between the binder and the glass bead is increased due to the increase of the surface tension of the glass beads surface-treated with plasma.

Experimental Example 2.

The retroreflective fabric prepared in Example 1 and Comparative Example 4 was cut into a 300 mm × 300 mm square size to prepare a fabric specimen prepared at a magnification of 240 times using a microscope to observe the microstructure. The microstructure results are shown in FIG.

Figure 2 on the right is a microstructure of the retroreflective fabric of Example 1, the figure on the left is a microstructure of the retroreflective fabric of Comparative Example 4.

2, in the case of the retroreflective fabric prepared in the embodiment of the surface-modified glass beads according to the present invention, the glass bead powder compared to the retroreflective fabric prepared in the comparative example was not the surface-modified glass beads Acidity showed an improved effect.

This phenomenon increased the surface tension of plasma-modified glass beads and improved dispersibility during mixing with the binder, which in turn reduced the amount of glass beads needed to achieve the desired brightness while simultaneously reducing the amount of binder added. It can be effective.

As mentioned above, specific portions of the present disclosure have been described in detail, and it is apparent to those skilled in the art that such specific techniques are merely preferred embodiments, and thus the scope of the present disclosure is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (12)

Retroreflective composition comprising glass beads surface-treated with plasma.
The method of claim 1,
The glass bead is a retroreflective composition, characterized in that treated with at least one activator selected from the group consisting of reactive discharge gas, compressed air and a combination thereof as an activator in the plasma active space.
The method of claim 1,
The glass bead is a retroreflective composition, characterized in that it has a refractive index of 1.7 to 2.5 and more than 98% transparency.
The method of claim 1,
The glass bead is retroreflective composition, characterized in that consisting of spherical particles having an average particle diameter of 30 to 90㎛.
The method of claim 1,
The retroreflective composition further comprises a binder, a thickener and a solvent.
The method of claim 5,
The retroreflective composition further comprises at least one additive selected from the group consisting of a dispersant, a curing agent, a curing accelerator, an ultraviolet absorber, a yellowing agent, a light diffusing agent, a surfactant, an antistatic agent, and a mixture thereof. Retroreflective composition comprising.
fabric; And
Retroreflective fabric comprising a retroreflective layer containing a glass bead surface-treated with a plasma applied on the fabric.
The method of claim 7, wherein
The fabric is a retroreflective fabric, characterized in that the surface modified by plasma.
The method of claim 7, wherein
The glass bead is retroreflective fabric, characterized in that having a refractive index of 1.7 to 2.5 and more than 98% transparency.
The method of claim 7, wherein
The glass bead is retroreflective fabric, characterized in that consisting of spherical particles having an average particle diameter of 30 to 90㎛.
Modifying the surface of the glass beads with plasma;
Mixing the modified glass beads with a binder to prepare a retroreflective composition; And
A method of manufacturing a retroreflective fabric comprising applying the retroreflective composition to a surface of a fabric to form a retroreflective layer.
The method of claim 11,
The fabric is a method of manufacturing a retroreflective fabric, characterized in that the fabric is modified surface by plasma.

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