KR20110043803A - Anti-counterfeit fiber by electrospinning, manufacturing method thereof and security products their in these fibers - Google Patents

Abstract

PURPOSE: A method for fabricating non-woven fabric by electrospinning is provided to prevent counterfeit and to produce security product. CONSTITUTION: A method for fabricating non-woven fabric comprises: a step of dissolving polymer resin and functional dye in an organic solvent; a step of performing electrospinning to prepare an electrospinning solution; and a step of performing electrospinning. The organic solvent is selected from ketone, aromatic hydrocarbon, carboxylic acid, and alcohol of 1-7 carbon atoms. The polymeric resin is selected from the group consisting of polyurethane, cellulose acetate, polyvinyl acetate, ethylcellulsoe, polystyrene, polyamide, polyvinyl acetal, and polyvinyl butyral.

Description

Anti-counterfeit fiber by electrospinning, manufacturing method etc. and security products their in these fibers}

The present invention relates to an anti-counterfeiting nonwoven fabric by electrospinning, a method for manufacturing the same, and a security product using the same. Specifically, a fiber exhibiting functionality by mixing a special pigment with a nonwoven fabric produced by electrospinning, and a method for manufacturing the same. It relates to a security product using the same.

Looking at the anti-counterfeiting functional fiber used in the prior art as follows. Fibers with fluorescence properties are melted or dispersed in a synthetic resin for textiles with white or colored fluorescent pigments or dyes and made into fibers by injection or fixed by reacting fluorescent dyes on the surface of the fibers, It is manufactured using the method of manufacturing with ink, printing, coating, and coating | covering a fiber. Related patents thereof include Japanese Patent Laid-Open No. 63-196719 (1988), Japanese Patent Laid-Open No. 63-165517 (1988), and Japanese Patent Laid-Open No. 2-200811 (1990). These fluorescent fibers are made of short fibers, and a small amount is added to the paper making process to make paper, but it is hard to see visually.However, when the paper is exposed to ultraviolet rays, it is easily observed because the short fibers are excited by the ultraviolet rays and fluoresce. It has the effect of preventing forgery.

Patents related to fibers with enhanced fluorescence properties are as follows. Korean Patent No. 1993-0025561 describes a forgery preventing fiber in which the visible color and the fluorescent color are different by visually dyeing a fluorescent dye that is first dyed to visually see the fiber and then dyeing a fluorescent dye that is expressed in a different color. Korean Patent Laid-Open No. 1999-0073638 describes a forgery preventing fiber that produces colored verbs in the form of colored clothes by cutting the fibers in the form of dyeing by fusing the fibers and dyeing the outside and not the inside. In Korean Patent Application No. 2001-0112666, the appearance color of the fiber has little or white color, and includes both a phosphor and a fluorescent material having different emission wavelengths, and thus shows a fluorescent color upon external stimulation such as ultraviolet irradiation. It describes an anti-counterfeiting fiber that displays a phosphorescent color when the stimulus is removed. In Korean Patent No. 2000-0076051, after manufacturing short fibers of an outer core composite fiber composed of an outer component and an inner component, short fibers, that is, short fibers are added to a solvent for dissolving the inner component, so that only a part of the inner component is dissolved. It describes a dichroic short fiber manufactured by removing the short fiber so that the color of the sock end and the middle part are different.

All of the techniques investigated above are in the form of fibers by uniaxial spinning (monofilament), and functionality is added to each of the characteristics by mixing colored pigments, fluorescent pigments, etc. in the fabrication process or dyeing and dyeing in a later process.

Korean Patent 1998-0069360 describes an anti-counterfeiting paper with a double perforated donut-shaped silver plate, and International Patent 2007-144657 describes a 2 to 5 mm star after coating a functional material on a material such as paper or film. This paper deals with the use of planchettes, cut or stamped into shapes or circles, in the manufacture of paper.

The present inventors intended to increase the anti-counterfeiting function by adding a non-woven fabric made of nano-sized fibers by electrospinning to a certain size to add to the sheet for security products. The present inventors produced a nano-sized functional nonwoven fabric by electrospinning an electrospinning spinning solution prepared by dissolving a polymer resin and a functional dye in an organic solvent, and then cutting it into short fibers and inserting a small amount into a manufacturing process of a security product. It is used for special products such as banknotes, bonds, passports, ID cards, etc. to identify the authenticity by showing the functionalities such as the color of pigments, the fluorescence or infrared absorption characteristics of UV rays, and the discoloration characteristics of solvents. The present invention has been accomplished by discovering that it can be used as a functional element with anti-counterfeiting element.

It is an object of the present invention to provide a method for producing a counterfeit nonwoven fabric by electrospinning. Another object of the present invention is to provide a security product containing the anti-counterfeiting fibers by the electrospinning. It is another object of the present invention to provide a security product which is prevented from forgery and tampering and is easy to identify the authenticity.

The present invention relates to a method of manufacturing a non-woven fabric for preventing anti-counterfeiting by electrospinning, and in particular, by mixing a special pigment to the non-woven fabric produced by electrospinning, the color or color of ultraviolet pigments or the absorption of infrared rays, solvents It is to produce a fiber exhibiting various functionalities such as discoloration characteristics.

In addition, the present invention relates to a security product using an anti-counterfeiting nonwoven fabric by electrospinning, specifically, a color or ultraviolet ray by a colored pigment by a special pigment mixed when manufacturing the anti-counterfeiting nonwoven fabric by electrospinning. Fluorescence or infrared absorption characteristics by, the discoloration characteristics by the solvent is expressed, etc. can verify the authenticity.

In addition, the anti-counterfeiting nonwoven fabric by the electrospinning according to the present invention can be used in special products, such as banknotes, bonds, passports, identification cards that require security can be used as an authenticity identification element and a functional element to prevent forgery. .

Hereinafter, the present invention will be described in more detail.

The anti-counterfeiting nonwoven fabric by electrospinning of the present invention is composed of a polymer resin dissolved in a specific solvent and a special material for giving functionality.

Depending on the type of the dye constituting the anti-counterfeiting nonwoven fabric by the electrospinning, when the contact with a specific solvent, the dye dissolves so that the dye color spreads widely, solvent discoloration characteristics, ultraviolet fluorescence characteristics, infrared absorption characteristics, colored pigments You can check the authenticity due to color.

The anti-counterfeiting nonwoven fabric by electrospinning of the present invention is prepared through the following steps:

1) preparing an electrospinning spinning solution by dissolving a polymer resin and a functional dye in an organic solvent; And

2) preparing a nano-sized functional nonwoven fiber by electrospinning the spinning solution of step 1).

The polymer resin of step 1) may be used as long as it is dissolved in a specific solvent, specifically, polyurethane dissolved in a mixed solvent of formamide and tetrahydrofuran, cellulose acetate or polyvinylacetate, and toluene dissolved in acetone. Ethyl cellulose or polystyrene to be dissolved, Polyamide soluble in formic acid, Polyvinyl acetal to be dissolved in ester, Ethyl cellulose or polyvinyl butyral to be dissolved in alcohol having 1 to 7 carbon atoms (for example, ethanol, butanol, isopropyl alcohol, etc.) Etc., It is preferable to use one or more selected from the group consisting of polyurethane, cellulose acetate, polyvinylacetate, ethyl cellulose, polystyrene, polyamide, polyvinyl acetal and polyvinyl butyral.

The special material for giving the functionality of step 1) is a water-insoluble and soluble dye, fluorescent dye or infrared absorbing dye which is dissolved in an organic solvent. Examples of representative dyes of the oil-soluble dyes are yellow dyes and red dyes. (solvent red 122), blue dye (solvent blue 70), black dye (solvent black 27), and examples of fluorescent dyes are Lomogen F yellow 083 (BASF), Lumogen F red 305 (BASF), Lumogen F blue 650 (BASF), and examples of dyes for giving infrared absorption function include Epolight 1125 (Epolin, light green, absorption wavelength 950nm, dissolved in acetone and toluene), Epolight 1178 (Epolin, brown, absorption wavelength 1073nm, acetone and Soluble in toluene).

The organic solvent of step 1) is selected from ketones, aromatic hydrocarbons, carboxylic acids, esters and alcohols having 1 to 7 carbon atoms, specifically, selected from acetone, toluene, formic acid, ethanol, isopropyl alcohol and butanol It is preferable to be.

The functional dye of step 1) is mixed in an amount of 0.1 to 1.0% by weight based on the weight of the polymer resin, and the mixture of the polymer resin and the dye is contained in an amount of 1 to 5% by weight with respect to the electrospinning spinning solution to exhibit functionality. do.

  The electrospinning of step 2) dissolves the resin, which is transformed into a fiber, into a solvent and gives an electric field when the resin solution falls through the small nozzle, generating a force opposite to the surface tension by charge or dipole repulsion on the drop surface. Jet of the resin solution is generated to form fibers in nano units. Unlike the general fiber manufacturing method, the formed fiber has a very thin fiber and is generally attached to the fiber and the fiber in the form of a nonwoven fabric. The main variables and factors in electrospinning include the concentration of resin and solvent, the temperature and humidity of the spinning process, the applied eyepiece, the diameter of the tip from which the resin solution is ejected, and the shape of the collecting part for collecting the fiber. Since it is possible to apply only to this, it is not specifically limited.

The electrospinning of step 2) may use alternating current or direct current, and is preferably carried out under conditions of a voltage of 15 to 35 kV (20 kV in the embodiment) and a radiation distance of 5 to 20 cm.

The anti-counterfeiting nonwoven fabric by electrospinning prepared by the above manufacturing method has a diameter of 400 to 700 nm, depending on the degree of dye content, cobweb-shaped and colored fibres. It has a function of fibrous form, fibrous form of fluorescence when irradiated with ultraviolet rays, and fibrous form that absorbs infrared rays in the infrared region and looks black. Such non-woven fibers are used in the form of pieces (silver discs) punched in a circular, square, rectangular or star shape by a short fiber cut into 0.1 to 5 mm or a blue hollow needle.

The silver plate manufactured by the above method can give a fiber form, color, fluorescence, and infrared effect, which are difficult to forge, by adding a small amount to a process for manufacturing a sheet or paper for security products.

The present invention also provides a security product containing the anti-counterfeiting non-woven fabric produced by the electrospinning. The security product is composed of 99.99 to 99.9999% by weight of cotton fibers and 0.0001 to 0.01% by weight of anti-counterfeiting nonwoven fibers. The anti-counterfeiting nonwoven fabric has a diameter of 400 to 700nm, and cut into pieces (silver plate) punched in a circular, square, rectangular, or star shape by a short fiber or a blue hole needle cut to a length of 0.1 to 5.0 mm. It is mixed and subjected to the papermaking process.

The security product of the present invention includes an anti-counterfeiting nonwoven fabric and cotton fiber prepared by electrospinning a spinning solution containing a polymer resin, a functional dye, and an organic solvent. The anti-counterfeiting nonwoven fabric produced by the electrospinning is prepared as described above.

The security product manufactured according to the method of the present invention includes anti-counterfeiting nonwoven fabrics by electrospinning as anti-counterfeiting and tamper proof elements, so that forgery and tampering is difficult and the authenticity of the contents is easy to identify. In other words, the security product produced according to the method of the present invention is in contact with the organic solvent, the dye is present on the surface and the inside of the paper is dissolved color, or after contact with the organic solvent to check the fluorescence by shining the ultraviolet lamp, It absorbs infrared light in the infrared region and makes it look black. Therefore, when the modulators use an ink eraser containing an organic solvent for the purpose of tampering with the printed or written content with ink on a security product manufactured according to the method of the present invention, the dye present in the paper of the modulation site due to the organic solvent The color changes due to the color change, and it is easy to determine whether the modulation is performed. In addition, when counterfeiters circulate the printed matter printed on the security paper manufactured according to the method of the present invention, the forged printed matter can be easily judged by authenticity by contacting with an organic solvent or the like.

When the anti-counterfeiting nonwoven fabric by electrospinning according to the present invention in the form of a piece (silver) punched into a circular, square, rectangular or star shape by a single fiber or a blue hollow frame, if a small amount is contained in the security product There is a feature that can identify the authenticity of the paper by the presence of non-woven fibers that can not be represented in the form of silver, specific solvent discoloration characteristics, infrared absorption characteristics, fluorescence characteristics by ultraviolet light. Such anti-counterfeiting non-woven fabrics by electrospinning can be used as authenticity identification elements of banknotes, passports, checks, securities and special products that require security. In addition, the security paper containing a non-woven fabric for anti-counterfeiting by electrospinning according to the present invention also prevents forgery and tampering of security paper, such as securities, secret documents, it is easy to evaluate the forgery and tampering.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

[ Example  1] Manufacture of Security Paper I

Electrospinning was performed to make a polyurethane nonwoven fabric. Polyurethane used 99.5g of pellethane 2363-80AE material from Dow (USA), and 0.5g of Lumogen F Red 305 (BASF, perylene), a red fluorescent dye, was added to give a non-woven fabric with fluorescence. Dimethylformamide (DMF) and tetrahydrofuran (THF), which are solvents of urethane and red fluorescent dye, were dissolved in 250 mL of a mixed solvent mixed at 50:50 to obtain a solution concentration of 40%.

Electrospinning was performed using the Oriental Electronics Model SJ305A, the voltage was 20kV, the radiation distance is 15cm, the collector diameter was 100nm in the prepared solution in a glass pipette and spun. The average fiber diameter of the electrospun nonwoven fabric was 500 nm, which appeared to be a white nonwoven fabric to the eye, but when irradiated with ultraviolet light, it was seen as a red fluorescent fiber.

The spun yarn was carved into a circle with a diameter of 1 mm using a punching needle (a machine for drilling stamps). During the manufacturing process of banknote paper, a circular nonwoven fabric prepared above was added at 0.002% by weight to prepare a paper by a conventional paper manufacturing method.

In the paper thus prepared, circular silver plaques were distributed per 3 to 10/100 cm ² , and when illuminated with an ultraviolet lamp, red circular silver plaques were observed, and when viewed under a microscope, the shape of the nonwoven fabric such as spider web was confirmed.

[ Example  2] Manufacture of Security Paper II

Electrospinning was performed to make a nonwoven fabric made of cellulose acetate. 99.45 g of cellulose acetate was used. To impart blue fluorescence to the nonwoven fabric, blue fluorescent dye Lumogen F Red 650 (BASF, naphthalimide) was added at 0.5 g and the blue dye C.I. No solvent blue 70 (BASF, Neozapon Blue 807) was added at 0.05 g. Cellulose acetate, blue fluorescent dye, and blue dye were dissolved in 250 mL of acetone, a solvent of cellulose acetate, a blue fluorescent dye, and a blue dye, so that the concentration of the solution was 40%.

Electrospinning was spun into a glass pipette with a gas solution at a voltage of 20 kV, a spinning distance of 10 cm, and a collector diameter of 100 nm. The average fiber diameter of the electrospun nonwoven fabric was 600 nm. Other experiments were carried out in the same manner as in Example 1.

The paper thus produced was not visible to the eye, but when viewed under a microscope, it was a pale blue circular nonwoven fabric. When acetone was dropped on the paper, the blue dye of the nonwoven fabric melted, and the color of the solvent was discolored to turn blue.

[ Example  3] Manufacture of Security Paper III

In the same manner as in Example 1, Epolight 1125 (Epolin, light green, absorbing wavelength 950 nm), which is a dye for imparting infrared absorption characteristics, was further added at 0.1 g, and the final solution concentration was 40%. The nonwoven fabric thus produced appeared very light brown and showed red fluorescence when irradiated with ultraviolet rays, and appeared black at a wavelength of 950 nm, which is an infrared region.

Claims (17)

1) preparing an electrospinning spinning solution by dissolving a polymer resin and a functional dye in an organic solvent; And 2) preparing a nano-sized functional nonwoven fiber by electrospinning the spinning solution of step 1); Method for producing a non-woven fabric for preventing counterfeit by electrospinning comprising a. The method of claim 1, The polymer resin is at least one selected from the group consisting of polyurethane, cellulose acetate, polyvinylacetate, ethyl cellulose, polystyrene, polyamide, polyvinyl acetal and polyvinyl butyral. Method for producing a non-woven fabric for anti-counterfeit. The method of claim 1, The organic solvent is a ketone, an aromatic hydrocarbon, a carboxylic acid, an ester and a method for producing a counterfeit nonwoven fabric by electrospinning characterized in that the alcohol having 1 to 7 carbon atoms. The method of claim 3, The organic solvent is a method for producing a counterfeit nonwoven fabric for electrospinning, characterized in that selected from acetone, toluene, formic acid (formic acid), ethanol, isopropyl alcohol and butanol. The method of claim 1, The functional dye is a water-insoluble and soluble dye, fluorescent dyes or infrared dyes which are dissolved in an organic solvent. The method of claim 1, The functional dye is an anti-counterfeiting nonwoven fabric manufacturing method of the electrospinning, characterized in that mixed by 0.1 to 1.0% by weight relative to the weight of the polymer resin. The method of claim 1, The mixture of the polymer resin and the dye is a method for producing a counterfeit nonwoven fabric by electrospinning, characterized in that 1 to 5% by weight based on the spinning solution. The method of claim 1, Electrospinning of the step 2) can be used for alternating current or direct current, voltage 15 to 35 kV, the production method of the anti-counterfeiting nonwoven fabric by electrospinning characterized in that it is carried out under the conditions of 5 to 20cm spinning distance. The method of claim 1, Method for producing a counterfeit non-woven fabric for electrospinning, characterized in that the diameter of the functional nonwoven fabric 400 to 700nm. A security product comprising an anti-counterfeiting nonwoven fabric and a cotton fiber produced by electrospinning a spinning solution containing a polymer resin, a functional dye, and an organic solvent. The method of claim 10, The polymer resin is at least one member selected from the group consisting of polyurethane, cellulose acetate, polyvinylacetate, ethyl cellulose, polystyrene, polyamide, polyvinyl acetal, and polyvinyl butyral, and the organic solvent is a ketone Selected from aromatic hydrocarbons, carboxylic acids, esters and alcohols, wherein the functional dye is a water-insoluble and soluble dye, fluorescent dye or infrared dye which is dissolved in an organic solvent. The method of claim 10, The functional dye is a security product, characterized in that mixing in 0.1 to 1.0% by weight relative to the weight of the polymer resin. The method of claim 10, The mixture of the polymer resin and the dye is a security product, characterized in that 1 to 5% by weight based on the spinning solution. The method of claim 10, Electrospinning can be used alternating current or direct current, security products, characterized in that carried out under the conditions of voltage 15 to 35 kV, radiation distance 5 to 20cm. The method of claim 10, Security product, characterized in that the anti-counterfeiting nonwoven fabric diameter of 400 to 700nm. The method of claim 15, The anti-counterfeiting nonwoven fabric is a security product, characterized in that in the form of pieces punched in a circular, square, rectangular or star shape by a short fiber or a blue hollow frame cut to a length of 0.1 to 5.0mm. The method of claim 10, The anti-counterfeit non-woven fabric is a security product, characterized in that it contains 0.0001 to 0.01% by weight based on the total weight of the security product.