KR101839480B1 - Nail sticker and method for manufacturing thereof - Google Patents

Abstract

The present invention relates to a nail sticker and more particularly to a nail sticker which can be easily detached and attached to a nail or a nail without using an organic solvent such as acetone, It can be attached to the curved surface naturally. It can be cut cleanly without damaging or damaging the shape in the course of the sticker cutting, has excellent storage stability that can be stored for a long time after opening the product without any separate sealing means, and can be realized with a very slim thickness A nail sticker and a manufacturing method thereof.

Description

NAIL STICKER AND METHOD FOR MANUFACTURING THE SAME

The present invention relates to a nail sticker and more particularly to a nail sticker which can be easily detached and attached to a nail or a nail without using an organic solvent such as acetone, It can be attached to the curved surface naturally. It can be cut cleanly without damaging or damaging the shape in the course of the sticker cutting, has excellent storage stability that can be stored for a long time after opening the product without any separate sealing means, and can be realized with a very slim thickness A nail sticker and a manufacturing method thereof.

As interest in beauty has increased recently, more and more users are trying to express beauty and personality by using manicure.

However, it takes a comparatively long time to apply and polish the nail polish and the like, and a general user who is unfamiliar with such a task has a problem that it takes a long time and it is difficult to produce a desired aesthetic feeling.

In order to solve such a problem, sticker type nail decoration means has been proposed. However, until now, the commercially available nail decorating means has a problem of applying solvent to the nail portion and attaching the sticker.

In order to solve this problem, a sticker having an adhesive layer on one side of the nail decorating means has been proposed. However, it is difficult to adhere easily to the curved surface of the hand / toenails due to lack of flexibility of the sticker, There is a problem in that the replacement period of the battery is very short.

In recent years, stickers which attempt to improve the flexibility of the adhesive layer by providing a solvent with an increased content in the adhesive layer have been disclosed. However, in the process of cutting the sticker into a nail shape, the adhesive layer having a high solvent content is difficult to cut, Or the cut shape of the adhesive layer is broken into a distorted state, thereby deteriorating the appearance of the product.

Further, there is a problem that the color of the sticker is damaged due to the disintegration of the sticker at the time of cutting, and the quality of the product is remarkably deteriorated, such as the adhesion force due to the damage of the adhesive layer.

Furthermore, sealing of the product is very important to maintain the content of the solvent until the sticker is attached to the hands / toenails, and the solvent is evaporated from the adhesive layer without a separate sealing means, resulting in a problematic deterioration in adhesiveness and flexibility. In addition, when the product is not used immediately after opening the product, the adhesiveness and flexibility of the product deteriorate due to the evaporation of the solvent, which makes it difficult to store the product for a long time and the storage stability is poor.

Therefore, it is urgently required to develop a nail sticker which is easily removable to the hands / toenails and easily attached to the outer surface of the curved surface of the hand / nail to facilitate cutting and storage stability.

Korean Patent Publication No. 10-1239735

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-described problems, and it is an object of the present invention to provide a method of manufacturing a cigarette which can easily attach and detach to a nail or a nail without using an organic solvent such as acetone, It can be attached to the curved surface of the hands and toenails. It can be cut cleanly without being broken or damaged in the process of cutting the sticker. It has excellent storage stability that can be stored for a long time after opening the product even without a separate sealing means. It is an object of the present invention to provide a nail sticker that can be implemented and a method of manufacturing the same.

In order to solve the above-mentioned problems, the present invention relates to a method for producing a polyisocyanate compound, which comprises reacting a diisocyanate component containing an aromatic diisocyanate, a first diol component containing at least a hydroxyl group at both ends thereof and a second diol component having a carboxyl group, A base layer formed from a prepolymer and a polyurethane polymer to which a diamine component has been reacted; An adhesive layer formed on one side of the substrate layer; A decorative pattern layer formed on the other surface of the substrate layer; And a protective layer formed on the decorative pattern layer.

According to an embodiment of the present invention, the first diol component may have a number average molecular weight of 950 to 8,000.

The diisocyanate component and the first diol component may be reacted at a molar ratio of 1.8 to 2.0: 1.0.

In addition, the first diol component and the second diol component may be contained at a molar ratio of 1.5 to 1.0: 1.0, and may be reacted with the diisocyanate component, respectively.

The diisocyanate component may further include at least one of aliphatic diisocyanate and alicyclic diisocyanate, and at least one of the aliphatic diisocyanate and the alicyclic diisocyanate and the aromatic diisocyanate may have a molar ratio of 1: 1.5 to 2.0 .

The polyurethane polymer may have a number average molecular weight of 4,000 to 8,000.

Also, the diisocyanate component may include methylenediphenyl diisocyanate as an aromatic diisocyanate, and further includes isophorone diisocyanate as an alicyclic diisocyanate, and the first diol component may be a polypropylene having a number average molecular weight of 950 to 2200 Glycol.

In addition, the adhesive layer may include 50 to 70% by weight of an adhesive component and 30 to 50% by weight of nitrocellulose.

Also, the present invention is produced by forming an adhesive layer on one surface of a substrate layer, forming a decorative pattern layer on the other surface, and forming a protective layer on the decorative pattern layer, wherein the substrate layer comprises (1) an aromatic diisocyanate And a second diol component having a carboxy group to produce an isocyanate-terminated polyurethane prepolymer, wherein the isocyanate-terminated polyurethane prepolymer is at least one compound selected from the group consisting of: (2) mixing water with the isocyanate-terminated polyurethane prepolymer to prepare an aqueous solution; (3) adding a diamine component to the aqueous solution to prepare a polyurethane polymer; And (4) coating an aqueous solution containing the polyurethane polymer on a surface of the release paper to a predetermined thickness and drying the nail sticker.

According to an embodiment of the present invention, it is possible to further include neutralizing the isocyanate-terminated polyurethane prepolymer between steps (1) and (2).

The viscosity of the isocyanate-terminated polyurethane prepolymer before water is mixed in the step (2) may be 100,000 to 300,000 cps.

In addition, the viscosity of the polyurethane produced in the step (3) may be 40 to 200 cps.

In addition, the particle size of the polyurethane produced in the step (3) may be 40 to 200 탆.

According to the present invention, it is possible to easily attach and detach the nail or the toenails, to make the nail and the toenails feel as if the nail polish is applied when the nail is attached with a very slim thickness, And can be cut cleanly without damaging or damaging the shape in the course of the sticker cutting process and can be stored for a long time after the product is opened without the need of a separate sealing means.

1 (a) to 1 (c) are FTIR analysis results of an intermediate product and an end product in a process for producing a polyurethane aqueous dispersion according to Example 1 according to a preferred embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

In the case of the nail sticker according to the present invention, the adhesive layer is formed on one surface of the substrate layer, the decorative pattern layer formed on the other surface of the substrate layer, and the protective layer formed on the decorative pattern layer.

First, the substrate layer will be described.

The base layer enhances the film formability of the nail sticker and functions as a support member for the adhesive layer, the decorative patter layer and the like. The base layer provided on the conventional nail sticker has a problem that the flexibility is remarkably poor. Considering that the attachment surface of the nail sticker is a nail or a toe, that is, a curved surface rather than a flat surface, the nail sticker lacking flexibility has a problem that the edge is easily lifted based on the portion where the curvature increases, even when attached to the nail / toenails. In addition, even if the nail / toenails are manufactured so as to have a predetermined shape at first because the shape of each nail / nail is different from each other, it may be necessary to further cut the nails / nails at the time of the procedure in accordance with the shape / shape of the nails. However, the conventional nail sticker is easy to cut due to its poor cutability, and when the scissors or the knife touches the nail sticker, the nail sticker is cut off as it is cut when the scissors or the knife touches, so that the shape of the cut surface becomes very messy. In the case of nail stickers, the beauty of the appearance is very important, and if the cut surface is not clean, the aesthetics may be deteriorated. Accordingly, the present invention has been made to solve the above-mentioned problems through the base layer formed through the polyurethane polymer according to the present invention, and thus the present invention has been accomplished.

The polyurethane forming the substrate layer comprises a diisocyanate component comprising an aromatic diisocyanate, at least a first diol component comprising a hydroxy group at both ends, and a second diol component having a carboxyl group, wherein the reacted isocyanate- And a polyurethane polymer to which the diamine component is reacted.

First, the isocyanate-terminated polyurethane prepolymer is formed by reacting with a diisocyanate component containing an aromatic diisocyanate, a first diol component containing at least a hydroxyl group at both terminals and a second diol component having a carboxyl group.

The diisocyanate component comprises an aromatic diisocyanate.

The aromatic diisocyanate can be used without limitation in the case of a known aromatic diisocyanate, but is preferably selected from toluene diisocyanate, methylene diphenyl diisocyanate, p-phenylenediisocyanate, xylylene diisocyanate, 1,5- May include at least one member selected from the group consisting of isocyanate, isocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate and tetramethylxylylene diisocyanate, May contain at least one of isocyanate and methylene diphenyl diisocyanate, more preferably methylene diphenyl diisocyanate. By including an aromatic diisocyanate as the diisocyanate component, it is possible to more easily manufacture a polyurethane polymer having improved flexibility and cutting characteristics, to increase the elasticity of the polyurethane prepolymer, and to control the viscosity for easier coating It may be advantageous to use aliphatic or alicyclic isocyanate alone.

The diisocyanate component is preferably selected from the group consisting of isophorone diisocyanate, dicyclohexylmethane-dicyclohexylmethane-dicyclohexylmethane-dicyclohexylmethane-dicyclohexylmethane-dicyclohexylmethane- Alicyclic diisocyanates such as 4,4'-diisocyanate, trans-1,4-cyclohexane diisocyanate, cis-1,4-cyclohexane diisocyanate and norbornene diisocyanate, and 1,6-hexamethylene diisocyanate , Aliphatic diisocyanates such as (2,2,4) -trimethylhexamethylene diisocyanate, (2,4,4) -trimethylhexamethylene diisocyanate and lysine diisocyanate, and the like. More preferably, isophorone diisocyanate is added among these to further manifest the desired physical properties. It is good to use.

More preferably, the aliphatic diisocyanate and / or the alicyclic diisocyanate and the aromatic diisocyanate are contained in a molar ratio of 1: 1.5 to 2.0. If the aromatic diisocyanate is contained in an amount of less than 1.5 molar ratio, the molecular weight of the polyurethane prepolymer is small, the viscosity is low, and it is difficult to form a coating layer with the polyurethane polymer to be produced. Particularly, It can be very difficult to thinly mold. Further, there is a problem that the adhesive strength is lowered and the adhesive layer or the decorative pattern layer easily peels off. If the aromatic diisocyanate is present in an amount of more than 2.0, it is difficult to disperse the prepared polyurethane polymer in water, so that there is a problem that an additional organic solvent should be further provided. The coating property is lowered, There may be a problem that it easily peels off from the nail after attachment.

Next, the first diol component containing at least a hydroxyl group at both ends will be described. The first diol component may be a polyol and may be a polyol component usually used in the polymerization of a polyurethane. For example, it may be a polyether-based polyol or a polyester-based polyol, and preferably a polyether- More preferably at least one of polypropylene glycol and polytetramethylene glycol, and still more preferably polypropylene glycol. The polyether polyol preferably has a number average molecular weight of 950 to 8,000, more preferably 950 to 4200, and still more preferably 950 to 2200. The first diol component having such a specific type / number average molecular weight is advantageous in that the viscosity of the reactant is lower than that of the other kinds of polyols, and thus the neutralization is facilitated. However, even when polypropylene glycol is used, when the number average molecular weight is more than 8,000, there is a problem that the viscosity of the reactant is high and neutralization is difficult. When the number average molecular weight is less than 950, the viscosity is lowered, And it may be difficult to achieve the desired physical properties of the present invention.

The first diol component is preferably contained in a ratio of 1: 1.8 to 2.0 molar ratio with the above-mentioned diisocyanate component. If the diisocyanate component is contained in an amount of less than 1.8 molar ratio, the molecular weight of the synthesized polyurethane prepolymer increases, There is a problem that hydration may be difficult. In addition, it may be difficult to form a uniform base layer. In addition, if the diisocyanate component is contained in an amount exceeding 2.0 molar ratio, it is possible to increase hydratability and thus to form a uniform base layer, but it may be difficult to produce a base layer having a small thickness due to a decrease in mechanical strength.

Next, the second diol component having a carboxyl group will be described.

The second diol component is provided to increase the water dispersibility of the isocyanate-terminated polyurethane prepolymer. The second diol component having a carboxyl group can be used without limitation in the case of a diol component having at least one carboxyl group, and examples thereof include 2,2-dimethylol acetic acid, 2,2-dimethylol propionic acid, 2,2- , 2-dimethylolbutyric acid, 2,2-methylolvaleric acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, Diaminobutane sulfonic acid or 2,3-dihydroxypropylphenyl phosphate may be used singly or in combination of two or more thereof.

The second diol component having a carboxyl group may be contained at a molar ratio of 1: 1.0 to 1.5 with the first diol component described above. If the first diol component is contained in an amount of less than 1.0, the polyurethane particles become excessively small in the hydration step described later, and the coating properties are significantly lowered, so that it may be difficult to form the base layer, It may be difficult to realize the base layer, and the cut surface may be bad and the aesthetic appearance may be damaged. Further, when the first diol component is contained in an amount exceeding 1.5 molar ratio, it may be difficult to form a base layer having a uniform thickness, and thus the decorative pattern layer may be bent, thereby greatly deteriorating the appearance. In addition, the cut surface may be bad and the aesthetic appearance may be damaged.

Next, the diamine component which reacts with the above-mentioned polyurethane prepolymer will be described.

The diamine component is used to increase the molecular weight of the polyurethane prepolymer, and the component having at least two amine groups can be used without limitation. The diamine component may be selected from the group consisting of 1,2-ethylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,12-dodecanediamine, 1,2-propanediamine, Diamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine), isophoronediamine, 2,2- Tetramethylxylene diamine, and piperazine. Preferably, the diamine component may be piperazine for the purpose of manifesting desired physical properties.

The diamine component may be included in an amount of 3.0 to 4.5 parts by weight based on 100 parts by weight of the polyurethane prepolymer. If the diamine component is out of the above range, it may be difficult to produce a desired polyurethane polymer having a desired weight average molecular weight and particle diameter .

The weight average molecular weight of the polyurethane polymer formed by reacting the polyurethane prepolymer and the diamine component described above may be 4,000 to 8,000, thereby improving the coating property to thereby form the base layer with a uniform thickness, It is easy to prepare a polyurethane water-based dispersion capable of realizing this very clean base layer. If the weight average molecular weight of the polyurethane polymer is less than 4,000, there is a problem that the cut surface becomes dirty. When the weight average molecular weight exceeds 8,000, the surface coating may become uneven, the hydration may be difficult, There may be a problem of peeling.

According to a preferred embodiment of the present invention, the diisocyanate component forming the polyurethane prepolymer comprises methylenediphenyl diisocyanate as the aromatic diisocyanate, further comprising isophorone diisocyanate as the alicyclic diisocyanate, The first diol component may be a polypropylene glycol having a number average molecular weight of 950 to 2200 and through which the present invention may be well suited for producing polyurethane polymers which achieve all of the desired properties.

The polyurethane aqueous dispersion capable of forming the base layer as described above can be produced by a production method described below. However, the present invention is not limited thereto.

The polyurethane aqueous dispersion according to an embodiment of the present invention comprises (1) a diisocyanate component containing an aromatic diisocyanate, a first diol component containing at least a hydroxy group at both terminals and a second diol component having a carboxyl group, To produce an isocyanate-terminated polyurethane prepolymer; (2) mixing water with the isocyanate-terminated polyurethane prepolymer to prepare an aqueous solution; And (3) adding a diamine component to the aqueous solution to prepare a polyurethane polymer.

First, in step (1) according to the present invention, a diisocyanate component containing an aromatic diisocyanate, a first diol component containing at least a hydroxyl group at both ends thereof, and a second diol component having a carboxyl group are reacted to prepare an isocyanate- To prepare a polyurethane prepolymer.

The description of the specific types of the diisocyanate component, the first diol component and the second diol component used in the step (1), the molar ratio thereof, and the like are the same as those described above, The process will be described in detail.

In the step (1), the first diol component and the second diol component are put into a reactor and heated to 80 to 120 ° C, for example, 100 ° C to remove moisture that may be contained in the first diol component and the second diol component can do. Thereafter, the first diol component and the second diol component from which moisture has been removed may be diluted with at least one solvent such as acetone, methyl ethyl ketone, ethyl acetate, cyclohexanone, and methyl propyl ketone, and then the diisocyanate component may be added . At this time, the reaction temperature may be 75 to 90 ° C, for example 85 ° C, and the reaction may take place for 3 to 5 hours. The atmosphere inside the reactor may be a nitrogen atmosphere.

In addition, a catalyst for promoting the formation of a polyurethane prepolymer may be optionally used, and the catalyst may be a catalyst that is typically used in the formation of a polyurethane prepolymer, for example, dibutyltin dilaurate have.

Next, the method may further include neutralizing the isocyanate-terminated polyurethane prepolymer produced in step (1) in order to improve hydration and dispersibility before carrying out the step (2) described below.

Specifically, the isocyanate-terminated polyurethane prepolymer synthesized in step (1) is diluted with a solvent such as acetone, cooled to about 30 to 50 ° C, for example, to 45 ° C, and then the neutralizer is added thereto for about 20 to 60 minutes, A neutralization reaction can be performed for 45 minutes. The neutralizing agent may be selected from the group consisting of triethanolamine, aminomethylpropanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, phosphate, pyrophosphate, oleamine, dodecylamine, triamylamine, triethanolamine, triethylamine, tetrakis (hydroxypropyl) Ethylenediamine, diisopropylamine, and diisopropanolamine may be used. The content of the neutralizing agent added at this time can be selected in consideration of the degree of neutralization of the entire carboxyl group contained in the isocyanate-terminated polyurethane prepolymer, and thus the present invention is not particularly limited thereto.

Next, as step (2) according to the present invention, step (2) is performed by mixing water with the isocyanate-terminated polyurethane prepolymer to prepare an aqueous solution.

This step is a step of dispersing the neutralized isocyanate-terminated polyurethane prepolymer in water as a hydration step. In the hydration process, the particle size and viscosity of the aqueous polyurethane can be determined. It is important that the neutralized isocyanate-terminated polyurethane prepolymer is transferred to a high speed stirrer at 900 rpm or higher and slowly mixed with water while stirring at high speed. At this time, the amount of water to be injected may be 200 to 500 parts by weight based on 100 parts by weight of the isocyanate-terminated polyurethane prepolymer.

In addition, the viscosity of the isocyanate-terminated polyurethane prepolymer before mixing with water in the step (2) may be 100,000-300,000 cps. If the viscosity is less than 100,000 cps, the neutralization viscosity is low, And when the viscosity exceeds 300,000 cps, the neutralization viscosity is high, so it may be very difficult to form a base layer of uniform thickness with an aqueous solution containing the polyurethane polymer produced, and the flexibility is deteriorated, There may be a problem of peeling.

Then, in step (3) according to the present invention, a step of adding a diamine component to the aqueous solution to prepare a polyurethane polymer is carried out.

This step is a step for increasing the molecular weight of the hydrated isocyanate-terminated polyurethane prepolymer to produce a polyurethane polymer which can be implemented as a substrate layer and then have a clean cut surface. The types and doses of the diamine components are the same as those described above, and thus are omitted.

The step (3) may be performed at a temperature of 40 to 60 ° C for 40 to 80 minutes, but is not limited thereto.

The particle size of the polyurethane produced through the step (3) may be 40 to 200 탆. If the polyurethane particle size is less than 40 占 퐉, the mechanical strength of the base layer may be weakened and the cut surface may become dull and dirty. In addition, if the particle size exceeds 200 mu m, the coating may be difficult, the formed substrate layer may have a non-uniform surface, and the flexibility may be deteriorated to easily peel off the hand / toenails.

The aqueous solution containing the polyurethane polymer prepared in the above step (3) is then applied in a predetermined thickness on the release film in step (4), followed by drying to form a base layer.

The application of the aqueous solution may be performed by a known coating method, and the present invention is not particularly limited thereto. The aqueous solution may be dried at a temperature of 60 to 100 ° C for 1 to 60 minutes.

Next, the adhesive layer provided on one surface of the above-described base layer will be described.

The adhesive layer according to an embodiment of the present invention may include a viscous component and nitrocellulose.

The adhesive component may include an alkyl-methacrylate, which is an acrylic monomer, and may further include hydroxymethacrylate or hydroxyethyl acrylate to improve the flexibility of the pressure-sensitive adhesive. If the number of alkyl groups in the alkyl-methacrylate is more than 12, the cohesive force of the pressure-sensitive adhesive is excessively lowered. Therefore, the alkyl-methacrylate preferably has an alkyl group having 1 to 12 carbon atoms. Further, as the meta-acrylate having an alkyl group having 1 to 8 carbon atoms, there may be mentioned butyl-methacrylate, 2-ethylhexyl-methacrylate, ethyl-methacrylate, methyl- Acrylate, n-octyl-methacrylate, isooctyl-methacrylate, iso-butyl-methacrylate, - acrylate can be used.

On the other hand, if the amount of the hydroxymethacrylate is too small, the flexibility of the pressure-sensitive adhesive becomes too low to cause an initial adhesive force to be insufficient, and if it is contained excessively, the flexibility of the pressure-sensitive adhesive becomes excessively low to lower the cohesive force and the adhesion durability. Accordingly, it is preferable that the hydroxy methacrylate is contained in an amount corresponding to 0.05 to 0.3 times the weight of the alkyl-meta-acrylate.

In one embodiment, a solvent may be used to copolymerize the alkyl-meta-acrylate and hydroxy methacrylate, and at least one selected from acetone, methyl ethyl ketone, toluene and ethyl acetate may be used as the solvent.

If the amount of the solvent is too small, the application becomes difficult. When the amount is too large, the adhesive strength may be lowered. Therefore, the amount of the solvent is preferably in the range of 0.02 to 0.9 times the weight of the alkyl-methacrylate desirable.

In another embodiment, an initiator may be used to improve the efficiency of copolymerization of the alkyl-meta-acrylate and hydroxy methacrylate, and as the initiator benzoyl peroxide and / or azobisisobutyronitrile ; AIBN) can be used. If the amount of the initiator is too small, the yield of the copolymerization product is excessively low. If too much initiator is used, the copolymerization reaction may proceed rapidly, resulting in an excessive increase in the molecular weight of the copolymerization product. The amount is preferably in the range of 0.0002 to 0.1 times the weight of the alkyl-meta-acrylate.

According to an embodiment of the present invention, when preparing an acrylic copolymer, a monomer containing a cross-linkable functional group, mainly a vinyl monomer, is added to adjust the glass transition temperature of the nail sticker adhesive or to impart other functions and characteristics. And acrylic monomers may be further used. As preferred monomers therefor, acrylonitrile, methacrylamide, N-methylacrylamide, styrene, methylstyrene, vinyltoluene, glycidyl-metha-acrylate, May be used alone or in combination of two or more. The monomer containing the crosslinkable functional group reacts with the crosslinking agent to give a cohesive force or an adhesive strength by chemical bond so that the adhesive aggregation does not break down under high temperature or high humidity conditions.

Examples of the monomer containing a crosslinkable functional group which can be used in an embodiment of the present invention include 2-hydroxyethyl-metha-acrylate, 2-hydroxypropyl-metha-acrylate, 4-hydroxybutyl- Acrylate, methacrylate, 2-hydroxyethyleneglycol-methacrylate, 2-hydroxypropyleneglycol-methacrylate and the like, acrylic acid, methacrylic acid, acrylic acid diester, , Maleic anhydride, and the like, but the present invention is not limited thereto. The monomers may be used alone or in combination of two or more.

The content of the reinforcing agent is preferably in the range of 0.001 to 0.1 times the weight of the alkyl-meta-acrylate. If the amount of the reinforcing agent is too small, the pressure-sensitive adhesive tends to cause cohesive failure at high temperature or high humidity conditions, and the adhesive strength is decreased. When the content of the reinforcing agent is too large, the compatibility of the pressure- The cohesive force is increased and the stress relaxation ability is lowered.

The adhesive layer-forming coating solution can be prepared by mixing the adhesive component formed as described above with nitrocellulose. The nitrocellulose has a function of improving the durability of the nail sticker. If the content of the adhesive component is less than 50% by weight based on the total weight of the adhesive layer forming coating solution, the adhesive strength is lowered. If the content of the adhesive component exceeds 70% by weight based on the total weight of the adhesive layer forming coating solution, And the water-repellent adhesive strength is lowered.

Meanwhile, the coating layer-forming coating liquid may further include a polyfunctional crosslinking agent acting as a crosslinking agent. As the polyfunctional crosslinking agent, a tolylene diisocyanate adduct of isocyanate-based trimethylolpropane (TDI-1) may be applied. If the content of the polyfunctional crosslinking agent is too low based on the amount of the coating liquid, the cohesion of the coating liquid is decreased. If the polyfunctional crosslinking agent is excessive, the stability of the coating solution is deteriorated. Therefore, By weight to 20% by weight.

The adhesive layer forming coating solution may be applied to one side of the base layer and then formed into an adhesive layer through a heat treatment step. At this time, the heat treatment step may be performed at a temperature of 40 to 50 ° C. for 1 to 5 minutes.

Next, the decorative pattern layer will be described on the other side of the above-described base layer.

The decorative pattern layer is a layer that implements a shape, shape, and / or color that can enhance the aesthetics of the nail sticker. The decorative pattern layer may be formed in a known shape, shape and / or color by a known printing method or the like, so that the present invention is not particularly limited thereto.

Next, the protective layer formed on the above-described decorative pattern layer will be described.

The protective layer protects the decorative pattern layer from physical and chemical stimuli and performs a function of giving a gloss effect. The protective layer may be formed by coating a component known in the art, and a detailed description thereof will be omitted.

The manufactured nail sticker can then be cut and cut to a predetermined size in the form of nails / toenails. The cut nail sticker is excellent in cutting ability and it is easy to cut even in the additional cutting in the process of sticking the sticker to the actual nail / toenails, and the cut surface is clean, .

The present invention will now be described more specifically with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

≪ Example 1 >

First, polypropylene glycol having a number average molecular weight of 2000 as the first diol component and dimethylol propionic acid as the second diol component were mixed in a molar ratio of 1.2: 1 for the preparation of the water dispersion containing the polyurethane copolymer forming the substrate layer The mixture was charged into a reactor and heated to 100 to remove water. Then, 0.5 part by weight of acetone solvent was added to the first diol component and the second diol component, from which moisture was removed, relative to 100 parts by weight of the total weight of the first diol component and the second diol component. After diluting, methylenediphenyl diisocyanate and iso And a diisocyanate component mixed at a molar ratio of 1.8: 1 of boron diisocyanate. At this time, the dian cyanate component was added in an amount of 1.9 moles based on 1 mole of the total moles of the first diol component and the second diol component. Thereafter, the reaction was carried out at a reaction temperature of 85 in a nitrogen atmosphere and a dibutyltin dilaurate catalyst for about 4 hours to prepare an isocyanate-terminated polyurethane prepolymer.

Thereafter, 2.0 parts by weight of acetone was added to 100 parts by weight of the prepared polyurethane prepolymer, diluted, and then cooled to 45. The neutralization reaction was carried out for about 45 minutes by adding triethylamine as a neutralizing agent.

Then, the polyurethane prepolymer having a neutralized viscosity of 120,000 cps was transferred to a high-speed stirrer, and 400 parts by weight of water was added to 100 parts by weight of the polyurethane prepolymer while rotating at 1000 rpm. Then, 2.5 parts by weight of piperazine was added to 100 parts by weight of the polyurethane prepolymer and reacted at 40 DEG C for 50 minutes to obtain a polyurethane prepolymer having a number average molecular weight of 14,062, a viscosity of 100 cps, a solid content of 25% by weight, Mu m. The prepared dispersion was coated on a PET release film and hot-air dried at 100 占 폚 for 45 minutes to prepare a base layer having a thickness of 200 占 퐉.

Then, to form an adhesive layer, 10 parts by weight of hydroxy methacrylate, 80 parts by weight of acetone, 3 parts by weight of benzoyl peroxide as an initiator, and 100 parts by weight of a silane coupling agent (KBM403 , Shin-Etsu Co., Ltd.), and the mixture was stirred at room temperature for 2 hours. Thereafter, 66.7 parts by weight of a nitrocellulose resin was added to 100 parts by weight of isopropyl-metha-acrylate and hydroxy methacrylate in the crosslinking solution, a tolylene diisocyanate adduct of isocyanate-based trimethylolpropane (TDI-1 ) Was mixed to prepare an adhesive layer forming coating solution. The adhesive layer forming coating solution was coated on one side of the substrate layer and then dried at 45 ° C for 3 minutes to form an adhesive layer having a thickness of 30 μm from which acetone had been removed .

Thereafter, a white manicure was printed on the other surface of the substrate layer so as to have a thickness of 30 占 퐉, and then silk printing was repeated four times with a transparent manicure so as to have a thickness of 25 占 퐉 on the top of the silk- Thick nail sticker was prepared.

≪ Examples 2 to X >

The nail sticker as shown in Table 1 or 2 was prepared as a base layer prepared by changing the composition of the base layer as shown in Table 1 or Table 2,

≪ Comparative Examples 1 and 2 &

Except that the aromatic diisocyanate component was omitted or the second diol component was omitted as shown in Table 2 below to prepare a base layer to prepare a nail sticker as shown in Table 2 below.

<Experimental Example 1>

The following physical properties of the polyurethane water dispersion for preparing the substrate layers prepared in Examples and Comparative Examples were evaluated and shown in Tables 1 and 2.

1. Measurement of particle size of polyurethane particles

The average particle size and particle size distribution of the polyurethane particles were measured at room temperature after dispersing the samples in water using a Malvern light scattering (Model RCS 4700) instrument after the samples were diluted with water and ultrasonically dispersed.

2. Viscosity and solids measurement

Since the viscosity of the prepared polyurethane was low after the dispersion was completed, it could not be measured precisely. Therefore, the average viscosity was measured three times from 25 times using a Rion VT-04 viscometer and a No. 3 spindle used for measuring emulsion adhesive viscosity The solid content was determined by measuring the values before and after drying in an electric oven at 105 for 3 hours as prescribed in KS. At this time, the weight of each sample was 1 g.

<Experimental Example 2>

The instrument used in this experiment was Bio Rad FT-IR (Model FTS-175C). The measurement conditions were as follows: The sample was dried in a thin film form (about 0.1 μm) and dried at 25 ° C.

(A) the isocyanate-terminated polyurethane prepolymer before the neutralization reaction, (b) the isocyanate-terminated polyurethane prepolymer after the neutralization reaction, and (c) the polyurethane in the final polyurethane water- FTIR analysis was performed on the above-mentioned samples, and the results are shown in Figs. 1 (a) to 1 (c).

Specifically, in the spectrum of FIG. 1 (a), a peak near 2200 cm ^-1 appears strongly, which is a strong characteristic of the characteristic peak of -NCO as the isocyanate of the polyurethane prepolymer is terminated, It can be confirmed that a polyurethane prepolymer at the isocyanate end was prepared.

In FIG. 1 (b), the peak near 2200 cm ^-1 after the neutralization step is strong, indicating that triacetylamine, which is a neutralizing agent, is more reactive with the carboxylic acid present in the second diol component than the isocyanate present at the end of the reaction It can be seen as mainly reacting.

May determine the Fig. 1 (c) Does the -NCO peak in the vicinity of 2200cm ^-1 spectral image is not destroyed in which the isocyanate is completely destroyed are seen as the peaks of about the nature of the -NCO peak near 2200cm ^-1 does not appear .

<Experimental Example 3>

The following properties of the nail sticker in the examples and comparative examples were evaluated and shown in Tables 1 and 2.

1. Coating uniformity of substrate layer

The coating uniformity of the base layer was evaluated. Specifically, the surface of the substrate layer was measured through a surface roughness meter. Relative Examples and Comparative Examples were relatively converted based on the measured arithmetic mean roughness (Ra) of Example 1 of 100%. When the calculated percentage is less than 100%, the coating layer has a higher coating uniformity than that of Example 1, and when it exceeds 100%, the coating layer has a lower coating uniformity than that of Example 1.

2. Is the cut surface clean

The prepared nail sticker was cut with scissors, and the cut surface was observed with an optical microscope to evaluate the degree of cleanliness such as whether the cut surface was broken. The specimens were cut to a length of 1 cm in both width and height, 100% when there was no abnormality with respect to any one cut surface, Percentages are calculated and shown.

[Table 1]

[Table 2]

As can be seen from Tables 1 and 2 above,

It can be seen that the coating uniformity of the substrate layer and the cleavage of the cut surface of the nail sticker are significantly poor in the comparative example as compared with the examples.

Further, in Examples 10 and 13, it can be confirmed that the physical properties of the first diol and the second diol are significantly lower than those of Examples 1, 11 and 12 as the diol deviates from the preferred range according to the present invention.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (13)

A diisocyanate component comprising isophorone diisocyanate and methylene diphenyl diisocyanate in a molar ratio of 1: 1.5 to 2.0, and a diol component comprising a polypropylene glycol having a number average molecular weight of 950 to 2200 and a second diol component having a carboxyl group At a molar ratio of 1.5 to 1.0: 1.0, wherein the diisocyanate component and the first diol component are reacted at a molar ratio of 1.8 to 2.0: 1.0, and an isocyanate-terminated polyurethane prepolymer obtained by reacting the isocyanate- A substrate layer formed by reacting, formed of polyurethane polymer particles having a particle size of 40 to 200 占 퐉;
An adhesive layer formed on one surface of the substrate layer;
A decorative pattern layer formed on the other surface of the substrate layer; And
And a protective layer formed on the decorative pattern layer. delete delete delete delete The method according to claim 1,
Wherein the polyurethane polymer has a number average molecular weight of 4,000 to 8,000. delete The method according to claim 1,
Wherein the adhesive layer comprises 50 to 70% by weight of an adhesive component and 30 to 50% by weight of nitrocellulose. A decorative layer is formed by forming an adhesive layer on one surface of a substrate layer, forming a decorative pattern layer on the other surface, and forming a protective layer on the decorative pattern layer,
(1) a diisocyanate component containing isophorone diisocyanate and methylene diphenyl diisocyanate in a molar ratio of 1: 1.5 to 2.0, and a diol component having a number average molecular weight of 950 to 2200, which is a polypropylene glycol, 2 diol component at a molar ratio of 1.5 to 1.0: 1.0, wherein the diisocyanate component and the first diol component are reacted at a molar ratio of 1.8 to 2.0: 1.0 to prepare an isocyanate-terminated polyurethane prepolymer step;
(2) mixing water with the isocyanate-terminated polyurethane prepolymer to prepare an aqueous solution;
(3) adding a diamine component to the aqueous solution to prepare polyurethane polymer particles having a particle size of 40 to 200 占 퐉; And
(4) a step of applying an aqueous solution having the polyurethane polymer particles on one side of the releasing paper to a predetermined thickness, followed by drying, wherein the isocyanate-terminated poly &Lt; / RTI &gt; further comprising neutralizing the urethane prepolymer. delete 10. The method of claim 9,
Wherein the viscosity of the isocyanate-terminated polyurethane prepolymer before water mixing in step (2) is 100,000 to 300,000 cps. 10. The method of claim 9,
Wherein the polyurethane produced in the step (3) has a viscosity of 40 to 200 cps. delete

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