KR20180078072A - Face luminous sign and face luminous sign manufactured by the same - Google Patents

Abstract

The present invention provides a flat fluorescent signboard capable of providing a uniform and clear color pattern of a character or an image and a manufacturing method thereof. The manufacturing method comprises the steps of: (a) positioning a light transmittance color sheet on a surface of a display; (b) applying an ultraviolet curing type synthetic resin composition on an upper side of the light transmittance color sheet of the step (a) and an upper side of the surface of the display where the light transmittance color sheet is not positioned; and (c) irradiating ultraviolet light to the applied ultraviolet curing type synthetic resin composition to cure.

Description

FIELD OF THE INVENTION The present invention relates to a method of producing a surface emitting luminescent signboard,

TECHNICAL FIELD The present invention relates to a method of manufacturing a surface-emitting signboard and a surface-emitting signboard produced thereby, and more particularly, to a method of manufacturing a surface-emitting signboard, which comprises applying a UV- And a surface-emitting signboard manufactured thereby.

Signboards are used to advertise to consumers the goods that are installed on the building, such as mutual goods and sales. For this purpose, the signboard can be easily recognized by the consumer and manufactured in a form that can be recognized more clearly than other signboards.

In recent years, stereoscopic character light-emitting signboards in which characters or graphics are shaped in a three-dimensional form have been widely used in order to enhance their identities. The three-dimensional character light-emitting signboard is constituted by arranging each character in a three-dimensional shape and connecting it to the base signboard. The three-dimensional character light-emitting signboard facilitates identification in a three-dimensional shape during the day and uses the light-emitting means provided in the nighttime to enhance the discrimination power of each character.

A conventional stereoscopic character light-emitting signboard forms a three-dimensional channel by using an epoxy resin to diffuse the light emitted from the light emitting means to the outside. At this time, the stereoscopic channel is manufactured by previously making a frame corresponding to the advertisement shape, filling the outer frame with an epoxy resin, and then heating and curing for a long time. Accordingly, the conventional stereoscopic character light-emitting signboard requires a considerable time for manufacturing the outer frame, filling epoxy resin, and heating and curing for a long time, so that the entire manufacturing process is troublesome and the production period is delayed. Korean Patent No. 10-1210663 proposes a method by ultraviolet curing as a conventional technique which solves the above problems.

On the other hand, in a conventional method of manufacturing a signboard, a color pattern of characters or images is drawn or printed on a display surface using an ink containing a pigment, an ultraviolet curable synthetic resin composition is applied thereon, Respectively.

However, according to the above-described method, not only is it necessary to take a long time to manufacture a signboard, but also in a letter or an image using the ink containing a pigment in the process of manufacturing a signboard, the pigment is aggregated or peeled, There is a problem that it is difficult to manufacture a high-quality signboard.

Korean Patent No. 10-1210663

The present invention has been conceived in order to solve the above problems of the prior art, and it is an object of the present invention to provide a method of manufacturing a signboard, in which, during the manufacturing process of a signboard, Etc., and to provide a method of manufacturing a surface-emitting signboard capable of providing a uniform and clear character or image color pattern.

In order to solve the above-mentioned problems, a method of manufacturing a surface-emitting signboard using an ultraviolet curing type synthetic resin composition having improved adhesion and hardenability is provided, because adhesive strength and curability of the ultraviolet curable synthetic resin composition should be greatly improved .

 It is another object of the present invention to provide a surface-emitting signboard manufactured by the above method.

The present invention relates to a method of manufacturing a surface-emitting signboard,

(a) positioning a light transmitting color sheet on a display surface;

(b) applying an ultraviolet curing type synthetic resin composition on the upper side of the light transmitting color sheet of the step (a) and the upper side of the display surface where the light transmitting color sheet is not located; And

(c) irradiating ultraviolet light to the applied ultraviolet curing type synthetic resin composition to cure the composition.

The light transmitting color sheet may be adhered or adhered to the display surface by using water, or by a pressure sensitive adhesive or an adhesive.

The light transmitting color sheet may be in the form of a letter, a figure, or an image.

The ultraviolet curable synthetic resin composition is prepared by mixing 80 to 120 parts by weight of urethane resin, MMA (Methyl Methacrylate), BMA (n-Butyl Methacrylate), IBMA (iso-Butyl Methacrylate) and EDMA (Ethyleneglycol Dimethacrylate ), And 5 to 15 parts by weight of a light diffusing agent,

Wherein the composition for ultraviolet curing comprises 40 to 70% by weight of an epoxy acrylate polymer represented by the following formula (1), 20 to 50% by weight of a polyester acrylate oligomer, 1 to 10% by weight of a photoinitiator comprising a compound represented by the following formula 0.1 to 5% by weight of an additive.

[ Chemical Formula 1 ]

In the above formula

a, b, and c are molar fractions, a is 0.5 to 0.7, b is 0.1 to 0.3, and c is 0.1 to 0.3, and a + b + c is 1.

[Formula 2]

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,

R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,

The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

In step (b), the ultraviolet curing type synthetic resin composition is applied to a thickness of 1 to 1.5 mm. In step (c), ultraviolet irradiation may be performed for 10 to 15 seconds using an ultraviolet curing machine.

The light diffusing agent may be silicon beads or silica.

The ultraviolet curable synthetic resin composition further comprises 20 to 30 parts by weight of a color pigment, and the color pigment may be a fluorescent color pigment having a nanoparticle size.

The present invention also provides a surface-emitting signboard manufactured by the method for manufacturing the surface-emitting signboard.

According to the method for producing a surface-emitting signboard of the present invention, a character or an image is formed by using a light-transmitting color sheet instead of forming a character or an image using the ink containing the pigment, It is possible to provide a color pattern of uniform and clear characters or images without causing problems such as pigment aggregation, peeling, protrusion of characters or images out of the pattern occurring in the image.

Further, according to the method for producing a surface-emitting signboard of the present invention, since the ultraviolet curing type synthetic resin composition having improved adhesion and curability is used, the ultraviolet curing type synthetic resin composition, which may occur when the light transmitting color sheet is used, A surface-emitting signboard can be produced.

Further, since the surface light-emitting signboard of the present invention is produced by the above-described method, a high-quality surface light-emitting signboard is provided by a color pattern of uniform and clear characters and images.

FIG. 1 schematically shows a manufacturing method of a surface-emitting signboard according to the present invention in accordance with the manufacturing line.

Hereinafter, the present invention will be described in detail.

As shown in FIG. 1, the present invention provides a method of manufacturing a surface-

(a) positioning a light transmitting color sheet (20) on a display (10) surface;

(b) applying an ultraviolet curing type synthetic resin composition (30) on the upper side of the light transmitting color sheet (20) and the upper side of the display (10) where the light transmitting color sheet is not located; And

(c) irradiating ultraviolet rays (40) to the coated ultraviolet curing type synthetic resin composition (30) to cure the ultraviolet curing type synthetic resin composition (30).

The light transmitting color sheet may be adhered with water, or the display may be adhered or adhered to the surface by a pressure-sensitive adhesive or an adhesive.

Since the method of producing a surface-emitting signboard of the present invention uses a light-transmitting color sheet as described above, it is possible to solve the problem of quality deterioration occurring when an ink containing a conventional pigment is used. However, The adhesion area of the composition is greatly lowered, so that the adhesive strength of the curing-type synthetic resin composition may be greatly lowered. Further, when the light transmitting color sheet is adhered using water, moisture is contained in the inside of the signboard, so that a greater adhesive force is required. Therefore, in the present invention, it is very important to improve the adhesion of the ultraviolet curing type synthetic resin composition.

Therefore, the present invention is characterized in that, in addition to the use of a light transmitting color sheet, the ultraviolet curing type synthetic resin composition has improved adhesion and curability.

The ultraviolet curable synthetic resin composition is prepared by mixing 80 to 120 parts by weight of urethane resin, MMA (Methyl Methacrylate), BMA (n-Butyl Methacrylate), IBMA (iso-Butyl Methacrylate) and EDMA (Ethyleneglycol Dimethacrylate ), And 5 to 15 parts by weight of a light diffusing agent,

Wherein the composition for ultraviolet curing comprises 40 to 70% by weight of an epoxy acrylate polymer represented by the following formula (1), 20 to 50% by weight of a polyester acrylate oligomer, 1 to 10% by weight of a photoinitiator comprising a compound represented by the following formula And 0.1 to 5% by weight of an additive.

 [ (1)

In the above formula

a, b, and c are molar fractions, a is 0.5 to 0.7, b is 0.1 to 0.3, and c is 0.1 to 0.3, and a + b + c is 1.

(2)

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,

R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,

The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

The epoxy-based acrylic polymer represented by Formula 1 includes an acrylate monomer including glycidyl acrylate and trimethylsilyloxyethyl group, thereby significantly improving the adhesion of the ultraviolet curable synthetic resin composition to the display surface and the light transmitting color sheet .

In addition, the photoinitiator represented by Formula 2 greatly improves the curability of the ultraviolet curing type synthetic resin composition.

In step (b), the ultraviolet curing type synthetic resin composition is preferably applied in a thickness of 1 to 1.5 mm. In step (c), ultraviolet light irradiation is preferably performed for 10 to 15 seconds using an ultraviolet curing machine.

As the light diffusing agent, known components in this field can be used without limitation, and specifically, silicon beads, silica, etc. can be preferably used.

The ultraviolet ray curable synthetic resin composition may further comprise 20 to 30 parts by weight of a color pigment. The color pigment may be any of those known in the art without limitation. Particularly, a fluorescent pigment of nanoparticle size is preferably used .

The ultraviolet curing type synthetic resin composition is applied by mixing with a solvent.

The solvent is not particularly limited as long as it is effective for dissolving the other components contained in the ultraviolet curing type synthetic resin composition. In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters are preferred.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

These solvents may be used alone or in combination of two or more.

The solvent is contained in an amount of 50 to 80% by weight based on the total weight of the ultraviolet curable synthetic resin composition. When the solvent is contained in the range of 50 to 80% by weight, the coatability can be improved.

In the present invention, the term " surface-emitting luminescent signboard "refers to a signboard in which the light emitted by the light emitting means is uniformly diffused on the display surface of the signboard and the entire display surface of the signboard is illuminated. The light emitting means is not particularly limited and may be, for example, an LED or a fluorescent lamp.

The transparent signboard of the present invention may be, for example, transparent acrylic, transparent glass or the like, but is not limited thereto.

The signboard of the present invention can be a figure, letter, number, symbol or a collection of the respective shapes.

The display surface of the present invention may be a flat surface, a curved surface, or the like depending on the shape of the signboard.

Hereinafter, the ultraviolet curing type synthetic resin composition of the present invention will be described in detail.

The ultraviolet curing liquid as the constituent component of the ultraviolet curing type synthetic resin composition of the present invention comprises 40 to 70% by weight of an epoxy acrylic polymer, 20 to 50% by weight of a polyester acrylate oligomer, 1 to 10% by weight of a photoinitiator and 0.1 to 5% .

Among the ultraviolet curable liquids, the epoxy-based acrylic polymer may preferably be represented by the following formula (1).

[Chemical Formula 1]

In the above formula

a, b, and c are molar fractions, a is 0.5 to 0.7, b is 0.1 to 0.3, and c is 0.1 to 0.3, and a + b + c is 1.

The epoxy-based acrylic polymer represented by Formula 1 includes an acrylate monomer including glycidyl acrylate and trimethylsilyloxyethyl group, thereby significantly improving the adhesion of the ultraviolet curable synthetic resin composition to the display surface and the light transmitting color sheet .

The weight average molecular weight of the epoxy-based acrylic polymer represented by Formula 1 may be in the range of 5,000 to 100,000.

The polyester acrylate oligomer used in the present invention is preferably chlorinated, and examples thereof include polyisocyanates such as ibis (EB) -436, 438, 584, 586 of UCB Co., MIRAMER SC ) 8000 series, and it is preferable to use at least one compound selected from these. When the amount of the polyester acrylate oligomer is more than 50% by weight, the water resistance becomes poor. When the amount of the polyester acrylate oligomer is less than 20% by weight, the adhesive property is poor and the polyester acrylate oligomer is easily separated from the display surface of the signboard.

Accordingly, it is preferable that the epoxy acrylate oligomer and polyester acrylate oligomer are used in an amount of 40 to 70% by weight of an epoxy acrylate oligomer and 20 to 50% by weight of a polyester acrylate oligomer, It is required to adjust the content within the above range according to the physical properties of the coating film forming the coating layer by using the ultraviolet curing type synthetic resin composition. However, when the epoxy acrylate oligomer is used in an amount of less than 40% by weight, the water resistance, solvent resistance, adhesion and the like are lowered. The total amount of the two acrylate oligomers is preferably not more than 90% by weight. If it exceeds the above range, it becomes difficult to adjust the viscosity to exhibit workability, and the above-described side effects will occur.

The photoinitiator used in the present invention may preferably include a compound represented by the following formula (2).

(2)

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,

R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,

The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

Examples of the compound of Formula 2 include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure TPO, Basf), ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate , Basf), etc. These may be used alone or in combination of two or more.

In addition, the photoinitiator represented by Formula 2 greatly improves the curability of the ultraviolet curing type synthetic resin composition.

As the photoinitiator of the present invention, a benzophenone-based compound, a benzyldimethalketal-based compound, an acetophenone-based compound, a benzylketal-based compound, or a mixture thereof may be used in addition to the compound represented by the formula -Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 1 -hydroxydimethylphenylgethone, and the like can be used.

The photoinitiator is preferably used in an amount of 1 to 10% by weight. The content of the photoinitiator can be controlled according to the operating conditions, that is, the working speed, the light amount of the ultraviolet irradiator, etc., and it is preferable that the content of the photoinitiator does not exceed 10% by weight.

The photoinitiator represented by Formula 1 and the other photoinitiator are preferably used in a weight ratio of 2: 8 to 8: 2.

As the additives used in the present invention, a surface slip and a leveling regulator may be used. As the surface slip and leveling regulator, a silicone compound or a silicone-modified polyacrylate may be used. Specifically, a blend of BYW BYK-306, 333, 355, 338 or RAD 2000 series from TEGO.

Such an additive is preferably used in an amount of 0.1 to 5% by weight of the ultraviolet hardening liquid. When the additive is used in an amount exceeding 5% by weight, the strength of the coating film is lowered, and the coating film is prone to flaking.

Careful approach is recommended because the additive may have a large influence on the composition of the coating even by a small amount. As the experience gained by the present inventors in experiments, it is considered desirable to reduce the possible content and to obtain a good result.

Defoaming agents as additives can be used in accordance with the specific circumstances in which the composition is used, such as BI-K-066, A-500, A-501, and the like.

The viscosity-controlling organic solvent as an additive is used for lowering viscosity suitable for a working method to which the ultraviolet curing liquid of the present invention is applied, like the above-mentioned additives, and an acetate compound, a ketone compound, an aromatic compound or a mixture thereof is used . The selection of the organic solvent is preferably determined in consideration of the operating speed, temperature, and the like.

In addition, a quencher may further be included as an additive. Examples of the quenching agent to be used include silica powder and synthetic polymer powders such as polyethylene, polypropylene and polyolefin. Specific examples thereof include SYLOID 244, OK-412, MAZUKASIL P-802Y and LANCO WAX PP-1362D, TF-1778, TF -1780. The use of such a quencher agent also serves to increase the viscosity, so that the quencher agent should be used within a range that does not affect workability and film performance.

The urethane resin as the constituent component of the ultraviolet curing type synthetic resin composition of the present invention comprises (1) a crystalline polyester polyol having a number average molecular weight of 2,000 or more and a polyol having a number average molecular weight of 100 to 500 Reacting an organic polyisocyanate having an average molecular weight of 100 or more with an NCO / OH equivalent ratio of 1.2 to 2.0 and diluting the organic polyisocyanate with a low boiling organic solvent free from active hydrogen; (2) lengthening the mixture of step (1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2- to 3-functional polyamine having a molecular weight of 200 or less, And (3) distilling the mixture of step (2) under reduced pressure to remove the organic solvent.

The urethane resin of the present invention is intended to improve the gloss and gloss of the resin composition treated on the display surface, and the specific production method thereof will be described in detail as follows.

The polyester polyol to be used in the step (1) is a polyol having a number average molecular weight of 2,000 or more, a polycaprolactone polyol condensed with? -Caprolactone and having a carbon number of 4 to 8 as an initiator, It is preferable to include a diol-condensed polyol having a linear structure of dicarboxylic acid having linear structure and 4 to 8 carbon atoms. The diol having a carbon number of 4 to 8 is preferably selected from the group consisting of butanediol, pentanediol, and hexanediol. As the dicarboxylic acid having a linear structure of 6 to 10 carbon atoms, adipic acid, Azelaic acid, and sebacic acid, but it is not limited thereto.

The polyester polyol having a number average molecular weight of 2,000 to 3,000 is preferably used in an amount of 65 to 75% by weight based on the solid content of the aqueous polyurethane resin. It is preferable that the step (1) includes a polyol having a number average molecular weight of 100 or more and 500 or less containing a nitrogen group and containing a bifunctional or more primary and secondary hydroxyl groups.

Such a polyol is preferably a cationic polyol which contains a nitrogen group in which an alkyl group such as an ethyl group, a methyl group or a butyl group is bonded to nitrogen and contains a hydroxyl group having two or more functional groups.

Specific examples of the cationic polyol include polyols corresponding to the following formula (1): < EMI ID =

(3)

In the above formula, R is -CnHn + 1 and n is an integer of 1 to 3.

The urethane resin according to the present invention is prepared by using a cationic polyol having a number average molecular weight of 100 to 500, which contains such a nitrogen group and has a bifunctional or more primary and secondary hydroxyl groups, thereby improving the adhesion.

In the above formula, R is -CnHn + 1 and n is an integer of 1 to 3.

The urethane resin according to the present invention is prepared by using a cationic polyol having a number average molecular weight of 100 to 500, which contains such a nitrogen group and has a bifunctional or more primary and secondary hydroxyl groups, thereby improving the adhesion.

The content of the polyol having a number average molecular weight of 100 or more and 500 or less containing the nitrogen group and containing two or more functional hydroxyl groups is preferably contained in an amount of 2 to 8% by weight based on the solid content of the polyurethane resin. When the cationic polyol is used in excess, the adhesive strength of the adherend is lowered, and when a small amount of the polyol is used, a coating layer is not formed at a low temperature.

The organic polyisocyanate which can be used in the step (1) is not particularly limited, and aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate which are usually used can be used singly or in combination. Examples of such organic polyisocyanate compounds include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- or 1,4 Diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), bis- (4-isocyanatocyclohexyl) Isocyanatocyclohexylmethane, 1,3- or 1,4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato-3- Methylcyclohexyl) methane, 1,3- or 1,4-α, α, α ', α'-tetramethylxylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 2,2'-, 2,4'- or 4,4'-diisocyanatodiphenylmethane, 1,5'-naphthalene diisocyanate, p- or m-phenylene diisocyanate, xylene diisocyanate and Phenyl-4,4'-diisocyanate, and the like. Preferred are isomers in which the ratio of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is 65:35 or 80:20 and hexamethylene diisocyanate Can be used.

Among these compounds, use of an aromatic isocyanate compound is preferable from the viewpoints of mechanical properties and heat resistance. From the viewpoint of cohesion and adhesion, it is more preferable to use a compound of aromatic and alicyclic isocyanate.

From the viewpoint of obtaining a polyurethane resin having a more appropriate cohesive strength and adhesion, it is also preferable to use a bifunctional or lower polyisocyanate.

The isocyanate content of the final urethane resin solid content is preferably in the range of 10 to 25% by weight. Within this range, the polyol property in the urethane molecule is suitably maintained and the heat activity is preferably exhibited at a low temperature, have. That is, when the content of isocyanate is out of the above range, the initial adhesive strength is lowered.

Examples of the organic solvent which can be used in the step (1) include benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile, chloroform, methylene chloride, -Dichloroethane, 1,1,2-trichloroethane, tetrachlorethylene and N-methylpyrrolidone may be used alone or in combination. Particularly, among these organic solvents, acetone or methyl ethyl ketone is preferably used as a solvent having high solubility with polyurethane resin.

In the urethane resin of the present invention, the urethane resin obtained by the reaction of the isocyanate-terminated prepolymer with the polyamine chain-extending agent having a sulfonic acid salt contains a sulfonic acid ion group in an amount of 0.1 to 5% on the basis of the solid content weight percentage, The resin may be contained in a proportion of 40% or more of the solid content, more preferably 50 to 60%.

Examples of the polyamine having a sulfonate having a number average molecular weight of 600 or less used in the step (2) include α, ω-polypropylene glycol diamine-sulfonate containing a metal such as Na, K, Li and Ca, . Preferably, an alpha, omega-polypropylene glycol diamine-sulfonated sodium salt having a number average molecular weight of 550 can be used. The content of the polyamine is preferably 0.1 to 5% by weight based on the solid content of the aqueous polyurethane resin. , And more preferably 0.1 to 4%. If it is used in a smaller amount, the resin is hardly water-soluble, and if it is used in an excess amount, the viscosity increases and the desired solid content may be decreased.

The first to second-order functional polyamines having a molecular weight of 200 or less used in the step (2) serve as a chain extender for the low molecular weight urethane resin obtained above. As described above, when the above-mentioned chain extender made of a polyamine having a molecular weight of 200 or less is used, the cohesive force of the urethane resin can be improved by increasing the molecular weight. In order to improve the cohesion of the urethane resin, it is necessary to adjust the molecular weight of the polyamine having a molecular weight of 200 or less to 100 or less.

Particularly typical examples of polyamines having a molecular weight of 200 or less include 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, piperazine, NN'-bis- (2-aminoethyl) piperazine, 1-amino- (4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- or 1,4-diamine Diamines such as minocyclohexane and 1,3-diaminopropane; Polyamines such as diethylenetriamine and triethylenetetramine; And hydrazine derivatives such as hydrazine and adipinic acid hydrazide, and hydrazine, 1,2-diaminoethane and the like are preferable. The poly

The amine is preferably contained in an amount of 0.05 to 2%, more preferably 0.1 to 1%, based on the solid content of the aqueous polyurethane resin.

In the production of the urethane resin according to the present invention, an emulsifier may be used in addition to the main components. Typical examples of such emulsifiers include polyoxyethylene polyoxypropylene glycol ether type, polyoxyethylene nonylphenyl ether type, polyoxyethylene octylphenyl ether type, polyoxyethylene lauryl ether type, polyoxyethylene laurate type, polyoxyethylene Nonionic emulsifiers such as alkyl ether type, sorbitan derivative type and polyoxyethylene polycyclic phenyl ether type, anionic emulsifiers such as alkyl benzene sulfonate type and dialkyl succinate sulfonate type, and cationic emulsifiers. Among these emulsifiers, it is preferable to use a nonionic emulsifier and an anionic emulsifier. The emulsifier may be added in an amount of 0 to 5% by weight based on the solid content of the polyurethane resin. When such an emulsifier is used, it is preferable to emulsify and disperse the emulsifier after previously adding it to water in the emulsion dispersion process. However, an emulsifier may be added after the emulsification and dispersion step. These emulsifiers may be used alone or in combination.

Further, in the production of the urethane resin according to the present invention, a urethane-forming catalyst may be used if necessary. Representative examples of the catalyst for urethane formation include various nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine, various metal salts such as potassium acetate, zinc stearate and tin octylate, and dibutyl tin dilaurate And various organic metal compounds.

The acrylic resin is selected from the group consisting of MMA (Methyl Methacrylate), BMA (n-Butyl Methacrylate), IBMA (iso-Butyl Methacrylate) and EDMA (Ethyleneglycol Dimethacrylate) as constituent components of the ultraviolet curing type synthetic resin composition of the present invention . The acrylic resin plays a role in helping maintain adhesion between the display surface and the coating layer.

The light diffusing agent is preferably silicon beads or silica as a constituent component of the ultraviolet curing type synthetic resin composition of the present invention. These are in powder form, so they should be mixed with UV curing liquid, urethane resin and acrylic resin before use.

As the constituent component of the ultraviolet-curing type synthetic resin composition of the present invention, the color pigment is preferably a fluorescent pigment of nanoparticle size.

In one preferred embodiment, the color pigment is selected from the group consisting of azo pigments, phthalocyanine pigments, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, , Quinacridone pigments, and transparency color pigments.

As the azo pigments, Pigment Red 3, 5, 48: 1, 48: 2, 48: 3, 48: 4, 53: 1, 53: 2, 57: 1, children. Pigment Yellow 1, 3, 83, City. Pigment Orange 16, 13 and the like; As the phthalocyanine pigment, Pigment Blue 15, 15: 3, 17 and C.I. C.I. Pigment Green 7 and the like; Examples of the anthraquinone pigments include indanthrene blue pigments such as condensed polycyclic organic pigments, Pigment Blue 60 (Indanthrene Blue CI Pigment Blue 60); Examples of the thioindigo pigments include thioindigo magenta pigment, Pigment Vilol 38 (Thioindigo Magenta C.I. Pigment Vilot 38); Examples of the perynone-based pigments include perynone orange, Pigment Orange 43 (Perinone Orange C.I. Pigment Orange 43), and examples of the above-mentioned perylene pigment include Perylene Maroon City. Pigment Red 179 (Perylene Maroon C.I. Pigment Red 179); Examples of the quinacridone pigments include quinacridone red cyanide, Pigment Violet 19 (Quninacridone Red C. I. Pigment Violet 19); Examples of the transparent color pigments include, but are not limited to, Pigment Red 177 (CI Pigment R177 (red)), Pigment Green 36 (CI Pigment G36 (green)), Pigment B15: 6 (blue) and Pigment Blue 15: 6 (C.I. Pigment Yellow 139 (CI Pigment Y139 (yellow)), Pigment V23 (violet), and the like.

The ultraviolet curable synthetic resin composition of the present invention, which is prepared as described above, forms a coating film having a thickness of 1 to 1.5 mm on the display surface of a signboard. The method of forming the coating film is not particularly limited, but it is preferable to use a spray method so as to smoothly finish the surface.

The coated board is passed through an ultraviolet curing machine to conduct ultraviolet curing reaction. The UV curing reaction can be carried out for 10 to 15 seconds, preferably 10 seconds. As a preferred embodiment, the equipment used for ultraviolet curing may be any ultraviolet curing apparatus which is known in the market, in which ultraviolet rays are emitted at a certain amount and rate.

According to such a production method, the surface-emitting signboard of the present invention can be produced. The present invention provides a surface-emission signboard produced by the above-described production method of the present invention.

The surface-emitting signboard of the present invention can be widely applied to interior signboards, advertising signboards, etc. because it has a short curing time and can dramatically shorten the production time of signboards, has excellent surface gloss and is easy to maintain.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, but may be variously modified and changed.

Manufacturing example  1: Preparation of epoxy-based acrylic polymer

60 parts by weight of glycidyl acrylate, 20 parts by weight of 2-hydroxyethyl acrylate and 20 parts by weight of 2 - [(trimethylsilyl) oxy] ethyl acrylate were added to a 1 L reactor equipped with a cooling device for nitrogen gas flow- 20 parts by weight was added thereto. 120 parts by weight of ethyl acetate (EAc; ethyl acetate) was poured into the solvent, and nitrogen gas was purged for 30 minutes. The temperature was maintained at 60, 0.1 part by weight of AIBN (azobisisobutyronitrile) as a reaction initiator was added, and the reaction was carried out for 10 hours to prepare an epoxy-based acrylic polymer having a weight average molecular weight of 87,500.

Manufacturing example  2: Methacrylate  Preparation of Copolymer

100 parts by weight of ethyl acetate (EAc; ethyl aceate) was added to a 1 L reactor equipped with a cooling device to easily regulate the temperature and nitrogen gas was refluxed. 100 parts by weight of the epoxy-based acrylic polymer solid prepared in Preparation Example 1 , 25 parts by weight of isocyanato methyl methacrylate and 0.1 part by weight of dibutyl tin dilaurate (DBTDL). 40 and at normal pressure for 2 hours to prepare a methacrylate copolymer.

Example  1: Preparation of ultraviolet curing agent composition

30% by weight of MIRAMER SC 8000 manufactured by MIWON CORPORATION as a polyester acrylate oligomer, 3% by weight of Irgacure TPO (manufactured by Basf) as a photoinitiator, 60% by weight of a solid content of the methacrylate copolymer synthesized in Preparation Example 2, 3% by weight of 2,2-dimethoxy-2-phenylacetophenone, and 4% by weight of BYK-306 by BYK as a leveling regulator as an additive were mixed to prepare an ultraviolet curing agent composition.

Example  2: Preparation of urethane resin

173.2 parts of a polyester polyol (A) having a number-average molecular weight of 2,000 and condensation-polymerized with 1,4-butanediol and adipic acid; 177.8 parts of a polyester polyol (B) having a number-average molecular weight of 2,000 and condensation-polymerized with 1,6-hexanediol and adipic acid; And 11.7 parts of 3- (diethylamino) propane-1,2-diol (D) were dehydrated under 105 vacuum and cooled to 50 ° C. Subsequently, 48.7 parts of toluene diisocyanate (2,4-toluene diisocyanate and 2,6-toluene diisocyanate in a ratio of 80:20) and 47.0 parts of hexamethylene diisocyanate were added, followed by reaction at 70 to 75 for 3 hours. Then, 600 parts of acetone was added slowly to dissolve the prepolymer. The temperature was adjusted to 40, and 15.9 parts of α, ω-polypropylene glycol diamine-sulfonated sodium salt and 6.5 parts of 80% hydrazine aqueous solution were diluted with 80 parts of water and added. Subsequently, 413.9 parts by weight of water was slowly added to emulsify and disperse. The thus obtained emulsion was degassed at 40 to 50 with a vacuum pump to obtain a urethane resin having a nonvolatile content of 50% (SO ₃ content: 0.46% based on solids).

Example  3: Preparation of ultraviolet ray hardening type synthetic resin composition

100 g of the ultraviolet curing agent composition obtained in Example 1, 80 g of the urethane resin prepared in Example 2, 100 g of methyl methacrylate, 10 g of silicon beads, 20 g of a phthalocyanine pigment having a diameter of 200 nm and 170 ml of ethyl acetate were mixed to prepare an ultraviolet curable A synthetic resin composition was prepared.

Example  4: Light transmission Color sheet  Adhesive and ultraviolet curing type synthetic resin composition Coating layer  formation

Water was sprayed onto the bottom surface of the green-light transmitting color sheet cut on the upper surface of the transparent acrylic signboard smaller than the upper surface of the transparent acrylic signboard and attached on the display surface flat. On top of this, the ultraviolet-curable synthetic resin composition To form a coating film layer having a coating film thickness of 1 mm.

Example  5: Surface emission  Manufacture of signs (UV curing)

After the coating layer was formed, the coating layer was cured by irradiating ultraviolet rays for 10 seconds using an ultraviolet curing machine having the specifications shown in Table 1 below to produce a surface-emitting signboard.

Light source Hg, Multi UV Cooling system Air-cooled type power AC Three Phase 11V / 220V / 380 60Hz magnitude UV Specifications 1,500mm? 650mm? 1,600mm

Comparative Example  One: Surface emission  Manufacturing of signboards

A surface emitting signboard was prepared in the same manner as in Examples 4 and 5 except that the ultraviolet curing type synthetic resin composition prepared in Korean Patent No. 10-1210663 previously filed and patented by the present inventors was used.

Test Example  1: Adhesion evaluation

The surface-emitting signboard prepared in Example 5 and Comparative Example 1 was left for 24 hours at a temperature of 23 ° C and a relative humidity of 55%. Thereafter, a cutter knife was pushed into the bonding surface of the display and the ultraviolet ray curable synthetic resin composition coating layer, and the adhesive force was evaluated according to the degree of insertion of the blade of the cutter blade.

The evaluation criteria are as follows, and the results are shown in Table 2.

<Adhesive Strength Evaluation Standard>

◎: The blade of the cutter blade does not enter between the joint surfaces of the two substrates

O: The blade of the cutter knife enters 2 mm or less between the joint surfaces of the two substrates

DELTA: The blade of the cutter knife enters between 2 mm and 5 mm or less between the joint surfaces of the two substrates

X: The blade of the cutter blade reaches the end between the joint surfaces of the two substrates

division Adhesion The surface-emitting signboard of Example 5 ◎ The surface-emitting signboard of Comparative Example 1 △

As can be seen from the test results in Table 2, in the case of the surface emitting luminescent signboard of Example 5 manufactured using the ultraviolet ray hardening type synthetic resin composition of the present invention, the display and the ultraviolet ray hardening type signboard It can be seen that the adhesion between the resin composition coating layers is very excellent.

10: Display 20: Light transmitting color sheet
30: Ultraviolet curing type synthetic resin composition layer
40: UV curing machine

Claims (8)

A method of manufacturing a surface-emitting signboard,
(a) positioning a light transmitting color sheet on a display surface;
(b) applying an ultraviolet curing type synthetic resin composition on the upper side of the light transmitting color sheet of the step (a) and the upper side of the display surface where the light transmitting color sheet is not located; And
(c) irradiating ultraviolet light to the coated ultraviolet curable synthetic resin composition to cure the coated ultraviolet curable synthetic resin composition.
The method according to claim 1,
Wherein the light transmitting color sheet is adhered or adhered to the surface by using water or by a pressure sensitive adhesive or an adhesive.
The method according to claim 1,
Wherein the light transmitting color sheet is formed in a shape of a letter, a figure and an image.
The method according to claim 1,
The ultraviolet curable synthetic resin composition is prepared by mixing 80 to 120 parts by weight of a urethane resin, MMA (Methyl Methacrylate), BMA (n-Butyl Methacrylate), IBMA (iso-Butyl Methacrylate) and EDMA (Ethyleneglycol Dimethacrylate ), And 5 to 15 parts by weight of a light diffusing agent,
Wherein the composition for ultraviolet curing comprises 40 to 70% by weight of an epoxy acrylate polymer represented by the following formula (1), 20 to 50% by weight of a polyester acrylate oligomer, 1 to 10% by weight of a photoinitiator comprising a compound represented by the following formula And 0.1 to 5% by weight of an additive.
[ Chemical Formula 1 ]

In the above formula
a, b, and c are molar fractions, a is 0.5 to 0.7, b is 0.1 to 0.3, and c is 0.1 to 0.3, and a + b + c is 1.
[Formula 2]

Each of R ₁ and R ₂ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, Or an aryloxy group having 5 to 30 carbon atoms,
R ₃ is an alkyl group having 4 to 20 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms with or without a substituent, or an aryloxy group having 5 to 30 carbon atoms ego,
The substituent is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
The method according to claim 1,
Wherein the ultraviolet curing type synthetic resin composition is applied in a thickness of 1 to 1.5 mm in the step (b), and the ultraviolet ray irradiation is performed for 10 to 15 seconds using an ultraviolet curing machine in the step (c) .
The method according to claim 1,
Wherein the light diffusing agent is silicon beads or silica.
5. The method of claim 4,
Wherein the ultraviolet curable synthetic resin composition further comprises 20 to 30 parts by weight of a color pigment, wherein the color pigment is a fluorescent pigment of nanoparticle size.
A surface-emitting signboard produced by the method of any one of claims 1 to 7.

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