KR102397057B1 - Ink composition for cosmetic containers capable of both thermal and uv curing, cosmetic container comprising same and manufacturing method of cosmetic container - Google Patents

Abstract

The present invention relates to an ink composition for a cosmetic container capable of simultaneous heat curing and UV curing, a cosmetic container including the ink composition, and a method for manufacturing the cosmetic container. The present invention has an excellent drying property of the ink composition itself, so that the printing efficiency can be increased according to the reduction of the drying time in the case of mass printing.

Description

Ink composition for cosmetic container capable of thermal curing and UV curing at the same time, and method for manufacturing cosmetic container and cosmetic container including the same

The present invention relates to an ink composition for a cosmetic container capable of thermal curing and UV curing at the same time, a cosmetic container comprising the same, and a method for manufacturing the cosmetic container.

In general, a cosmetic container is composed of a body and a lid, and after accommodating the cosmetic contents inside the container, it is stored by blocking the entrance with the lid. Cosmetic containers of a general structure configured as described above are made of plastic or glass, and patterns and letters including logos are directly printed on the surface or stickers are attached to display contents or brands.

Although the quality of the contents of these cosmetic containers is the most important, cosmetic containers designed to evoke an aesthetic that is differentiated from other products greatly motivate women, who are the main buyers, to purchase. It is implemented to improve consumer satisfaction by delivering information such as a trademark or brand name to the user through a method of printing the included text or picture, and to satisfy the user's visual aesthetics.

Printing and marking are in the same vein that the desired image and text are realized by applying ink to the object, but printing uses a plate to directly contact the object or transfer ink within 1mm from the object, so it is only possible on thin and flat materials such as paper. It is possible, and the function can be performed even if the marking is 10mm away from the object, so it has the feature of being free from the shape and material of the object.

In conventional printing, an ink composition is applied to the cosmetic container itself to increase print adhesion and dryness, and curing is performed through thermal curing treatment or UV irradiation to indicate the brand or component content. However, when only thermal curing treatment is performed, the printing object is deformed or the durability of the printed material is not good, which causes problems. Since the material is expensive, the manufacturing cost is greatly increased, the process is also complicated, and there is a risk of breakage.

As such, the printed material included in the conventional cosmetic container has a problem in that price competitiveness is lowered due to an increase in unit price as the manufacturing process is complicated. In order to solve this problem, research on manufacturing a nameplate by molding a fabric such as fabric or leather has been conducted. However, fabric or leather has a very difficult problem in processing, such as torn fabric in the process of forming patterns such as stationery, pictures, trademarks or brand names due to the characteristics of the material. In addition, there is a problem in that the manufacturing cost increases because a complicated process is required to implement the pattern.

Accordingly, the present inventors have developed an ink composition that can include both thermal curing and UV curing in a suitable manner without modifying the properties of the ink itself without the need for an economical and complicated process in the printed matter included in the cosmetic container.

Domestic Patent Publication No. 10-2019-0103454

The present invention relates to an ink composition for a cosmetic container capable of thermal curing and UV curing at the same time, a cosmetic container comprising the same, and a method for manufacturing the cosmetic container.

An exemplary embodiment of the present specification is a mixed resin comprising a dispersing agent in which a hydrophilic monomer and a lipophilic monomer are randomly copolymerized in a mass ratio of 4 to 6: 1 and a weight average molecular weight of 5,000 to 10,000 g/mol and a repeating unit of Formula 1 below ; a solution having at least one silane; oxidation stabilizers; and a curing accelerator, wherein the curing accelerator includes an organophosphorus compound and a mixture, and the mixture includes a cobalt metal, a manganese metal, an amino alcohol, and a solvent.

[Formula 1]

In Formula 1,

m is an integer from 1 to 1,000.

In an exemplary embodiment of the present application, it is intended to provide an ink composition comprising 15 parts by weight or more and 30 parts by weight or less of the mixed resin based on 100 parts by weight of the ink composition.

In an exemplary embodiment of the present application, the ink comprising 1 part by weight or more and 10 parts by weight or less of the solution having the at least one silane, and 0.1 parts by weight or more and 5 parts by weight or less of the oxidation stabilizer based on 100 parts by weight of the ink composition It is intended to provide a composition.

In an exemplary embodiment of the present application, 5 parts by weight or more and 20 parts by weight or less of the organic phosphorus compound based on 100 parts by weight of the curing accelerator; And To provide an ink composition comprising 80 parts by weight or more and 95 parts by weight or less of the mixture.

In an exemplary embodiment of the present application, the ink composition has a thermal curing rate of 40% or more and 50% or less within a temperature range of 40° C. to 70° C., UV intensity of 80 mW/cm ² , and UV light with an exposure amount of 160 mJ/cm ² An object of the present invention is to provide an ink composition having a photocuring rate of 90% or more when irradiated.

In an exemplary embodiment of the present application, the ink composition further comprises at least one selected from the group consisting of an adhesive, a pigment including at least one selected from the group consisting of Red, Green and Black, a surfactant, and a tackifier An object of the present invention is to provide an ink composition.

In an exemplary embodiment of the present application, the case core; a pretreatment layer provided on the surface of the case core; an ink treatment layer including a cured product of the ink composition according to the present application provided on a surface opposite to the surface in contact with the case core of the pretreatment layer; And to provide a cosmetic container comprising a case layer provided on the opposite surface of the surface in contact with the pre-treatment layer of the ink treatment layer.

In an exemplary embodiment of the present application, the pretreatment layer has a surface energy of 50mM/m or more, and a surface number average contact angle of 90° or less is to provide a cosmetic container.

In an exemplary embodiment of the present application, the pretreatment layer is a metal; Or to provide a cosmetic container that is a non-porous substrate.

In an exemplary embodiment of the present application, the thickness of the ink processing layer is 1 nm or more and 100 nm It is intended to provide a cosmetic container that is as follows.

In an exemplary embodiment of the present application, manufacturing a case core by injecting plastic; applying a pretreatment layer to the surface of the case core; Heating the case core and the pretreatment layer, producing a low-temperature heating state of 40 ℃ to 70 ℃; applying the ink composition of any one of claims 1 to 6 to the heated pretreatment layer; And after applying the ink composition, UV intensity 80mW/cm ² , It is to provide a method of manufacturing a cosmetic container comprising the step of UV curing at an exposure amount of 160mJ/cm ² .

In an exemplary embodiment of the present application, after the step of applying the ink composition to the heated pretreatment layer, the curing rate of the ink composition is to provide a method of manufacturing a cosmetic container that is 40% or more and 50% or less.

Finally, in an exemplary embodiment of the present application, after applying the ink composition, after UV curing at an ultraviolet intensity of 80 mW/cm ² , and an exposure amount of 160 mJ/cm ² , further comprising the step of polishing the cosmetic container An object of the present invention is to provide a method for manufacturing a cosmetic container.

The ink composition according to the present application does not modify the properties of the ink itself, and before the ink composition is printed on the print object to be printed, the substrate to be printed is first heat treated and heated to apply the ink composition At the same time, it promotes thermal curing to form an ink composition layer in a semi-cured state, and then features an ink composition comprising a specific composition and component capable of short UV curing for complete curing.

In particular, the transparent ink composition according to the present application includes a mixed resin in the composition; a solution having at least one silane; oxidation stabilizers; And by including a specific amount of the curing accelerator, thermal curing and UV curing can be achieved at the same time as described above, and when coated on the surface of a substrate to be printed, the ink composition itself has excellent drying properties, so that it dries in a large amount of printing. It has a feature that can increase the printing efficiency according to the decrease in time.

That is, in the case of the ink composition according to the present application, in order to solve problems such as a decrease in print quality, which is a problem in which only thermal curing proceeds, an increase in process cost, which is a problem in which only UV curing proceeds, and damage to a printed object, thermal curing is performed. and a specific curing accelerator capable of simultaneously undergoing UV curing.

1 to 7 are diagrams showing printing results according to Examples 1 to 3 and Comparative Examples 1 to 4 according to the present application.

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

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

An exemplary embodiment of the present specification is a mixed resin comprising a dispersing agent in which a hydrophilic monomer and a lipophilic monomer are randomly copolymerized in a mass ratio of 4 to 6: 1 and a weight average molecular weight of 5,000 to 10,000 g/mol and a repeating unit of Formula 1 below ; a solution having at least one silane; oxidation stabilizers; and a curing accelerator, wherein the curing accelerator includes an organophosphorus compound and a mixture, and the mixture provides an ink composition comprising cobalt metal, manganese metal, aminoalcohol and a solvent.

[Formula 1]

In Formula 1,

m is an integer from 1 to 1,000.

In conventional printing, an ink composition is applied to the cosmetic container itself to increase print adhesion and dryness, and curing is performed through thermal curing treatment or UV irradiation to indicate the brand or component content. However, when only thermal curing treatment is performed, the printing object is deformed or the durability of the printed material is not good, which causes problems. Since the material is expensive, the manufacturing cost is greatly increased, the process is also complicated, and there is a risk of breakage.

The ink composition according to the present application does not modify the properties of the ink itself, and before the ink composition is printed on the print object to be printed, the substrate to be printed is first heat treated and heated to apply the ink composition At the same time, it promotes thermal curing to form an ink composition layer in a semi-cured state, and then features an ink composition comprising a specific composition and component capable of short UV curing for complete curing.

Hereinafter, materials included in the ink composition will be described.

In an exemplary embodiment of the present application, the hydrophilic monomer and the lipophilic monomer are randomly copolymerized in a mass ratio of 4 to 6: 1, and a dispersing agent having a weight average molecular weight of 5,000 to 10,000 g/mol and a repeating unit of Formula 1 is included. It may include a mixed resin.

In the case of the mixed resin, including polyvinyl pyrrolidone-based resin containing the repeating unit of Formula 1, it is a material with excellent water adsorption property, and it has excellent adsorption with ink and diffusion into the inside of the ink, so that the drying rate of the ink after printing It can be used as a substance to increase

In particular, in the case of the mixed resin, a hydrophilic monomer and a lipophilic monomer are randomly copolymerized in a mass ratio of 4 to 6: 1 and a dispersing agent having a weight average molecular weight of 5,000 to 10,000 g/mol is included together, and the number of polyvinyl pyrrolidone In the case of using only the polyvinyl pyrrolidone resin, aggregation of the polyvinyl pyrrolidone resin occurs, and when the ink composition is applied in a desired shape, stains and color imbalance due to ink aggregation occur. However, in the case of the mixed resin according to the present application, the above conditions It was possible to solve the above problem by including a dispersing agent that satisfies

In the exemplary embodiment of the present application, the dispersant included in the mixed resin may be randomly copolymerized with a hydrophilic monomer and a lipophilic monomer in a mass ratio of 4 to 6: 1 and a weight average molecular weight of 5,000 to 10,000 g/mol.

The hydrophilic monomer may be a compound including a carboxyl group, a compound including a hydroxy group, and the like, but is not limited thereto. For example, the hydrophilic monomer may be acrylic acid or methacrylic acid. The hydrophilic monomer may serve as a functional group to have solubility in a solvent.

The lipophilic monomer may be at least one selected from the group consisting of styrene, 2-ethyl hexyl acrylate, butyl acrylate and hexyl acrylate, but is not limited thereto. The lipophilic monomer can physically bind the pigment.

The dispersant may be a random copolymer in which a hydrophilic monomer and a lipophilic monomer are randomly polymerized.

In writing an exemplary embodiment of the present application, the dispersant has a weight average molecular weight of 5,000 to 10,000 g/mol, preferably a weight average molecular weight of 5,000 to 8,000 g/mol, and more preferably a weight average molecular weight of 5,000 to 6,000 g /mol.

In an exemplary embodiment of the present application, the dispersant may be randomly copolymerized with a hydrophilic monomer and a lipophilic monomer in a mass ratio of 4 to 6: 1, specifically 4 to 5: 1 in a mass ratio, more specifically 4:1 mass ratio can be satisfied.

The content of the dispersant in the mixed resin may satisfy 10 to 30 parts by weight, more preferably 10 to 20 parts by weight, and most preferably 10 to 15 parts by weight based on 100 parts by weight of the mixed resin.

That is, as the dispersant satisfies the range of the weight average molecular weight and the monomer mass ratio, bonding between the polyvinylpyrrolidone resin and the solvent included in the composition is facilitated, so that the polyvinylpyrrolidone resin has excellent dispersion characteristics. will have

In an exemplary embodiment of the present application, it provides an ink composition comprising 15 parts by weight or more and 30 parts by weight or less of the mixed resin based on 100 parts by weight of the ink composition of the mixed resin.

In an exemplary embodiment of the present application, the molecular weight of the mixed resin may be 100,000 g/mol or more and 5,000,000 g/mol or less.

In another exemplary embodiment, the weight average molecular weight of the mixed resin is 100,000 g/mol or more and 5,000,000 g/mol or less, preferably 100,000 g/mol or more and 1,000,000 g/mol or less, and more preferably 100,000 g/mol or more. It may be 500,000 g/mol or less.

In the exemplary embodiment of the present application, m in Formula 1 may be an integer of 1 to 1,000, preferably an integer of 10 to 500, and more preferably an integer of 20 to 100.

The weight average molecular weight is one of the average molecular weights for which molecular weight is not uniform and the molecular weight of a certain polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight may be measured through Gel Permeation Chromatography (GPC) analysis.

As the weight average molecular weight of the mixed resin according to the present application satisfies the above weight range, it satisfies the viscosity range of the ink composition including the same in a specific range, and the viscosity is controlled so as not to be too thin to coat the substrate to be printed. This is excellent, and it has a characteristic that can increase the ease of coating by controlling the viscosity not to be high.

In particular, when composed of the mixed resin, the surface of the coating layer forms a sticky and wet feel, and when the viscosity range exceeds a specific range, it may be difficult to form a continuous product in a roll shape in a mass printing process, As it satisfies the above weight average molecular weight range, it has a characteristic capable of solving the above problem.

In an exemplary embodiment of the present application, it provides an ink composition comprising 15 parts by weight or more and 30 parts by weight or less of the mixed resin based on 100 parts by weight of the ink composition.

In another exemplary embodiment, based on 100 parts by weight of the ink composition, 15 parts by weight or more of the mixed resin may be included, and 30 parts by weight or less, preferably 25 parts by weight or less, 24 parts by weight or less, 23 parts by weight or less , more preferably 22 parts by weight or less, and most preferably 21.5 parts by weight or less.

When the mixed resin included in the present invention satisfies the above range, the ink composition containing the same is coated on the substrate to be printed and the printing process is performed. By increasing the drying rate of the ink, it can have characteristics suitable for mass printing.

That is, the present inventors have developed a material (ink composition according to the present invention) that can increase the quality and efficiency of printing regardless of the type and physical properties of the substrate to be printed. It was found that the efficiency was maximized and the characteristics suitable for mass production processes were found.

In an exemplary embodiment of the present application, the ink composition may include a solution having at least one silane.

Suitable silanes for use in the above ink compositions are, for example, (3-aminopropyl)triethoxysilane (APS), 1,2-bis(triethoxysilyl)ethane (BTSE), glycidyl-oxypropyl -trimethoxysilane (GPS), tetraethoxysilane (TEOS), vinyltriethoxysilane (VTES), bis[3-(trimethoxysilyl)propyl]amine, vinyltrimethoxysilane, methyltriethoxy silane (MTES), and combinations thereof.

The silane may be introduced into the composition as a solution containing at least one silane and an aqueous medium, an organic solvent, or a combination thereof.

The aqueous medium may include, for example, tap water, purified water, distilled water, and/or deionized water. The water may be distilled and/or deionized to a purity of about 0.5 μS/cm to about 40 μS/cm (e.g., about 1.0 μS/cm to about 30 μS/cm or about 5.0 μS/cm to about 25 μS/cm). there is.

The organic solvent includes, for example, a polar organic solvent. In some embodiments, an organic solvent such as acetone, ethanol, methanol, isopropanol, and/or ethyl acetate may be present. Optionally, the solution containing at least one silane may comprise a combination of an aqueous medium and an organic solvent.

The aqueous medium or media contains in solution at least about 5% by volume, at least about 10% by volume, at least about 15% by volume, at least about 20% by volume, at least about 25% by volume, at least about 30% by volume, at least about 35% by volume, At least about 40% by volume, at least about 45% by volume, at least about 50% by volume, at least about 55% by volume, at least about 60% by volume, at least about 65% by volume, at least about 70% by volume, at least about 75% by volume, at least about 80% by volume, at least about 85% by volume, at least about 90% by volume, or at least about 95% by volume.

The organic solvent is present in solution in at least about 5% by volume, at least about 10% by volume, at least about 15% by volume, at least about 20% by volume, at least about 25% by volume, at least about 30% by volume, at least about 35% by volume, at least about 40% by volume, at least about 45% by volume, at least about 50% by volume, at least about 55% by volume, at least about 60% by volume, at least about 65% by volume, at least about 70% by volume, at least about 75% by volume, at least about 80% by volume %, at least about 85% by volume, at least about 90% by volume, or at least about 95% by volume.

Optionally, the solution with the at least one silane may comprise an aqueous medium which may comprise, for example, acetone, ethanol, methanol, isopropanol, and/or ethyl acetate in an amount of up to about 90 volumes.

In the exemplary embodiment of the present application, the solution having at least one silane is 1 part by weight or more and 10 parts by weight or less, preferably 3 parts by weight or more and 10 parts by weight or less, more preferably based on 100 parts by weight of the ink composition. 5 parts by weight or more and 10 parts by weight or less, and most preferably 8 parts by weight or more and 10 parts by weight or less.

The ink composition includes a solution having at least one silane, and when it contains fine particles such as general silicon oxide, it may have a characteristic of accelerating ink adsorption, but decrease in transparency and increase in viscosity according to the use of the particles themselves Problems such as this may occur, and accordingly, the ink composition according to the present application includes the solution having at least one silane in the content portion as described above, thereby increasing the transparency of the composition itself and improving durability in the printing process. have possible characteristics.

In an exemplary embodiment of the present application, the ink composition may include an oxidation stabilizer.

The oxidation stabilizer has a characteristic capable of stabilizing the coating produced from the ink composition by forming a dense structure by forming a silane network with a solution having at least one silane according to the present application.

That is, it means a material having properties that make the resulting coating more inert to the reaction.

The oxidation stabilizer is mercaptobenzothiazole (MBT), benzotriazole (BTA), salicylaldoxime, dithiooxamide, quinaldic acid, thioacetamide, 8-hydroxyquinoline (HXQ), and mixtures thereof. may include

In an exemplary embodiment of the present application, the oxidation stabilizer provides an ink composition comprising 0.1 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the ink composition.

In another exemplary embodiment, the oxidation stabilizer is 0.1 parts by weight or more and 5 parts by weight or less, preferably 1 part by weight or more and 3 parts by weight or less, more preferably 1.5 parts by weight or more and 2 parts by weight based on 100 parts by weight of the ink composition may be included in sub-parts.

As the oxidation stabilizer according to the present application is included in the ink composition in the above content range, it has a feature capable of protecting the surface of the substrate to be printed, and in particular, when the substrate to be printed is a metal included in the lid of a cosmetic container, the metal surface itself It has the effect of inhibiting corrosion by making it inert, and thus has the characteristic of increasing the durability of the printed matter in the future.

In the ink composition of the present application, the solution having at least one silane and the oxidation stabilizer are included together to form a silane network with the solution having the oxidation stabilizer and at least one silane to form a dense structure, It may have a characteristic capable of increasing the durability of the transparent ink composition.

In an exemplary embodiment of the present application, the ink composition may include a curing accelerator.

In an exemplary embodiment of the present application, the curing accelerator is an organic phosphorus compound; and mixtures.

In particular, as the curing accelerator of the present application includes an organic phosphorus compound and a mixture at the same time, thermal curing in a specific temperature range can be performed and at the same time, UV curing through UV irradiation is also made, so the ink according to the present invention It becomes possible to represent the properties of the composition.

In one embodiment of the present application, as the curing accelerator, a known curing accelerator may be used, and an amine-based compound such as tributylamine, 1,8-diazabicyclo(5,4,0)undecene-7, etc.; Imidazole compounds such as 2-methylimidazole, 2-ethylimidazole and 1,2-dimethylimidazole, organophosphorus compounds to which phosphorus is bonded only by covalent bonds such as triphenylphosphine, tetraphenylphosphine Organophosphorus compounds, such as a salt type organophosphorus compound to which phosphorus is couple|bonded by covalent bond, such as phonium tetraphenylborate, and an ionic bond, etc. are mentioned, It is not limited to these. In particular, at least one organic phosphorus compound such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate has a great effect of improving the curing rate and must be included in the curing accelerator of the ink composition according to the present application. As it is included, it will have characteristics that can cause thermal curing in a specific temperature range.

In the exemplary embodiment of the present application, the mixture included in the curing accelerator may include a cobalt metal, a manganese metal, an amino alcohol, and a solvent. In particular, by including a certain portion of the mixture as described above, it has a characteristic capable of proceeding with UV curing, and also may not cause deterioration of print quality.

As the amino alcohol used in the present invention, all known and commonly used amino alcohols can be used. For example, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, dibutylethanolamine, methylethanolamine, Methyldiethanolamine, ethylethanolamine, n-butylethanolamine, n-butyldiethanolamine, t-butylethanolamine, t-butyldiethanolamine, dimethylisopropanolamine, dimethylbutanolamine, dimethylhexanolamine, dimethylamino phenol and the like, and one or two or more selected from them may be used, and in particular, diethanolamine, diethylethanolamine, dibutylethanolamine, and n-butyldiethanolamine are preferred.

As the cobalt and manganese metals used in the present invention, all known and commonly used metals can be used. For example, aliphatic monocarbonates having 7 to 12 carbon atoms such as octylate and neodecanoate, tall fatty acid salts, naphthenates, etc. can be heard

The ratio of amino alcohol and cobalt metal used is not particularly limited, but the content of amino alcohol is preferably 3 parts by weight or less with respect to 1 part by weight of cobalt metal of cobalt metal. , which is preferable from the viewpoint of good adhesion.

The ratio of the manganese metal and the cobalt metal used is not particularly limited, but the manganese metal content is preferably in the range of 1.0 parts by weight or less based on 1 part by weight of the cobalt metal. It is preferable from a good point.

And, for example, when the storage state after preparing the paint is the same, compared to the curing accelerator consisting of cobalt metal and amino alcohol, the curing accelerator consisting of cobalt metal, manganese metal and amino alcohol is semi-cured (半硬化) (without tackiness) is characterized by a fast time.

In one embodiment of the present application, the solvent may be a commonly used organic solvent, toluene, ethyl acetate, etc. may be used, and a polar aprotic solvent may be used. That is, in general, a solvent capable of dissolving all of the solutes in the ink composition may be used without limitation.

In an exemplary embodiment of the present application, it provides an ink composition comprising 5 parts by weight or more and 20 parts by weight or less of the curing accelerator based on 100 parts by weight of the ink composition.

In another exemplary embodiment, based on 100 parts by weight of the ink composition, 5 parts by weight or more and 20 parts by weight or less, preferably 5 parts by weight or more and 15 parts by weight or less, more preferably 5 parts by weight or more and 10 parts by weight or more It may include the following.

In an exemplary embodiment of the present application, 5 parts by weight or more and 20 parts by weight or less of the organic phosphorus compound based on 100 parts by weight of the curing accelerator; and 80 parts by weight or more and 95 parts by weight or less of the mixture; provides an ink composition comprising.

The curing accelerator according to the present application is 5 parts by weight or more and 20 parts by weight or less, preferably 5 parts by weight or more and 15 parts by weight or less, more preferably 5 parts by weight or more and 10 parts by weight based on 100 parts by weight of the curing accelerator. may be included below.

The curing accelerator according to the present application may be included in an amount of 80 parts by weight or more and 95 parts by weight or less, preferably 85 parts by weight or more and 95 parts by weight or less, more preferably 90 parts by weight or more and 95 parts by weight or less, based on 100 parts by weight of the curing accelerator. there is.

The present inventors found that when the ink composition according to the present application contains a specific composition and content, the drying rate is increased, and at the same time, as the curing accelerator having a specific composition is included as described above, thermal curing in a low temperature heating state It was found that semi-curing can be achieved through UV curing, and complete curing can be achieved through UV curing. That is, it was found that the existing problems when subjected to a single UV curing or thermal curing process can be solved, and the drying rate of the ink composition itself is excellent, and has a characteristic capable of increasing the efficiency of the printing process.

In an exemplary embodiment of the present application, the ink composition has a thermal curing rate of 40% or more and 50% or less within a temperature range of 40° C. to 70° C., UV intensity of 80 mW/cm ² , and UV light with an exposure amount of 160 mJ/cm ² When irradiated, it provides an ink composition that has a photocuring rate of 90% or more.

That is, in the case of the ink composition according to the present application, as the curing accelerator is included in a specific composition and content portion as described above, the degree of curing in a specific temperature range and UV intensity can be adjusted as described above, and a cosmetic container including the same later It has the characteristics of improving print quality and print durability.

In an exemplary embodiment of the present application, the ink composition provides an ink composition that further comprises a polyurethane-based polymer.

In the case of the polyurethane-based polymer, it is a material that may be included in an amount of 0.1 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the ink composition. Accordingly, it is possible to excellently adjust the viscosity, and has a characteristic capable of increasing the durability of the ink composition itself.

In particular, in general, a polyester acrylate oligomer, an epoxy acrylate oligomer, or a polyurethane-based polymer may be used in the composition. However, the polyester acrylate oligomer has good solvent resistance and scratch resistance, but poor processability. Epoxy acrylate oligomer has excellent hardness and solvent resistance, but there is a problem in that yellowing occurs. The polyurethane-based polymer satisfies most of the physical properties required for the substrate layer to be printed, such as processability, solvent resistance, hardness, and adhesion, and has an excellent effect in processability in particular. Accordingly, the transparent ink composition according to the present application may include a polyurethane-based polymer.

The urethane-based polymer is preferably formed through a urethane acrylate-based oligomer that does not include a benzene ring in terms of adhesion, curability, hardness, and the like.

In an exemplary embodiment of the present application, 70 to 95 parts by weight of the bifunctional polyol based on 100 parts by weight of the urethane-based polymer and 5 to 30 parts by weight of the trifunctional polyol based on 100 parts by weight of the polyurethane polymer may be included.

As the above weight range is satisfied, the viscosity range of the ink composition can be adjusted to a specific range.

In the present application, the polyol is oxidized with an initiator such as a polyfunctional alcohol or aromatic amine having two or more hydroxyl groups (Hydroxyl Group, -OH) or amine groups (Amine Group, -NH ₂ ) in the molecule As a material obtained by reacting propylene (Propylene Oxide, PO) or ethylene oxide (EO) under specific conditions, it is a raw material for manufacturing a urethane-based polymer together with isocyanate, and the polyol is PPG (propylene glycol), PTMEG (tetramethylene glycol) ), PEG (ethylene glycol) polyester and propylene oxide (Propylene Oxide, PO) or ethylene oxide (EO) reacted may mean a material having two functional groups or three functional groups.

In an exemplary embodiment of the present application, the ink composition has a viscosity of 50 cPs or more and 150 cPs or less under conditions of 25°C and 50% relative humidity.

In another exemplary embodiment, the viscosity of the ink composition may be 50 cPs or more and 150 cPs or less, preferably 50 cPs or more and 80 cPs or less, at 25°C and 50% relative humidity.

In the case of the ink composition, the composition and content included in the composition satisfy the range according to the present application. In this case, the viscosity range may satisfy a specific range, and the coating property when coating the substrate to be printed by adjusting the viscosity not to be too thin This is excellent, and it has a characteristic that can increase the ease of coating by controlling the viscosity not to be high.

In an exemplary embodiment of the present application, the ink composition further comprises at least one selected from the group consisting of an adhesive, a pigment including at least one selected from the group consisting of Red, Green and Black, a surfactant, and a tackifier A transparent ink composition is provided.

In an exemplary embodiment of the present application, the case core; a pretreatment layer provided on the surface of the case core; an ink treatment layer including a cured product of the ink composition according to the present application provided on a surface opposite to the surface in contact with the case core of the pretreatment layer; And it provides a cosmetic container comprising a case layer provided on the opposite surface of the surface in contact with the pre-treatment layer of the ink treatment layer.

In an exemplary embodiment of the present application, the case core includes all of the core that may contain the contents of the cosmetic container or the lid part that separates the contents of the cosmetic container, PET (polyethylene terephthalate), polyester, PC (Polycarbonate), PI (polyimide), PEN (polyethylene naphthalate), PEEK (polyether ether ketone), PAR (polyarylate), PCO (polycylicolefin), polynorbornene, PES (polyethersulphone), glass, metal and COP (cycloolefin polymer) may include any one or more selected from the group consisting of.

In an exemplary embodiment of the present application, the pretreatment layer is used for pretreatment of the substrate to be printed and may be used to improve adhesion and print quality of the ink treatment layer including the cured product of the ink composition later, and the material can widely use a known material, specifically, the pretreatment layer is a metal; Or it provides a cosmetic container that is a non-porous substrate.

The thickness of the pretreatment layer is 1 nm or more and 100 nm or less, preferably 5 nm or more and 50 nm or less, more preferably 10 nm or more and 50 nm or less.

As the thickness of the pretreatment layer satisfies the above range, printing performance and efficiency may increase during a subsequent printing process. to have sufficient characteristics to

In an exemplary embodiment of the present application, the pretreatment layer may have a surface energy of 50mM/m or more, and a surface number average contact angle of 90° or less.

That is, as the pretreatment layer according to the present application is included, the layer has a surface energy of 50mM/m or more and a surface number average contact angle of 90° or less, thereby greatly improving the surface adhesion of the ink. will have

As described above, when printing is performed on the substrate to be printed without using the pretreatment layer, the ink is not uniformly transferred to the print target, and the adhesion of the ink is further reduced, so that the printing material is peeled off when an external force is applied. Accordingly, the present application includes a pre-treatment layer including a transparent ink composition on a substrate to be printed in advance, thereby increasing printing efficiency and also having a feature that can be applied to a mass process.

In an exemplary embodiment of the present application, manufacturing a case core by injecting plastic; applying a pretreatment layer to the surface of the case core; Heating the case core and the pretreatment layer, producing a low-temperature heating state of 40 ℃ to 70 ℃; applying the ink composition of any one of claims 1 to 6 to the heated pretreatment layer; And after applying the ink composition, UV intensity 80mW/cm ² , It provides a method of manufacturing a cosmetic container comprising the step of UV curing at an exposure amount of 160mJ/cm ² .

That is, the ink composition according to the present application has a curing accelerator of a specific content and composition as mentioned above, and is characterized in that thermal curing and UV curing are performed simultaneously, particularly in the manufacture of cosmetic containers according to the present application. , manufacturing the case core by injection of plastic; applying a pretreatment layer to the surface of the case core; and a pre-heating step comprising heating the case core and pretreatment layer to create a low-temperature heating state of 40° C. to 70° C., and as the ink composition is applied, the semi-cured ink composition is included in the printing process Therefore, stability and process cost can be effectively reduced.

After that, after applying the ink composition, the ink composition is completely cured to form an ink treatment layer, including UV curing at an ultraviolet intensity of 80 mW/cm ² , and an exposure amount of 160 mJ/cm ² When only conventional thermal curing is performed It has a feature that can effectively control the problems of UV curing and the problems in the case of only UV curing.

In an exemplary embodiment of the present application, after the step of applying the ink composition to the heated pretreatment layer, the curing rate of the ink composition is 40% or more and 50% or less It provides a method of manufacturing a cosmetic container.

That is, by applying the ink composition on the heated pretreatment layer to make the ink composition in a semi-cured state, the curing rate is adjusted to satisfy the range of the curing rate, thereby improving printing stability and printing quality. .

In an exemplary embodiment of the present application, after the ink composition is applied, the UV intensity of 80 mW/cm ² , the UV curing step at an exposure amount of 160 mJ/cm ² After the step of UV curing, the cosmetic container further comprising the step of polishing the cosmetic container A manufacturing method is provided.

That is, the step of luster processing is an operation to highlight the external image of the cosmetic container itself, and is not limited thereto, as long as it is a type of varnish processing used in the art.

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

< production example >

<Preparation of ink composition>

Ink compositions satisfying the composition and content of Table 1 were prepared, respectively. In Table 1 below, each means a content part of each composition included in the composition based on 100 parts by weight of the ink composition.

mixed resin solution with at least one silane Oxidation Stabilizer hardening accelerator etc
(solvent or polyurethane) Example 1 Dispersant: PVP 1 = 85: 15
(21.5 parts by weight) Silane 1: 8 Stabilizer 1:1.5 Curing accelerator 1: 5 Solvent: 64 Example 2 Dispersant: PVP 2= 85: 15
(15 parts by weight) Silane 2: 10 Stabilizer 2:2 Cure accelerator 2: 10 Solvent: 62
Polyurethane: 1 Example 3 Dispersant: PVP 1 = 85: 15
(21.5 parts by weight) Silane 2: 8 Stabilizer 2:1.5 Cure accelerator 2: 5 Solvent: 64 Comparative Example 1 Dispersant: PVP 1 = 85: 15
(21.5 parts by weight) Silane 1: 8 Stabilizer 1:1.5 - Solvent: 69 Comparative Example 2 Dispersant: PVP 2= 85: 15
(15 parts by weight) Silane 2: 10 Stabilizer 2:2 Curing accelerator 3: 10 Solvent: 62
Polyurethane: 1 Comparative Example 3 Dispersant: PVP 1 = 85: 15
(21.5 parts by weight) Silane 2: 8 Stabilizer 2:1.5 hardener 4: 5 Solvent: 64 Comparative Example 4 PVP 1: 21.5 parts by weight Silane 1: 8 Stabilizer 1:1.5 Curing accelerator 1: 5 Solvent: 64

In Table 1, the mixed resin used, the solution having at least one silane, the oxidation stabilizer, the curing accelerator and other components were as follows.

- Mixed resin

Dispersant: Styrene (10.0 g, 0.139 mol) and acrylic acid (40.0 g, 0.148 mol) were mixed with 60.0 g of isopropyl alcohol in a flask equipped with a reflux device, and nitrogen was slowly added to remove oxygen in the flask. removed. Here, 0.35 g of BPO (BPO) was added and the temperature was raised to 90 °C, followed by polymerization for 6 hours. After polymerization was completed, isopropyl alcohol was removed by distillation, and the polymer dispersant was solidified. 10.0 g of the solidified dispersant was dissolved with a 10% NaOH solution to adjust the pH to 9, and distilled water was added to prepare a final dispersant of 50.0 g.

As a result of GPC analysis, which can measure molecular weight, the weight average molecular weight (Mw) of the synthesized polymer dispersant was 5,821 g/mol.

PVP 1: Polyvinylpyrrolidone of Samjeon/KANTO's P3918 was used, and the weight average molecular weight of the polyvinylpyrrolidone was 360,000 g/mol.

PVP 2: EAST CHEM's K30 polyvinylpyrrolidone was used, and the polyvinylpyrrolidone had a weight average molecular weight of 400,000 g/mol.

- at least one silane solution with

silane 1: 30 g of a sample satisfying the composition of (3-aminopropyl)triethoxysilane (APS):vinyltriethoxysilane (VTES)=90:10 was added to a 1-neck round bottom flask. Thereafter, 1000 ml of a solvent according to the distilled water:ethanol=95:5 ratio was added, and a silane 1 solution satisfying 30% of the total silane concentration was prepared.

silane 2: 25 g of a sample satisfying the composition of (3-aminopropyl)triethoxysilane (APS):methyltriethoxysilane (MTES)=80:20 was put into a 1-neck round bottom flask. Thereafter, 1000 ml of a solvent according to a ratio of distilled water:ethanol=95:5 was added, and a silane 1 solution satisfying 25% of the total silane concentration was prepared.

- Oxidation stabilizer

Stabilizer 1: Mercaptobenzothiazole (MBT)

Stabilizer 2: Benzotriazole (BTA)

- hardening accelerator

Curing accelerator 1: 5 parts by weight of organophosphorus compound tetraphenylphosphonium tetraphenylborate and cobalt metal; Curing accelerator 1 was prepared by including 95 parts by weight of a mixture containing amino alcohol and water.

Curing accelerator 2: 10 parts by weight of an organophosphorus compound triphenylphosphine and a manganese metal; Curing accelerator 2 was prepared by including 90 parts by weight of a mixture containing amino alcohol and water.

Curing accelerator 3: The organophosphorus compound triphenylphosphine 100 was used.

hardening accelerator 4: manganese metal; Curing accelerator 4 was prepared by including 100 parts by weight of a mixture containing amino alcohol and water.

- etc

Solvent: An organic solvent was prepared in an Erlenmeyer flask to satisfy 75 parts by weight of acetone, 15 parts by weight of ethyl acetate, and 10 parts by weight of propylene glycol monomethyl ether based on 100 parts by weight of the total organic solvent.

Polyurethane: 70 parts by weight of a bifunctional polyol (SC2204 by KPX) and 30 parts by weight of a trifunctional polyol (SC3314 by KPX) with respect to 100 parts by weight of a polyol in a 2L reactor, H12MDI, an isocyanate, was added, and then 100 parts by weight of toluene was added.

<Production of cosmetic containers>

The case core was manufactured by injecting plastic, and a pretreatment layer was applied so that the ink composition was smoothly adhered to the surface of the case core, and then the case core and the pretreatment layer were heated to produce a low temperature heating state of 60°C.

Thereafter, the ink composition according to Table 1 was applied to the heated pretreatment layer, and UV curing was performed at an ultraviolet intensity of 80 mW/cm 2 and an exposure amount of 160 mJ/cm 2 to cure the ink composition.

1 to 7 are diagrams showing printing results according to Examples 1 to 3 and Comparative Examples 1 to 4 according to the present application.

Specifically, FIGS. 1, 3 and 5 are diagrams showing the printing results according to Examples 1, 2 and 3, respectively, and by first heat-treating and heating the substrate to be printed, which is the object of printing, the ink composition It was confirmed that the print quality was excellent by accelerating thermal curing at the same time as coating the ink composition layer in a semi-cured state, and then proceeding with a short UV curing process for complete curing.

2 shows the printing result according to Comparative Example 1, specifically, it does not include the curing accelerator according to the present application, so thermal curing and UV curing are not smoothly performed. It was confirmed that it was not printed properly.

4 shows the printing results according to Comparative Example 2, specifically, not the curing accelerator according to the present application, but corresponds to a case including a curing accelerator including only an organic phosphorus compound, and heat according to the heated substrate to be printed. Curing can be made, but the subsequent UV curing is not performed smoothly, so it can be confirmed that the print quality is not good and the printing is not clear.

6 shows the printing result according to Comparative Example 3, specifically, it corresponds to a case where a curing accelerator including only a mixture, not a curing accelerator according to the present application, is included. As a result, it was confirmed that the print quality was not good and the printing was not clearly done.

7 shows a printing result according to Comparative Example 4, which corresponds to a case in which the dispersant according to the present application is not included as a mixed resin. In this case, it was confirmed that the polyvinyl pyrrolidone resin was agglomerated and, in the ink composition including the pigment, the ink agglomeration occurred and the print quality was deteriorated.

The transparent ink composition according to the present application includes a mixed resin in the composition; a solution having at least one silane; oxidation stabilizers; And by including a specific amount of the curing accelerator, thermal curing and UV curing can be achieved at the same time as described above, and when coated on the surface of a substrate to be printed, the ink composition itself has excellent drying properties, so that it dries in a large amount of printing. It was confirmed that it has a characteristic capable of increasing the printing efficiency according to the decrease in time.

That is, in the case of the ink composition according to the present application, in order to solve problems such as a decrease in print quality, which is a problem in which only thermal curing proceeds, an increase in process cost, which is a problem in which only UV curing proceeds, and damage to a printed object, thermal curing is performed. and a specific curing accelerator capable of simultaneously undergoing UV curing.

Claims (13)

A mixed resin comprising a dispersing agent in which acrylic acid and styrene are randomly copolymerized in a mass ratio of 4 to 6: 1, and a weight average molecular weight of 5,000 to 10,000 g/mol, and a repeating unit represented by the following Chemical Formula 1;
a solution having at least one silane;
oxidation stabilizers; and a curing accelerator;
In an ink composition comprising a,
The curing accelerator comprises an organophosphorus compound and a mixture,
The mixture is an ink composition comprising a cobalt metal, a manganese metal, an amino alcohol and a solvent:
[Formula 1]

In Formula 1,
m is an integer from 1 to 1,000. The ink composition of claim 1, wherein the ink composition comprises 15 parts by weight or more and 30 parts by weight or less of the mixed resin based on 100 parts by weight of the ink composition. The ink composition of claim 1, wherein the ink composition comprises 1 part by weight or more and 10 parts by weight or less, and 0.1 parts by weight or more and 5 parts by weight or less of the oxidation stabilizer, based on 100 parts by weight of the ink composition. The method according to claim 1, based on 100 parts by weight of the curing accelerator
5 parts by weight or more and 20 parts by weight or less of the organophosphorus compound; and
An ink composition comprising; 80 parts by weight or more and 95 parts by weight or less of the mixture. The method according to claim 1, wherein the ink composition has a thermal curing rate of 40% or more and 50% or less within a temperature range of 40°C to 70°C, and when irradiated with ultraviolet rays at an ultraviolet intensity of 80mW/cm ² , an exposure amount of 160mJ/cm ² , An ink composition having a photocuring rate of 90% or more. The ink composition of claim 1, wherein the ink composition further comprises at least one selected from the group consisting of an adhesive, a pigment including at least one selected from the group consisting of Red, Green, and Black, a surfactant, and a tackifier. case core;
a pretreatment layer provided on the surface of the case core;
an ink treatment layer comprising a cured product of the ink composition of any one of claims 1 to 6 provided on the opposite surface of the surface in contact with the case core of the pretreatment layer; and
a case layer provided on a surface opposite to the surface of the ink processing layer in contact with the pretreatment layer;
A cosmetic container comprising a. The cosmetic container according to claim 7, wherein the pretreatment layer has a surface energy of 50 mM/m or more, and a surface number average contact angle of 90° or less. The method according to claim 7, wherein the pretreatment layer is a metal; Or a cosmetic container with a non-porous substrate. The method according to claim 7, wherein the thickness of the ink processing layer is 1 nm or more and 100 nm A cosmetic container that is the following. manufacturing a case core by injecting plastic;
applying a pretreatment layer to the surface of the case core;
Heating the case core and the pretreatment layer, producing a low-temperature heating state of 40 ℃ to 70 ℃;
applying the ink composition of any one of claims 1 to 6 to the heated pretreatment layer; and
After the ink composition is applied, UV curing at an ultraviolet intensity of 80 mW/cm ² , an exposure amount of 160 mJ/cm ² ;
A method of manufacturing a cosmetic container comprising a. The method of claim 11, wherein after applying the ink composition to the heated pretreatment layer, the curing rate of the ink composition is 40% or more and 50% or less. The method according to claim 11, after applying the ink composition, UV intensity 80mW/cm ² , UV curing at an exposure amount of 160mJ/cm ² After the step of UV curing, the method of manufacturing a cosmetic container further comprising the step of polishing the cosmetic container.

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