KR101988703B1 - Ink composition for inkjet printing, inkjet printed steel sheet using the same - Google Patents

Abstract

[0001] The present invention relates to a composition for ink-jet printing which is easy to realize a metal texture and an ink-jet printed steel sheet using the same, and an aspect of the present invention is to provide a composition for ink-jet printing comprising polymer particles having a large number of pores, Lt; / RTI >

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a composition for ink-jet printing,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for ink-jet printing and an ink-jet printed steel sheet using the same. More particularly, the present invention relates to a composition for ink-

Inkjet printing technology can implement various patterns and images, and the demand of the market is expanding, and there is an increasing demand for patterning with various textures. In order to realize the metallic texture, metal particles must be mixed with the ink, and solvent-based ink having a metal texture has been developed and commercialized. However, solvent-based ink has problems such as discharge of VOC, There is a problem due to the discoloration or deformation of the ink, the increase in the process ratio, and the like.

However, it is difficult to dissolve a dispersant in a solventless ultraviolet curing type ink, and it is difficult to prevent precipitation of a metal powder having a high specific gravity because of low viscosity of the inkjet ink itself, and it is difficult to realize a metal texture.

One of the objects of the present invention is to provide a composition for an inkjet print which can easily realize a metal texture and an inkjet printed steel sheet using the same.

An aspect of the present invention provides a composition for ink jet printing comprising polymer particles having a plurality of pores and having a metal thin film formed on the surface thereof.

Another aspect of the present invention provides an inkjet printed steel sheet comprising a base steel sheet and a coating layer formed on the surface of the base steel sheet, the coating layer comprising polymer particles having a plurality of pores and having a metal thin film formed on the surface thereof.

As one of various effects of the present invention, the composition for ink-jet printing according to the present invention has an advantage that metal texture can be easily realized.

1 is a photograph of polymer particles having a metal thin film formed on its surface.
2 is a photograph of an appearance of an inkjet printed steel sheet manufactured according to an embodiment of the present invention.

Hereinafter, the composition for inkjet printing, which is one aspect of the present invention, will be described in detail.

An inkjet printing composition according to an aspect of the present invention includes polymer particles having a plurality of pores and having a metal thin film formed on the surface thereof.

As described above, conventionally, in order to realize a metal texture on an ink-jet printed steel sheet, metal particles have simply been mixed in a composition for ink jet printing. In the case of a solvent-based ink, dispersion of metal particles in the composition can be achieved by adding a dispersant It is not easy to dissolve the dispersing agent in the case of the composition for inkjet printing of the ultraviolet hardening system of the solventless type and also it is not easy to prevent precipitation of the metal powder having a high specific gravity because of low viscosity of the ink itself, It is not easy to realize a composition for ink-jet printing having an ultraviolet curing system.

Therefore, the inventors of the present invention have found that, by changing the outline, the metal particles themselves are not added to the composition for ink-jet printing, but the metal thin film is formed on the surface of the polymer particles having a small specific gravity, ≪ / RTI >

However, it has been confirmed that when the metal thin film is formed on the surface of a conventional polymer, the effect of preventing the precipitation due to the reduction of the specific gravity of the metal-containing particles is insufficient. Thus, it is confirmed that the object of the present invention can be achieved effectively.

In order to further maximize the effect of the present invention, it is more preferable to form a metal thin film on the surface of the polymer particles having cavities formed therein. This is because the specific gravity of the metal-containing particles is remarkably low, This is because the dispersibility is remarkably improved.

According to one non-limiting example, the average particle size of the polymer particles having the metal thin film formed on the surface thereof may be 50 to 2000 nm. If the average particle diameter is less than 50 nm, the effect of realizing the metal texture may be deteriorated due to the diffuse reflection of the particles. On the other hand, if the average particle diameter is more than 2000 nm, the nozzleability of the head nozzle may be deteriorated. Here, the average particle diameter means the equivalent circular diameter of the polymer particles having the metal thin film formed thereon.

According to one non-limiting example, the ratio of volume to volume of the polymer particles in which the metal foil is formed may be between 8: 1 and 8: 7. If the ratio is less than 8: 1, the effect of decreasing the specific gravity by cavitation may not be sufficient. On the other hand, if the ratio is more than 8: 7, There is a possibility of being deformed.

In the present invention, the structure and the specific kind of the polymer particle having a plurality of pores are not particularly limited, but according to an example which is not limited, it may have a core-shell structure, and more specifically, A core layer polymer polymerized from a monomer, and at least one cell layer polymer surrounding the core layer polymer. At this time, a cavity may be formed inside the core layer polymer.

The core layer polymer is a spherical nanoparticle that forms a micelle and is preferably an amphipathic polymer for affinity with a cell surrounding the core, and more specifically, the core layer polymer comprises a hydrophilic acid monomer and an ethylenically unsaturated It is preferable that the copolymer is a copolymer of monomers.

The hydrophilic acid monomer is not particularly limited, but is, for example, an ethylenically unsaturated carboxylic acid. Monoalkyl esters of unsaturated carboxylic acids or vinyl benzoic acid and the like can be used.

Examples of the ethylenically unsaturated monomer include, but are not limited to, aromatic vinyl monomers such as styrene, methylstyrene, halogenated styrene and divinylbenzene; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; Diene-based monomers such as butadiene and isoprene; (Meth) acrylamide and derivatives thereof such as N-butoxymethyl (meth) acrylamide; Carboxylic acid vinyl esters such as vinyl acetate; Vinyl halides such as vinyl chloride; Vinylidene halides such as vinylidene chloride; Or vinylpyridine can be used, and two or more kinds of the monomers can be used.

The cell layer polymer may be used without limitation as long as it can maintain the shape of particles, for example, spherical or tube shapes, during the manufacturing process. For example, the cell layer polymer may be an interlayer polymer that is a copolymer of a hydrophilic acid monomer and an ethylenically unsaturated monomer; And an outer layer polymer surrounding the intermediate layer polymer and polymerized from a hydrophobic monomer, and may optionally include more functional layers.

Here, the types of the hydrophilic acid monomer and the ethylenically unsaturated monomer are as described above. On the other hand, hydrophobic monomers include, for example, aromatic vinyl monomers such as styrene, methylstyrene, halogenated styrene and divinylbenzene; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; Diene-based monomers such as butadiene and isoprene; Carboxylic acid vinyl esters such as vinyl acetate; Vinyl halides such as vinyl chloride; Vinylidene halides such as vinylidene chloride; Or vinyl pyridine.

In the present invention, the method for producing the polymer particles having a large number of pores as described above is not particularly limited, and examples thereof include emulsion polymerization, radical polymerization, ion polymerization, suspension polymerization, urethane polymerization, . However, if it is produced by emulsion polymerization, the following method can be used as a preferable example.

The core layer polymer may be synthesized by using distilled water as a reaction medium and emulsifying a monomer capable of emulsion polymerization, emulsifying a chain transfer agent as a surfactant, if necessary, and then introducing a water-soluble initiator into the reaction. More specifically, an emulsion obtained by emulsifying a monomer as a surfactant is emulsified with an ultrasonic emulsifier, and the emulsion is introduced into a reactor, and nitrogen is introduced to maintain the inside of the reactor in a nitrogen atmosphere. The core layer polymer can be synthesized by raising the temperature of the reactor to 50-1000 ° C using an oil bath and then introducing a water-soluble initiator to initiate the reaction.

Here, the monomers capable of emulsion polymerization are as described above. Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, Cationic surfactants such as stearyl trimethyl ammonium chloride and the like, and nonionic surfactants such as nonyl phenyl ether can be used. Particularly, in the present invention, a cationic surfactant can be preferably used in order to improve the adhesion with a substrate when a coating agent is used. The reaction ratio of the monomer to the surfactant is preferably 1: 0.001 to 0.2, more preferably 0.005 to 0.1. If the reaction ratio of the monomer and the surfactant is out of the above range, there is a problem that the state of the emulsion is unstable.

Examples of the water-soluble initiator include persulfate-based agents such as ammonium persulfate, sodium persulfate, potassium persulfate and the like, 4,4-azobis Azo-based initiators such as 4-azobis (4-cyanovaleric acid) and azobis (2-amidinopropane) dihydrochloride may be used, The amount of the monomer to be used may be 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight based on the amount of the monomer.

As the chain transfer agent, those conventionally used in emulsion polymerization may be used.

Further, in order to form the intermediate layer before the step of forming the cell layer polymer, for example, it may further include forming an intermediate layer polymer which is a copolymer of an aqueous acid monomer and an ethylenically unsaturated monomer in the presence of the core layer polymer. The monomers in the cell layer are as described above, and the polymerization method described above can be used for the emulsion polymerization method.

On the other hand, the cavity inside the particle can be formed by a method of swelling the core particle by incorporating an alkaline substance into the core layer polymer. In the present invention, the kind of the alkaline substance is not particularly limited, and for example, ammonia, ethanolamine, triethanolamine, 5-amino-1-pentanol, diethanolamine, propylamine and dipropylamine can be used . The size of the cavity can be appropriately adjusted depending on the amount of the alkaline substance to be incorporated and the time of incorporation.

In the present invention, the specific kind of the metal thin film formed on the surface of the polymer particle having a plurality of pores is not particularly limited. For example, the metal constituting the metal thin film is composed of Zn, Mg, Au, Ag, Lt; / RTI > On the other hand, the metal thin film may be a normal stainless steel (STS) thin film.

In the present invention, the thickness of the metal thin film is not particularly limited. However, for example, the thickness of the metal thin film may be 10 to 200 nm. If the average thickness of the metal thin film is less than 10 nm, the metal texture effect may not be realized. On the other hand, if the average thickness exceeds 200 nm, the process cost is excessively increased, The jetting property may be deteriorated.

In the present invention, a method of forming a metal thin film on the surface of a polymer particle having a plurality of pores is not particularly limited. However, examples of the method include, but are not limited to, electroplating, physical vapor deposition (PVD) Aerosol deposition, dipping, and the like.

In the present invention, the content of the polymer particles having the metal thin film formed in the composition for ink-jet printing is not particularly limited, but may be 1 to 30 parts by weight based on 100 parts by weight of the composition for ink jet printing . If the content is less than 1 part by weight, the metal texture effect may not be exhibited. On the other hand, if the content is more than 30 parts by weight, the metal particles may not be adhered to the printing surface and may peel off.

In the present invention, other than the polymer particles having the metal thin film formed thereon, the specific types of components that can be included in the inkjet printing composition are not particularly limited, and they may be composed of components contained in a composition for general solvent-based ink or composition for ultraviolet curable ink . However, in the case of solvent-based inks, as described above, there are problems due to discharge of VOC, discoloration or deformation of the material due to thermal curing, increase in the process ratio, etc. Therefore, The remaining components other than the polymer particle formed with the thin film will be described in detail.

Acrylic Monomer

The acrylic monomer participates in the photocuring reaction and serves as a binder in the coating layer.

The acrylic monomer may be contained in an amount of 50 to 80 parts by weight, preferably 65 to 80 parts by weight, based on 100 parts by weight of the inkjet printing composition. If the content of the acrylic monomer is less than 50 parts by weight, the viscosity becomes excessively high, so that the application of the inkjet ink to the steel material may be difficult, and if it exceeds 80 parts by weight, the physical properties of the coating film may be adversely affected.

According to one example, the acrylic monomer may be a mixture of one or more of a monofunctional acrylic monomer, a bifunctional acrylic monomer, and a polyfunctional acrylic monomer.

Further, according to one example, the monofunctional acrylic monomer used as the acrylic monomer may be one or a mixture of two or more selected from the group consisting of alkyl acrylate, aryl acrylate, alkoxy acrylate, and tetrahydrofurfuryl acrylate .

According to one example, the bifunctional acrylic monomer used as the acrylic monomer may be one or a mixture of two or more selected from the group consisting of tripropylene glycol diacrylate and hexanediol diacrylate.

According to an example, the polyfunctional acrylic monomer used as the acrylic monomer may be one or a mixture of two or more selected from the group consisting of trimethyl propane ethoxylate triacrylate and trimethyl propane triacrylate.

Acrylic Oligomer

The acrylic oligomer also participates in the photo-curing reaction and acts as a binder in the coating layer. Here, the acrylic oligomer means an oligomer having at least one acrylic group in the molecule.

The acrylic oligomer may be contained in an amount of 10 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the inkjet printing composition. When the content of the acrylic oligomer is less than 10 parts by weight, adhesion, workability, solvent resistance and the like may be deteriorated. On the other hand, when the content of the acrylic oligomer is more than 30 parts by weight, the viscosity becomes too high and injection becomes difficult, This can be difficult.

According to one example, the acrylic oligomer is selected from the group consisting of epoxy acrylate, urethane based modified epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic acrylate, silicone acrylate, melamine acrylate, acrylic acrylate, An acrylate derivative, and a polythiol acid acetal-based acrylate, may be used alone or in admixture of two or more.

ore Initiator

The photoinitiator serves to initiate the photo-curing reaction. In the present invention, the content of the photoinitiator is not particularly limited, but may be 1 to 10 parts by weight based on 100 parts by weight of the inkjet printing composition. If the amount is less than 1 part by weight, the photocuring reaction may not be sufficiently carried out. If the amount is more than 10 parts by weight, the physical properties of the coating layer may be deteriorated.

According to one example, the photoinitiator may be benzophenone, diphenoxylbenzophenone, anthraquinone, xanthone, thioxanthone, or benzyl. Initiators such as Micure HP-8, Irgacure 819, Darocur TPO and Micure CP-4, which are commercially available photoinitiators, may be used, but the present invention is not limited thereto.

Other additives

The composition for ink-jet printing of the present invention may contain, in addition to the above-described components, a defoaming agent, a leveling agent, an adhesion promoter, a light stabilizer, an antioxidant, an ultraviolet absorbent, a heat polymerization inhibitor, a smoothing agent, a dispersant, And 0.01 to 10 parts by weight of at least one additive selected from the group consisting of When the additive is added within the above-mentioned content range, the effect of the additive can be exhibited without changing the physical properties of the coating film.

The antifoaming agent is for removing bubbles generated during coating, and specific examples thereof include TEGO Airex 920, TEGO Airex 932, BYK 088, and BYK 1790.

The leveling agent is for improving the surface appearance and scratch resistance. Specific examples thereof include TEGO Glide 410, TEGO Glide 440, TEGO Rad 2250, BYK-UV 3500 and BYK-UV 3510.

The adhesion promoting agent is for improving the adhesion with the base steel sheet. Specific examples thereof include acrylic phosphate based adhesion promoters such as hydroxyethyl acryloyl phosphate or hydroxyethyl methacrylate phosphate.

The light stabilizer is for the purpose of facilitating storage stability, and specific examples thereof include phenolic antioxidants, alkylated monophenols, alkylthiomethyl phenols, hydroquinones, alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkyl An alicyclic amine, an allyl amine, a diarylamine, a polyarylamine, an acylamino group, an aldehyde group, an aldehyde group, a hydroxyl group, Phenol, oxamide, metal deactivator, phosphite, phosphonite, benzylphosphonate, ascorbic acid, hydroxylamine, nitrone, thiosynergist, benzofuranone, or indolinone. In addition, products of BASF such as Tinuvin 292, Tinuvin 144 or Tinuvin 622LD, which are commercially available light stabilizers; And SANKYO products such as Sanol LS-770 (sanol LS-770), Sanol LS-765 (sanol LS-765), Sanol LS-292 (sanol LS-292) or Sanol LS-744 Can be used.

Antioxidants are used to prevent oxidation reactions and ultimately facilitate storage. Specific examples include Irganox 1010, Irganox 1035, Irganox 1076 or Irganox 1222 Irganox 1222) available from BASF.

The ultraviolet absorber is for enhancing the photo-curing reaction efficiency during the photo-curing reaction. Specific examples thereof include Tinuvin P, Tinuvin 234, Tinuvin 320 or Tinuvin 328 (Tinuvin 328); And Sumisorb 110, Sumisorb 130, Sumisorb 140, Sumisorb 220, Sumisorb 250, Sumoisorb 320, (Sumisorb 320) or Sumisorb 400 (Sumisorb 400).

The thermo-alloyed paper is intended to enhance the photo-curing reaction efficiency by preventing the reaction from being terminated by thermal side reactions. Specific examples thereof include HQ, THQ and HQMME.

Smoothing agents and dispersants are used for smooth dispersion in solvents and can be selected from commercial additives manufacturers such as BYK, TEGO and EFKA.

Examples of the antistatic agent include antioxidants such as polyoxyethylene alkyl ethers, polyoxyethylene amines, glycerin or sorbitol fatty esters, alkyl sulfonates such as alkyl sulfonates, alkyl Benzenesulfonate, alkylsulfate, and alkylphosphate; quaternary ammonium salts or mixtures thereof.

The silane coupling agent is used for improving the adhesive strength of the inkjet printing composition of the present invention. Specific examples thereof include methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylethoxysilane, gamma-chloropropylmethoxysilane , Vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltriacetoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- ( Aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl (meth) acrylate, vinyltrimethoxysilane, vinyltrimethoxysilane, Trimethoxysilane, or mixtures thereof.

Hereinafter, the inkjet printed steel sheet, which is another aspect of the present invention, will be described in detail.

Another aspect of the present invention is an inkjet printed steel sheet comprising a base steel sheet and a coating layer formed on the surface of the base steel sheet and having a plurality of pores and including polymer particles having a metal thin film formed on the surface thereof.

In the present invention, the kind of the base steel sheet is not particularly limited, but for example, the base steel sheet is not limited to cold-rolled steel sheet; Hot - rolled steel; galvanized steel; Aluminum-plated steel sheet; A coated steel sheet containing cobalt, molybdenum, tungsten, nickel, titanium, manganese, iron, magnesium, tin, copper or a mixture thereof; Or an aluminum alloy plate to which silicon, copper, magnesium, iron, manganese, titanium, zinc or a mixture thereof is added.

The coating layer is formed on the surface of the base steel sheet to realize a metal texture. The components that can be contained in the coating layer and the composition range thereof are as described above.

In the present invention, the thickness of the coating layer is not particularly limited, but may be, for example, 0.1 to 15 袖 m which is not limited. If the thickness is less than 0.1 mu m, there is a fear that the metal texture is not properly realized. On the other hand, if the thickness is more than 15 mu m, the print layer may peel off or become uncured after printing.

2 is a photograph of an appearance of an inkjet printed steel sheet manufactured according to an embodiment of the present invention. Referring to FIG. 2, it can be visually confirmed that a metal texture can be easily implemented despite using an ultraviolet curable ink.

Claims (18)

A polymer particle having a plurality of pores and a metal thin film formed on the surface,
A cavity is formed in the interior of the polymer particle,
The ratio of the volume of the hollow polymer particles to the volume of the hollow polymer particles is 8: 1 to 8: 7,
The polymer particles may be,
A core layer polymer polymerized from a monomer comprising a hydrophilic acid monomer;
An intermediate layer polymer surrounding the core layer polymer and consisting of a copolymer of a hydrophilic acid monomer and an ethylenically unsaturated monomer; And
A cell layer polymer surrounding the intermediate layer polymer and polymerized from a hydrophobic monomer;
Wherein the ink composition for ink-jet printing is a composition for ink-jet printing.
delete delete The method according to claim 1,
Wherein the average particle diameter of the polymer particles having the metal thin film formed therein is 50 to 2000 nm.
delete The method according to claim 1,
Wherein the metal constituting the metal thin film is at least one selected from the group consisting of Zn, Mg, Au, Ag, Cu and Al.
The method according to claim 1,
Wherein the metal thin film is a stainless steel thin film.
The method according to claim 1,
Wherein the metal thin film has a thickness of 10 to 200 nm.
The method according to claim 1,
Wherein the polymer particles having the metal thin film are contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the total composition.
The method according to claim 1,
50 to 78 parts by weight of an acrylic monomer, 10 to 40 parts by weight of an acrylic oligomer and 1 to 10 parts by weight of a photoinitiator.
11. The method of claim 10,
Wherein the acrylic monomer is a mixture of one or more of a monofunctional acrylic monomer, a bifunctional acrylic monomer, and a polyfunctional acrylic monomer.
11. The method of claim 10,
The acrylic oligomer may be at least one selected from the group consisting of epoxy acrylate, urethane-based modified epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic acrylate, silicone acrylate, melamine acrylate, acrylic acrylate, polythiol acrylate derivatives And a polythiol ester, and a mixture of two or more selected from the group consisting of acetal-based acrylates.
11. The method of claim 10,
Wherein the photoinitiator is a benzophenone-based, diphenoxybenzophenone-based, anthraquinone derivative, xanthone derivative, thioxanthone derivative, or benzyl-based inkjet print composition.
11. The method of claim 10,
Wherein the composition further comprises at least one additive selected from the group consisting of a defoaming agent, a leveling agent, an adhesion promoter, a stabilizer, an antioxidant, an antistatic agent, an ultraviolet absorber, a thermosetting agent and a silane coupling agent.
And a coating layer formed on the surface of the base steel sheet and including polymer particles having a plurality of pores and having a metal thin film formed on the surface thereof,
The polymer particles may be,
A core layer polymer polymerized from a monomer comprising a hydrophilic acid monomer;
An intermediate layer polymer surrounding the core layer polymer and consisting of a copolymer of a hydrophilic acid monomer and an ethylenically unsaturated monomer; And
A cell layer polymer surrounding the intermediate layer polymer and polymerized from a hydrophobic monomer;
And an ink jet printing plate.
16. The method of claim 15,
The base steel sheet includes a cold-rolled steel sheet; Hot - rolled steel; galvanized steel; Aluminum-plated steel sheet; A coated steel sheet containing cobalt, molybdenum, tungsten, nickel, titanium, manganese, iron, magnesium, tin, copper or a mixture thereof; Or an aluminum alloy plate to which silicon, copper, magnesium, iron, manganese, titanium, zinc or a mixture thereof is added.
16. The method of claim 15,
Wherein the coating layer comprises 1 to 30 parts by weight of polymer particles having the metal thin film formed thereon.

16. The method of claim 15,
Wherein the coating layer has a thickness of 0.1 to 15 占 퐉.

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