KR20190106546A - Uv-curable matt paint composition and coating film using the same - Google Patents

Abstract

The present invention relates to a UV-curable matte paint composition which can be applied to products having low gloss degree with gloss of 5% or less and is suitable for a surface decoration sheet of furniture and home appliances due to excellent hardness, stain resistance, fingerprint resistance and fume prevention function, and to a coating film using the same and, more specifically, to a UV-curable matte paint composition which can be applied to products having low gloss degree with gloss of 5% or less, and to a coating film using the same. The coating film shows noticeable gloss difference (fume phenomenon) from the surroundings as a matting agent on a surface of a coating paint film is detached by local external force applied to the coating paint film, thereby having an excellent effect in preventing the fume phenomenon.

Description

UV curable matte coating composition and coating film using same {UV-CURABLE MATT PAINT COMPOSITION AND COATING FILM USING THE SAME}

The present invention relates to a UV-curable matte coating composition and a coating film using the same, and more particularly, it can be applied to a product having a low gloss with a gloss (gloss) of 5% or less, hardness, stain resistance, fingerprints and fumes The present invention relates to an ultraviolet curable matt coating composition suitable for furniture, home appliances, exterior decoration sheets, and the like, and a coating film using the same.

In general, the surface is subjected to surface treatment in order to enhance the aesthetics of the exterior case, architectural interior, furniture, etc., and the surface treatment of the article is variously made according to the use and design of the product.

In particular, matte films can reflect light externally, preventing eye fatigue and the release of packaged contents and giving the elegance of products, such as food packaging, book covers, shopping bags, or the like. It is used for labeling paper, and its usage is gradually increasing.

However, the UV-curable matte film used in the past has a phenomenon in which a scratch appears due to a noticeable difference in gloss (fume phenomenon) as the matting agent on the surface is detached partially due to an external impact in a product having a gloss of 5% or less. (Korean Patent Nos. 10-1231508 and 10-1534621).

Therefore, in order to solve the above problems, for example, Korean Patent No. 10-1567924 (matte coating composition and coating method using the same), Patent Application No. 10-2014-0191677 (UV curing type matte coating composition and coating method using the same) As described above, an imprinting film was developed by a transfer method using a matte film.

However, the coating film prepared by the prior art is difficult to achieve a low gloss of less than 5% gross, high manufacturing price is low economical, the need for the development of a matte film with excellent economical efficiency to meet the user desires and no fume phenomenon by this atmosphere. .

 The present invention is to solve the conventional problems as described above, the purpose is to exhibit a uniform matting effect of less than 5% gloss, UV curable matte coating composition excellent in fume, stain resistance, scratch resistance and coating using the same To provide a film.

According to an aspect of the present invention for achieving the above object, 3 to 10 parts by weight of acidic silica particles having a hydrogen ion concentration or acidity (pH) of 1 to 6; 0.2 to 5 parts by weight of monofunctional acrylate having an amine group; 1 to 10 parts by weight of acrylate having an ethylene oxide group; 1 to 5 parts by weight of silane-modified acrylate represented by Formula 1 below; 10 to 30 parts by weight of polyfunctional acrylate; 2 to 6 parts by weight of photoinitiator; 0.5 to 5 parts by weight of the additive; And 40 to 70 parts by weight of a diluent is provided.

[Formula 1]

(R ₁ O) ₃ -Si- (CH ₂ ) ₃ -O-CH ₂ -CH (OH) -CH ₂ -OCO-R ₂ -CO ₂ -CH ₂ -R ₃

In Chemical Formula 1,

R ₁ = H, CH ₃ , C ₂ H ₅

R ₂ = alkyl or alkene having 2 to 10 carbon atoms

R ₃ = (CH ₂ = CHOCOCH ₂ ) ₂ -C-CH ₂ OCH ₂ C (CH ₂ OCOCH = CH ₂ ) ₃

to be.

In one embodiment, the acidic silica particles having a pH of 1 to 6 are for the quenching of the coating film, and strong ionic bonds through the acid-base reaction between the basic acrylic monomer and the silica surface during drying and UV curing of the coating layer. Forming, may comprise 3 to 10 parts by weight relative to the total coating composition.

In one embodiment, the average particle diameter of the silica particles is preferably 1um or more and less than 5um.

In one embodiment, the monofunctional acrylate having the amine group is acrylamide, N-methanol acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-vinylpyrrolidin. It may include one or more components selected from the group consisting of 4-acryloyl morpholine.

In one embodiment, the monofunctional acrylate having the amine group may include 0.2 to 5 parts by weight relative to the total composition. According to this configuration, the reactive amine group is a monomer having a very low viscosity and very high reactivity with the silica surface, and enhances adhesion by ionic bonding through an acid-base reaction. In addition, when the amine group is introduced into the polymer, it is difficult to form a strong bond with the silica surface because the molecular migration in the polymer is not smooth. In addition, the presence of unsaturated hydrocarbons in the amine group can form a network through the photocuring reaction with the polyfunctional acrylate to improve the chemical resistance and alkali resistance.

In one embodiment, the acrylate having an ethylene oxide group, phenol (ethyleneoxy) ₂ acrylate, phenol (ethyleneoxy) ₄ acrylate, nonylphenol (ethyleneoxy) _2-8 acrylate, (2-8 mol) ) Phenol (meth) acrylate, ethylene oxide addition (2-10 mol) 1,6-hexanediol diacrylate, bisphenol A (3-30 mol of ethylene oxide addition) di (meth) acrylate, ethylene oxide addition (3 At least one component selected from the group consisting of trimethylolpropane (meth) acrylate, propylene oxide addition (3 moles) trimethylolpropane tri (meth) acrylate, and ethylene oxide addition pentaerythritol tetraacrylate It may include.

Here, the acrylate having the ethylene oxide group serves to improve the leveling and coating properties of the coating film. Silica, a metal oxide, has poor coating properties, and can be used to improve the coating properties of metal oxides by using a binder or a good coating property. Ethylene oxide groups not only improve the wettability of the surface of the substrate but also increase the compatibility with the metal oxides to make the coating surface feel better. It is desirable to include 1 to 10 parts by weight relative to the total coating composition by incorporating such performance and / or effects.

In one embodiment, the silane-modified acrylate includes 1 to 5 parts by weight based on the total composition. The silane-modified acrylate represented by the above [Formula 1] acts as a crosslinking agent to induce an organic-inorganic hybrid bond with an inorganic silica through the silane group, and increases the degree of curing through the optical crosslinking reaction through the acrylate group to increase the network structure. Can be formed. The organic-inorganic hybrid bond suppresses scratch resistance of the coating film and breakage of the coating film, and suppresses phase separation between organic and inorganic phases that occur during the curing process after coating, thereby maintaining the coating film with uniform physical properties.

In one embodiment, the multifunctional acrylate has the purpose of increasing the hardness of the coating film by increasing the degree of light curing of the coating film. It may include 10 to 30 parts by weight relative to the total coating composition. In this case, the photocurable resin may include at least one component selected from the group consisting of acrylacrylate and urethane acrylate in trifunctional to 10 functional groups.

In one embodiment, the additives include dispersants, leveling agents, antioxidants, and the like. The dispersant increases the dispersibility of the silica particles, the leveling agent increases the wettability of the surface of the substrate to suppress the crater phenomenon of the coating surface, and the antioxidant improves weather resistance. It is preferable to include 0.5 to 5 parts by weight relative to the total coating composition in consideration of the functions or effects of the components.

In one embodiment, the diluent is methyl ethyl ketone (MEK), ethyl acetate (EA), butyl acetate (BA), isopropyl alcohol (IPA), butanol ( BuOH), methyl isobutyl ketone (MIBK), diacetone alcohol (DAA), toluene (Toluene) and one or more selected from the group consisting of these mixed solvents can be used. 40 to 70 parts by weight relative to the total coating composition.

In one embodiment, the UV-curable matte coating composition may be used within 2 to 6 parts by weight of the photoinitiator relative to the entire resin composition in order to cure the coating after coating. Photoinitiators that can be used can be classified into chemical groups within their molecular structure. As the chemical structure that can be used, ketal series, acetophenone series, sulfide series, benzoate series, benzophenone series, spin series, benzoylformate series and the like can be used.

According to another aspect of the present invention for solving the technical problem, the base layer; And a coating layer formed on the base layer, wherein the coating layer is provided on one side thereof with a coating film prepared by UV curing an ultraviolet curable matte coating composition.

In one embodiment, the substrate layer is polyethylene terephthalate (PET, G-PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene (PS) It may include any one selected from polyvinyl chlorite (PVC), acrylonitrile-styrene-acrylic (Acrylonitrile, ASA) materials.

Here, the substrate layer may have a thickness of 20 ~ 2,000㎛. The coating thickness of the composition is usually 1-20um, and the production speed is 1-100m per minute.

In one embodiment, the coating process for the coating layer is made in two steps, the first step comprises the step of coating the gravure or microgravure on the surface of the substrate and then drying. The dilution solvent may be removed during the drying process. The second step is a light irradiation step that includes the step of completely curing the dried coating layer. According to this curing process, the uncured coating layer that is not completely cured can be completely cured. The amount of light irradiation is preferably in the range of 50 to 500 mJ / cm 2 for the curing process of optimum efficiency.

According to the ultraviolet curable matte coating composition of the present invention and the matte film using the same according to the present invention, the manufactured matte coating composition is very excellent in fume, substrate adhesion, surface hardness, scratch resistance, film processability (flexibility) and pollution resistance. great.

According to the present invention, it can be used for various decoration purposes, in particular, it is possible to provide a matte film suitable for realizing the shape of the exterior of the furniture, home appliances, doorway decoration.

1 schematically illustrates a cross section of a matte film according to Example 1 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail. In the case of surface treatment using the conventionally invented silica, the physical properties are greatly changed depending on the degree of surface treatment. When the surface treatment is less, the bonding strength with the resin is very weak, and fume is generated by desorption of the matting agent due to external impact. In order to achieve low gloss when the surface of silica is treated with a large amount of surface treatment agent, there is no effect of floating silica on the surface of the coating after coating drying. It becomes hard and a crack occurs.

Therefore, the present inventors have been studying to improve this conflicting problem, the combination of the acidic silica and the monomer having an amine group confirmed that the phenomenon of the fume caused by the difference in gloss due to the matting agent desorption by the external impact is improved. Thus, strong ionic bonds were formed through acid-base reactions between monomers having these amine groups and the acidic silica surface, thereby suppressing the quencher desorption and improving the fume. By introducing an acrylate having an ethylene oxide group, it complements the low substrate wettability and coating property of silica, increases the solution compatibility between the resin and the metal oxide silica, and induces an organic-inorganic hybrid bond with silane-modified acrylate. In addition, the scratch resistance is increased, and the photocuring reaction between acrylates increases the polyfunctional acrylate and the photocurability, thereby forming a network to form a rigid structure. A dispersing agent, a leveling agent, and antioxidant were added here, and the photocurable matte coating composition was completed.

In the case of the finished matte coating composition, the finished coating coating has the advantage that the substrate adhesion, flexibility, surface hardness, surface feel, stain resistance and fume are remarkably improved.

UV curable Matte  Paint composition

The ultraviolet curable matt coating composition according to the present embodiment, 3 to 10 parts by weight of the acidic silica particles having an acidity (pH) of 1 to 6; 0.2 to 5 parts by weight of monofunctional acrylate having an amine group; 1 to 10 parts by weight of acrylate having an ethylene oxide group; 1 to 5 parts by weight of silane-modified acrylate represented by Formula 1 below; 10 to 30 parts by weight of polyfunctional acrylate; 2 to 6 parts by weight of photoinitiator; 0.5 to 5 parts by weight of the additive; Diluent 40 to 70 parts by weight.

[Formula 1]

(R ₁ O) ₃ -Si- (CH ₂ ) ₃ -O-CH ₂ -CH (OH) -CH ₂ -OCO-R ₂ -CO ₂ -CH ₂ -R ₃

In Chemical Formula 1,

R ₁ = H, CH ₃ , C ₂ H ₅

R ₂ = alkyl or alkene having 2 to 10 carbon atoms

R ₃ = (CH ₂ = CHOCOCH ₂ ) ₂ -C-CH ₂ OCH ₂ C (CH ₂ OCOCH = CH ₂ ) ₃

to be.

The UV-curable matte coating composition may be used for coating purposes such as sheets, films, etc. At this time, the coating agent should have high stain resistance, surface hardness, and substrate adhesion, and should have excellent elongation so as not to cause cracks during the post-processing of the matte film. . In addition, fumes should not be generated after contact with nails or other objects during product processing or when used by consumers in daily life. When fumes are generated, the surface of the coating appears to be scratched due to a noticeable difference in gloss from the surroundings, leaving a big flaw in the aesthetics of the product. Therefore, the present invention is to solve these problems and to provide a coating product with a beautiful surface,

In this embodiment, the ultraviolet curable matte coating composition includes silica particles having an acidic surface charge, which is intended to form an ionic bond between the positive charge on the surface of the silica and the amine group to strengthen the adhesion. If the silica surface is neutral or alkaline, these ionic bonds cannot be formed. In addition, the surface-treated silica is excellent in coating properties and compatibility with the resin, but there is no fume improvement effect.

When the silica surface is treated with the silane coupling agent, when the surface treatment is less, the bonding strength with the resin is very weak, and fume is generated by the desorption of the matting agent due to external impact. At the time of treatment, silica does not float to the coating surface after coating drying, so the matting effect is remarkably decreased, and to realize low gloss of less than 5% of gloss, an excessively surface treated silica is used to make the coating film very hard and cracks are generated.

The acidic silica particles include 3 to 10 parts by weight based on the total coating composition. It is preferable that the average particle diameter of a silica particle is 1 micrometer or more and 5 micrometers or less. If less than 3 parts by weight compared to the coating composition is difficult to implement a low gloss, if more than 10 parts by weight has a disadvantage of poor coating uniformity.

The acrylate having the amine group includes 0.2 to 5 parts by weight relative to the total composition to increase adhesion to silica particles. Acrylate monomers with amine groups in the composition enhance adhesion by ionic bonds through acid-base reactions with positively charged silica particles. In general, ionic bonds through acid-base reactions form strong bonds.

In the case where the amine group is introduced into the polymer chain, it is difficult to form a strong bond with the metal deposition layer because the molecular migration in the polymer is not smooth. Silica particles must rise to the surface after coating to achieve a low gloss of less than 5% gloss. For this purpose, acrylates with low viscosity amine groups are suitable.

At this time, the acrylate having an amine group is a group consisting of acrylamide, N-methanol acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-vinylpyrrolidine, 4-acryloyl morpholine It may include one or more selected from.

When the acrylate having the amine group is less than 0.2% by weight of the entire composition, the effect of improving fume through ionic bonding with acidic silica particles is insufficient, and when more than 5% by weight, more silica particles may be added to coat the coating film. Sex is worse.

The acrylate having the ethylene oxide group is intended to complement the low substrate wettability and coating property of the silica and to improve the compatibility between the resin and the metal oxide silica. In addition, the ethylene oxide group gives the effect of improving the slip feeling of the coating film after coating curing. An acrylate having an ethylene oxide group contains 1 to 10 parts by weight based on the total composition.

When less than 1 part by weight relative to the total composition, the substrate wettability is less and the slip of the coating film is also inferior. When more than 10 parts by weight may cause a problem that the surface hardness of the coating film is lowered.

In view of this, acrylates having ethylene oxide groups include phenol (ethyleneoxy) ₂ acrylate, phenol (ethyleneoxy) ₄ acrylate, nonylphenol (ethyleneoxy) _2-8 acrylate, (2-8 mol) phenol (Meth) acrylate, ethylene oxide addition (2-10 mol) 1,6-hexanediol diacrylate, bisphenol A (ethylene oxide addition 3-30 mol) di (meth) acrylate, ethylene oxide addition (3-15 Mole) trimethylolpropane (meth) acrylate, propylene oxide addition (3 mol) trimethylolpropane tri (meth) acrylate, ethylene oxide addition pentaerythritol tetra acrylate containing one or more components selected from the group consisting of can do.

The silane-modified acrylate may be represented by the following formula (1). A silane coupling agent is introduced into the acrylate to enable bonding with silica, which is an inorganic particle, and to induce a network structure between organic materials through a photocuring reaction. The silane-modified acrylate inhibits scratch resistance and breakage of the coating film through an organic-inorganic hybrid bond, and improves compatibility between organic and inorganic materials. The silane modified acrylate includes 1 to 5 parts by weight of the total composition. When less than 1 part by weight compared to the total composition, the organic-inorganic hybrid effect is less scratch resistance effect is less than 5 parts by weight, the coating film is hard due to economical and over-curing causes a problem of inflexibility.

In detail, a silane-modified acrylate synthesis example is described. First, a carboxylic acid having an ester (-COO) structure through ring-opening reaction with dipentaerythritol pentaacrylate (DPPA) and maleic anhydride After the (-COOH) structure is formed, the compound corresponding to [Formula 1] may be synthesized through glycidylpropyltriethyl silane (GPTS) and an epoxy ring-opening reaction.

[Formula 1]

(R ₁ O) ₃ -Si- (CH ₂ ) ₃ -O-CH ₂ -CH (OH) -CH ₂ -OCO-R ₂ -CO ₂ -CH ₂ -R ₃

In Chemical Formula 1,

R ₁ = H, CH ₃ , C ₂ H ₅

R ₂ = alkyl or alkene having 2 to 10 carbon atoms

R ₃ = (CH ₂ = CHOCOCH ₂ ) ₂ -C-CH ₂ OCH ₂ C (CH ₂ OCOCH = CH ₂ ) ₃

to be.

The polyfunctional acrylate has the purpose of increasing the light curing degree and the hardness of the coating film. 10 to 30 parts by weight relative to the total coating composition.

At this time, the photocurable resin is polyfunctional acrylate, trimethylolpropane (meth) acrylate, trifunctional urethane acrylate, glycerin triacrylate, pentaerythritol tri (meth) acrylate, tris 2-hydroxyethyl isocyanate Triacrylate, Ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate 6 It may include one or more components selected from the group consisting of functional urethane acrylate, 10 functional aliphatic urethane acrylate.

When the polyfunctional acrylate is less than 10 parts by weight of the total composition, the coating film curing degree is lowered, and the surface hardness is lowered. When the polyfunctional acrylate is more than 30 parts by weight, the coating film is hard and cracks are generated.

The additives include a dispersing agent, a leveling agent, an antioxidant, and the like to keep the coating surface smooth during gravure and microgravure coating and to improve substrate wettability, dispersibility of silica particles, and weather resistance. The dispersant increases the dispersibility of the silica particles, the leveling agent increases the wettability of the surface of the substrate to suppress the crater phenomenon of the coating surface, and the antioxidant improves weather resistance. 0.5 to 5 parts by weight relative to the total coating composition.

As the leveling agent, silicone-based shows excellent release property, and acrylic-based may be used. Commercially available leveling agents are BYK BYK-300 series and BYK-3500 series, Tego RAD-2000 series, dispersants BYK 100 series and Tegosa Dispers 600-700 series, and antioxidants BYK Tinuvin Use series.

The UV-curable matte coating composition may be used within 2 to 6 parts by weight of the photoinitiator relative to the total composition of the resin composition in order to cure the coating after coating. When the content of the initiator is less than 2 parts by weight of the coating composition, there is a high possibility of a problem in the coating film hardening, and when the content of more than 6 parts by weight has a disadvantage of poor weather resistance.

Photoinitiators that can be used can be classified into chemical groups within their molecular structure. As the chemical structure that can be used, ketal series, acetophenone series, sulfide series, benzoate series, benzophenone series, spin series, benzoylformate series and the like can be used.

Specific examples of photoinitiators used include 1-hydroxycyclohexyl-phenol-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethylketone, 1 -(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, benzophenone, 2,2-dimethoxy-2-phenylacetphenone, 2,2-diethoxy-2-phenylacetphenone, 2-hydroxy-2 -Methyl-1-propane-1-one, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethalanthraquinone, 2-methylthioxanthone, 2-ethyloxanthone , 2,4-dimethyl thioxanthone and 2,4-diethyloxanthone can be used, and one of these is preferably used alone or in combination of two or more thereof.

Commercially available photoinitiators include Ciba's products; Irgacure 184, 500, 2959, 754, 651, 369, 907, 1300, 819, 819DW, 2022, 2100, 784, 250, Darocur 1173, MBF, TPO, 4265 or Double Bond Chemicals: Doublecure BDK, TPO, One or more of TPO-L, 73W, 107, 173, 184, 200, 284, 560, 998, 1130, 1172, 1176, 1190, and 1256 can be used in combination. There is no particular limitation on the type of photoinitiator that can be used.

The diluent is not particularly limited as long as it is a solvent capable of controlling the viscosity of the matte coating composition without affecting the physical properties of the monofunctional acrylate having acidic silica particles and the amine group and the acrylate having an ethylene oxide group. Methyl ethyl ketone (MEK), ethyl acetate (EA), butyl acetate (BA), isopropyl alcohol (IPA), butanol (BuOH), methyl isobutyl ketone (MIBK) with excellent effects of improving the storage stability, dilution rate, etc. of the composition ), Diacetone alcohol (DAA), toluene (Toluene) and one or more selected from the group consisting of these mixed solvents can be used. 40 to 70 parts by weight relative to the total coating composition. When the content is less than 40 parts by weight, the solid content is high, which causes a problem in the gravure or microgravure coating. When the content is more than 70 parts by weight, the coating thickness is lowered.

Substrate films used are crystalline and amorphous polyethylene terephthalate (PET, G-PET), polycarbonate (PC), polymethylmethacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene ( PS), polyvinyl chlorite (PVC), acrylonitrile-styrene-acryl (Acrylonitrile, ASA) material of at least one of.

Matte  film

In this embodiment, the base layer; And a coating layer formed on the base layer, wherein the coating layer provides a matte film formed by UV curing the matte coating composition described above. The matte film may be referred to as a matte coated film or a coated film.

Figure 1 shows briefly the cross section of the matte film according to the present invention. As shown in FIG. 1, the matte film 100 according to the present embodiment includes a base layer 10 and a coating layer 20 formed of an ultraviolet curable matte coating composition according to the present invention.

The base layer is crystalline and amorphous polyethylene terephthalate (PET, G-PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene (PS) , Polyvinyl chlorite (PVC), acrylonitrile-styrene-acryl (Acrylonitrile; ASA) may include at least one. In addition, the surface of the substrate layer may be modified by a surface treatment known to those skilled in the art, for example, a surface treatment such as corona or plasma, to control adhesion and surface tension in a subsequent process.

A primer layer may be further included on or below the substrate layer 10. The primer layer may control the temperature transfer between the base layer 10 and the adjacent layer, and may improve the adhesion between the base layer 10 and the adjacent layer. As a suitable material for such a primer layer, one or more selected from the group consisting of acrylic resins, polyurethane resins, and polyester resins may be used.

The coating layer 20 may have a thickness of about 1 to 100 μm, specifically about 3 to 30 μm. If the thickness of the coating layer 20 is less than about 2㎛, there is a problem that it is difficult to ensure the thickness uniformity of the coating layer 20 according to the formation, if it exceeds about 100㎛, the coating layer 20 is hard to crack There is a problem that the weakness for the coating layer 20 excellent in fouling resistance and hardness in the above range can be implemented.

Matte  Film manufacturing method

In addition, the method of manufacturing a matte film according to the present embodiment, (a) coating the matte coating composition according to the invention on the base layer; And (b) drying and ultraviolet curing the coated matt coating composition.

Step (a) is a step of coating the matte coating composition according to the present invention on the base layer. Specific physical properties of the matte coating composition are as described above.

In the step (a), the coating layer may be performed according to at least one method selected from bar coating, roll coating, curtain coating, gravure coating, and microgravure coating, but is not limited thereto. Preferably, gravure and microgravure coatings are performed. Use the method. The microgravure coating method is suitable when coating appearance or precise thickness control is required, and the gravure coating method is easy as the method of lowering the production cost by increasing the production speed.

Step (b) is a step of UV curing the coated matte coating composition. In the step (b), the coated matte coating composition may be passed through a hot air drying line to remove the diluent, and may be UV cured at a light amount of about 50 to about 600 mJ / cm ² . There are approximately 50mJ the amount of light falling upon the curing rate of the ultraviolet ray irradiation under / cm ² issues, the quantity of light during the light irradiation to the substrate layer of about 600mJ / cm ² than there is a possibility that because of the yellowing furnace fruit stalk.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.

<Examples and Comparative Examples>

Example  One

5 parts by weight of the acidic silica particles and SS-335 (S-Schemtech, pH = 3.5, average particle diameter of 3.5 µm) with respect to 100 parts by weight of the ultraviolet curable matt coating composition; 0.5 part by weight of monofunctional acrylate having an amine group, N-vinylpyrrolidine (Aldrich, NVP); 8 parts by weight of an acrylate having an ethylene oxide group, Miramer M2100 (Miwon Corporation, 10 moles of ethylene oxide added difunctional acrylate); 16 parts by weight of polyfunctional acrylate, PN-3911 (polynetrone, 10 functional urethane acrylate); 4 parts by weight of a silane modified acrylate, PN-8100 (polynetron, 5-functional silane modified acrylate); Additive, 1 part by weight of RAD-2200N (tego, leveling agent), 2 parts by weight of BYK-103 (BYK, dispersant), 0.2 part by weight of Tinuvin 1130 (Ciba, antioxidant); Photoinitiator, 3 parts by weight of Irgacure 184 (Ciba, 1-hydroxy-cyclohexyl-phenol-ketone); A diluent, 23 parts by weight of methyl ethyl ketone (MEK), 5 parts by weight of diacetone alcohol (DAA), 27.3 parts by weight of butyl acetate (BA), 5 parts by weight of N-butanol (BuOH); An ultraviolet curable matt coating composition was prepared.

Thereafter, the UV-curable matte coating composition was coated with microgravure on the white G-PET 1,000 μm film (manufactured by Doosung Korea Co., Ltd.) at about 10 to 15 μm to form a coating layer, and after drying at 60 to 80 ^° C., 300 mJ / The coating layer was cured by ultraviolet irradiation with a light amount of cm ² to prepare a matte film.

Example  2

5 parts by weight of the acidic silica particles and SS-335 (S-Schemtech, pH = 3.5, average particle diameter of 3.5 µm) with respect to 100 parts by weight of the ultraviolet curable matt coating composition; 0.5 part by weight of monofunctional acrylate having an amine group, N-vinylpyrrolidine (Aldrich, NVP); 8 parts by weight of an acrylate having an ethylene oxide group, Miramer M3190 (Miwon Corporation, 9 moles of ethylene oxide added trifunctional acrylate); 16 parts by weight of polyfunctional acrylate, T003 (K-PX, TMPTA, trifunctional acrylate); 4 parts by weight of a silane-modified acrylate and PN-8100 (polynetron, 5-functional silane-modified acrylate); Additive, 0.5 parts by weight of BYK-333 (BYK, leveling agent), 2 parts by weight of BYK-103 (BYK, dispersant), 0.2 parts by weight of Tinuvin 1130 (Siva, antioxidant); Photoinitiator, 2.5 parts by weight of Irgacure 184 (Ciba, 1-hydroxy-cyclohexyl-phenol-ketone), 0.5 part by weight of Darocur TPO (Ciba, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide); Diluent, 20 parts by weight of methyl ethyl ketone (MEK), 8 parts by weight of ethyl acetate (EA), 27.3 parts by weight of butyl acetate (BA), 5 parts by weight of N-butanol (BuOH); An ultraviolet curable matt coating composition was prepared.

Thereafter, the UV-curable matte coating composition was coated with microgravure on the white G-PET 1,000 μm film (manufactured by Doosung Korea Co., Ltd.) at about 10 to 15 μm to form a coating layer, and after drying at 60 to 80 ^° C., 300 mJ / The coating layer was cured by ultraviolet irradiation with a light amount of cm ² to prepare a matte film.

Comparative example  One

4 parts by weight of spherical silica particles and SS-230 (S-chemtech, pH = 7, average particle diameter of 3.5 µm) with respect to 100 parts by weight of the ultraviolet curable matt coating composition; 10 parts by weight of monofunctional acrylate, hydroxypropyl acrylate (Aldrich, HPA, monofunctional acrylate); Polyfunctional acrylate, T003 (K-PX, TMPTA, trifunctional acrylate) 14 parts by weight, Miramer PU664 (Miwon Corporation, 6-functional urethane acrylate) 4 parts by weight; Additive, 0.5 parts by weight of BYK-333 (BYK, leveling agent), 2 parts by weight of BYK-103 (BYK, dispersant), 0.2 parts by weight of Tinuvin 1130 (Siva, antioxidant); Photoinitiator, 2.5 parts by weight of Irgacure 184 (Ciba, 1-hydroxy-cyclohexyl-phenol-ketone), 0.5 part by weight of Darocur TPO (Ciba, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide); Diluent, 28 parts by weight of ethyl acetate (EA), 28.3 parts by weight of butyl acetate (BA), 5 parts by weight of N-butanol (BuOH); An ultraviolet curable matt coating composition was prepared.

Thereafter, the UV-curable matte coating composition was coated with microgravure on the white G-PET 1,000 μm film (manufactured by Doosung Korea Co., Ltd.) at about 10 to 15 μm to form a coating layer, and after drying at 60 to 80 ^° C., 300 mJ / The coating layer was cured by ultraviolet irradiation with a light amount of cm ² to prepare a matte film.

Comparative example  2

4 parts by weight of spherical silica particles and SS-250N (S-Schemtech, pH = 7, average particle diameter of 5 µm, wax surface treatment) based on 100 parts by weight of the ultraviolet curable matte coating composition solid content; 6 parts by weight of monofunctional acrylate, hydroxypropyl acrylate (Aldrich, HPA, monofunctional acrylate); 18 parts by weight of polyfunctional acrylate, T003 (KPX, TMPTA, trifunctional acrylate), 4 parts by weight of Miramer PU664 (Miwon Corporation, 6-functional urethane acrylate); Additive, 0.5 parts by weight of BYK-333 (BYK, leveling agent), 2 parts by weight of BYK-103 (BYK, dispersant), 0.2 parts by weight of Tinuvin 1130 (Siva, antioxidant); Photoinitiator, 2.5 parts by weight of Irgacure 184 (Ciba, 1-hydroxy-cyclohexyl-phenol-ketone), 0.5 part by weight of Darocur TPO (Ciba, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide); Diluent, 20 parts by weight of methyl ethyl ketone (MEK), 13 parts by weight of ethyl acetate (EA), 28.3 parts by weight of butyl acetate (BA); An ultraviolet curable matt coating composition was prepared.

Thereafter, the UV-curable matte coating composition was coated with microgravure on the white G-PET 1,000 μm film (manufactured by Doosung Korea Co., Ltd.) at about 10 to 15 μm to form a coating layer, and after drying at 60 to 80 ^° C., 300 mJ / The coating layer was cured by ultraviolet irradiation with a light amount of cm ² to prepare a matte film.

Experimental Example

1) gloss rating

After curing the UV-curable matte coating composition to G-PET (Doosung Korea), the coating film thickness was applied to 10 ~ 15㎛, dried 60 ~ 80 ^o C, 30 sec, completely cured to 300mJ with a mercury lamp under oxygen atmosphere Let's do it. It was measured and measured with a polisher (60 ^o Gloss) (see Table 1).

2) substrate adhesion

After eleven straight lines were drawn on the coated surface of the film at intervals of 1 mm to make 100 squares, five peel tests were performed using a niche reflective tape CT-24. Three 100 squares were tested and recorded. After coating, the thickness of the printed layer was about 10 μm.

The test record results for the substrate adhesion are expressed as the ratio (n / 100) of the number n of the rectangles that do not peel out of the number 100 of the entire rectangles. For example, if not completely peeled off (100/100; at least 3 times) it was recorded as 'OK', otherwise it was recorded as 'NG' (see Table 1).

3) pencil hardness

The test was done by the pencil hardness tester. Measurement was carried out according to JIS K 5600-5-4 except that the tester was set so that the front part of the pencil applied a load of 250 g to the coating surface when the tester was in the horizontal position. The evaluation results are shown in Table 1 below.

4) Hume Evaluation

Using the matte coating compositions of Examples 1 and 2 and Comparative Examples 1 and 2, a coating sample was prepared to obtain a gloss of about 4% of gloss, and then rubbed with a fingernail. The results are shown in Table 1 below.

In Table 1, the minimal change in gloss is reported as 'O', the light change in gloss as 'Δ' and the severe change in gloss as 'X'.

5) Scratch Resistance

After rubbing strongly using steel wool # 0000, the degree of scratches was evaluated and the results are shown in Table 1 below.

In Table 1, the minimum change of the coating surface was recorded as 'O', the light change of the coating surface as '△', and the severe change of the coating surface was recorded as 'X'.

6) Pollution resistance

Vinegar, soy sauce, coffee, black magic, ethanol was dropped on the coating layer and then wiped off after 24 hours and inspected. The evaluation results are shown in Table 1 below.

In Table 1, the level of no trace is '5', and the detail level is '4', the level of trace is '4', the level of trace is '3', and the level of trace is '2'. These varying levels were recorded as' 1's respectively.

Evaluation item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polish 3.8 4.1 4.4 4.8 Adhesion OK OK NG OK Pencil hardness H H HB H Hum O O △ X Scratch resistance O O △ X Pollution resistance 5 5 4 4

As can be seen from Table 1, the Example shows a higher score than the Comparative Example in all items of the physical property evaluation. The reason why the Examples show higher scores in all items than the Comparative Examples is that the UV-curable matte coating composition showed excellent properties of fume, scratch resistance, and adhesion through an acid-base reaction and an organic-inorganic hybrid bond. It can be used for decoration films such as furniture and architectural exterior interiors.

The embodiments described so far are merely illustrative of the preferred embodiments of the present invention, and the scope of the present invention is not limited to the described embodiments, and those skilled in the art within the technical spirit and claims of the present invention. It will be understood that various changes, modifications, or substitutions may be made thereto, and such embodiments are to be understood as being within the scope of the present invention.

10: base material layer
20: coating layer
100: matte film

Claims (6)

3 to 10 parts by weight of acidic silica particles having an acidity (pH) of 1 to 6;
0.2 to 5 parts by weight of monofunctional acrylate having an amine group;
1 to 10 parts by weight of acrylate having an ethylene oxide group;
1 to 5 parts by weight of silane-modified acrylate represented by Formula 1;
10 to 30 parts by weight of polyfunctional acrylate;
2 to 6 parts by weight of photoinitiator;
0.5 to 5 parts by weight of the additive; And
UV curable matte paint composition comprising a diluent 40 to 70 parts by weight:
[Formula 1]
(R ₁ O) ₃ -Si- (CH ₂ ) ₃ -O-CH ₂ -CH (OH) -CH ₂ -OCO-R ₂ -CO ₂ -CH ₂ -R ₃
R ₁ = H, CH ₃ , C ₂ H ₅
R ₂ = alkyl or alkene having 2 to 10 carbon atoms
R ₃ = (CH ₂ = CHOCOCH ₂ ) ₂ -C-CH ₂ OCH ₂ C (CH ₂ OCOCH = CH ₂ ) ₃ . The ultraviolet curable matt coating composition according to claim 1, wherein the acidic silica particles have a particle size of 1 to 5 µm. The monofunctional acrylate having the amine group is acrylamide, N-methanol acrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, or N-vinylpyrrolidine. UV-curable matt coating composition comprising at least one component selected from the group consisting of 4-acryloyl morpholine. The acrylate having the ethylene oxide group is phenol (ethyleneoxy) ₂ acrylate, phenol (ethyleneoxy) ₄ acrylate, nonylphenol (ethyleneoxy) _{2 to 8} acrylate, (2 to 8) Mole) phenol (meth) acrylate, ethylene oxide addition (2-10 mole) 1,6-hexanediol diacrylate, bisphenol A (3-30 mole of ethylene oxide addition) di (meth) acrylate, ethylene oxide addition ( 3 to 15 moles) at least one selected from the group consisting of trimethylolpropane (meth) acrylate, propylene oxide addition (3 moles) trimethylolpropane tri (meth) acrylate, and ethylene oxide addition pentaerythritol tetra acrylate An ultraviolet curable matte coating composition comprising the component. Base layer; And a coating layer formed on the base layer,
The coating layer is a coating film, characterized in that the UV-curable matte coating composition of any one of claims 1 to 4 formed by ultraviolet curing. The method of claim 5, wherein the substrate layer is polyethylene terephthalate (PET, G-PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene ( PS), polyvinyl chlorite (PVC), acrylonitrile-styrene-acrylic (Acrylonitrile, ASA) material of any one selected from the coating film.

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