KR102016954B1 - Uv curing type matt paint composition, a decoration sheet applied the same and methods for manufacturing the decoration sheet - Google Patents

Uv curing type matt paint composition, a decoration sheet applied the same and methods for manufacturing the decoration sheet Download PDF

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KR102016954B1
KR102016954B1 KR1020140145412A KR20140145412A KR102016954B1 KR 102016954 B1 KR102016954 B1 KR 102016954B1 KR 1020140145412 A KR1020140145412 A KR 1020140145412A KR 20140145412 A KR20140145412 A KR 20140145412A KR 102016954 B1 KR102016954 B1 KR 102016954B1
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South Korea
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coating
urethane acrylate
weight
curable
paint composition
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KR1020140145412A
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Korean (ko)
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KR20160049168A (en
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권혜원
송예리
김유준
예성훈
박환석
유다영
남해림
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(주)엘지하우시스
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

First difunctional urethane acrylate oligomers prepared from linear polyester polyols; A second difunctional urethane acrylate oligomer having a larger weight average molecular weight than the first difunctional urethane acrylate; Polyfunctional acrylate monomers; And it provides a UV curable matte coating composition comprising a photoinitiator, a decor sheet and the method for producing the decor sheet and the like applied thereto.

Description

UV Curing Matte Coating Composition, Deco Sheet and Deco Sheet Manufacturing Method Using the Same {UV CURING TYPE MATT PAINT COMPOSITION, A DECORATION SHEET APPLIED THE SAME AND METHODS FOR MANUFACTURING THE DECORATION SHEET}

The present invention relates to an optical UV curable matt coating composition, a decor sheet and a decor sheet to which the same is applied.

In materials such as furniture, sinks and doors, coatings, decoration sheets or decoration sheets are mainly used for decoration purposes.

In the case of a UV-curable high-gloss coating material as a coating material, only a single color can be realized, and there is a problem in that yellowing of the applied paint and deterioration of glossiness with time are applied. In the case of the conventional UV curable matte coating composition, only the bifunctional oligomer is used to reduce the curing rate of the coating layer, leaving the uncured product, and it is difficult to absorb contaminants due to its poor rigidity.

In addition, the decor sheet used indoors are exposed to an environment vulnerable to contaminants, etc., and thus additionally require contamination resistance.

The present invention comprises a first difunctional urethane acrylate oligomer prepared from linear polyester polyols; A second difunctional urethane acrylate oligomer having a larger weight average molecular weight than the first difunctional urethane acrylate oligomer; An object of the present invention is to provide a UV curable matt coating composition including a multifunctional acrylate monomer and a photoinitiator.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention comprises a first difunctional urethane acrylate oligomer prepared from linear polyester polyols; A second difunctional urethane acrylate oligomer having a larger weight average molecular weight than the first difunctional urethane acrylate oligomer; Polyfunctional acrylate monomers; And photoinitiators; It provides a UV curable matt coating composition comprising a.

30 to 40 parts by weight of the first bifunctional urethane acrylate oligomer, 5 to 15 parts by weight of the second bifunctional urethane acrylate oligomer, and the multifunctional acrylate monomer based on 100 parts by weight of the UV-curable matte coating composition solid content It can provide a UV curable matt coating composition comprising 20 to 40 parts by weight.

The weight average molecular weight of the first bifunctional urethane acrylate oligomer may provide a UV curable matt coating composition of 10000 to 20000.

The weight average molecular weight of the second bifunctional urethane acrylate oligomer may provide a UV curable matt coating composition of 20000 to 30000.

The polyfunctional acrylate monomer is a UV curable type including at least one selected from pentaerythritol tri (meth) acrylate (PETIA), dipentaerythritol hexa (meth) acrylate (DPHA), and combinations thereof A matte coating composition can be provided.

The photoinitiator is benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, α, α-methoxy-α-hydroxyaceto Phenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-dimeth Oxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] It is possible to provide a UV curable matt coating composition comprising at least one selected from the group consisting of -1-butanone and combinations thereof.

It is possible to provide a UV curable matt coating composition further comprising an additive selected from the group consisting of dispersants, matting agents, antifoaming agents and combinations thereof.

The present invention is a substrate layer; And a coating layer formed on the base layer, wherein the coating layer provides a decor sheet formed by UV curing the matte coating composition as described above.

The base layer is translucent PVC (polyvinyl chloride) polyethylene terephthalate (PET; polyethylene terephthalate), polyethylene naphthalate (PEN; polyethylene naphthalate), polycarbonate (PC; Polycarbonate), cyclic olefin polymer or copolymer (Cyclic olefin polymer or It is possible to provide a decor sheet made of a copolymer or a methylene diphenyl diisocyanate (MDI).

The coating layer may provide a decor sheet having a thickness of 2 to 6㎛.

Curing rate of the coating layer may provide a decor sheet of 80 to 90%.

The present invention (a) coating a matte coating composition as described above on the base layer; (b) drying the coated matt paint composition in an oven; And (c) UV curing the dried matt paint composition.

In the step (a), the coating is a decoration sheet manufacturing method performed according to at least one method selected from bar coating (roll coating), roll coating (roll coating), curtain coating (curtain coating), gravure coating (gravure coating) Can be provided.

The drying in step (b) may provide a method for producing a decor sheet is performed for 1 to 2 minutes at a temperature of 50 to 80 ° C.

In the step (c), the curing may provide a method for producing a decor sheet is carried out in a 200 to 600mJ / cm 2 light amount.

The UV-curable matte coating composition according to the present invention comprises a bifunctional urethane acrylate oligomer and a polyfunctional acrylate monomer having a larger weight average molecular weight in a basic paint containing only a urethane acrylate oligomer prepared from a conventional linear polyester polyol. By including a certain part by weight to adjust the curing rate can be implemented a robust coating layer.

Therefore, the decor sheet according to the present invention may include a coating layer formed by curing the UV-curable matte coating composition, thereby realizing excellent elongation and at the same time improving pollution resistance.

1 is a schematic cross-sectional view of a decorative sheet according to an embodiment of the present invention.

While the present inventors have studied UV-curable matte coating compositions, bifunctional urethane acrylate oligomers and polyfunctional acryls having a larger weight average molecular weight in a basic paint containing only a bifunctional urethane acrylate oligomer in which a linear polyester polyol is based It was confirmed that the curing rate at the time of curing the paint can be adjusted by adjusting the weight part of the rate-based monomer, thereby completing the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.

Hereinafter, any configuration is formed on the "top (or bottom)" of the substrate or "top (or bottom)" of the substrate means that any configuration is formed in contact with the top (or bottom) of the substrate. However, it is not limited to not including other configurations between the substrate and any configuration formed on (or under) the substrate.

UV  Curable Matte  Paint composition

The present invention comprises a first difunctional urethane acrylate oligomer prepared from linear polyester polyols; A bifunctional urethane acrylate oligomer having a weight average molecular weight greater than that of the first bifunctional urethane acrylate oligomer; Polyfunctional acrylate monomers; And photoinitiators; It provides a UV curable matt coating composition comprising a.

The UV curable matte coating composition may be used for coating purposes such as sheets, steel sheets, films, etc. At this time, it should have an excellent elongation to improve the stain resistance of the coated body and prevent cracking of the coating layer. To this end, the UV-curable matt coating composition comprises a bifunctional urethane acrylate oligomer and a polyfunctional urethane acrylate oligomer having a larger weight average molecular weight than the bifunctional urethane acrylate oligomer prepared from a linear polyester polyol, after the coating coating While curing, a certain level of curing rate can be maintained while improving the stain resistance.

First, the UV-curable matte coating composition according to the present invention includes a first difunctional urethane acrylate oligomer, which is formed by polymerizing an isocyanate monomer and a polyol, and the isocyanate compound is an aliphatic isocyanate compound or an aromatic isocyanate compound. And at least one selected from combinations thereof, and the polyol may be a linear polyester polyol compound.

The first bifunctional urethane acrylate oligomer is prepared by reacting a linear polyester polyol with an isocyanate compound, and thus has excellent wear resistance, flexibility, and heat resistance than the urethane acrylate oligomer prepared by using a crystalline polyester polyol or a polyether polyol. There is an advantage.

The weight average molecular weight of the first difunctional urethane acrylate oligomer prepared from the linear polyester polyol may be about 10000 to about 20000. If the weight average molecular weight is less than the above range, there is a problem in elongation or there is a fear of uncured when exceeded.

The UV curable matte coating composition may contain about 30 parts by weight to about 40 parts by weight of the first bifunctional urethane acrylate oligomer prepared from a linear polyol polyester. If the first bifunctional urethane acrylate oligomer is included in less than about 30 parts by weight, abnormalities may occur in elongation. If the first bifunctional urethane acrylate oligomer is included in an amount of less than about 30 parts by weight, the physical properties may not be properly expressed due to uncuring.

The UV curable matt coating composition according to the present invention comprises a second difunctional urethane acrylate having a larger weight average molecular weight than the first difunctional urethane acrylate oligomer. When the polyfunctional monomer is added to the basic paint, the elongation falls below 150%, causing cracks in the coating layer. This problem is further caused by the addition of a second difunctional urethane acrylate oligomer having a large weight average molecular weight. It can be prevented by adding.

The weight average molecular weight of the second bifunctional urethane acrylate oligomer may be about 20000 to about 30000. When the weight average molecular weight is less than about 20000, cracks may occur during the elongation test, and when the weight average molecular weight exceeds about 30000, it may be difficult to express proper physical properties due to uncured hardness, deterioration of contamination resistance, and roll contamination during the process There is a concern.

The UV curable matte coating composition may contain about 5 to 15 parts by weight of the second bifunctional urethane acrylate oligomer based on 100 parts by weight of solids. When the second bifunctional urethane acrylate oligomer is included in less than about 5 parts by weight, the elongation may be degraded by additionally added multifunctional monomers, and when the second bifunctional urethane acrylate oligomer is included in an amount of more than about 15 parts by weight, curing may not be performed well. It may cause deterioration of fouling resistance.

In addition, the UV-curable matte coating composition according to the present invention includes a polyfunctional acrylate monomer, which increases the curing rate of the coating layer formed of the coating by adding monomers with high reactivity to make the coating film more hardened? It has the effect of improving pollution resistance by making the door less absorbed by contaminants.

 As the polyfunctional acrylate monomer, various acrylate monomers that can be photocurable may be used. For example, 1,2-ethylene glycol diacrylate, 1,12-dodetandiol acrylate, 1,4-butanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentylglycol adipate di ( Meta) acrylate, hydroxyl puivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate , Ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecane dimethanol ( Meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylpropane di ( Difunctional acrylates such as meta) acrylate, adamantane di (meth) acrylate, or 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional acrylates, such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional group acrylates, such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate Six functional group acrylates, such as a reactant, are mentioned, but it is not limited to this.

As the number of functional groups of the multifunctional acrylate monomer increases, the UV curing rate is excellent and the reactivity is good. Thus, a tetrafunctional or hexafunctional acrylate monomer is preferable, and pentaerythritol tri (meth) acrylate (PETIA), dipenta Erythritol hexa (meth) acrylate (DPHA) is more preferred.

The UV curable matte coating composition may be included in an amount of about 20 to about 40 parts by weight of the polyfunctional acrylate monomer based on 100 parts by weight of the solid content. When it contains less than about 20 parts by weight, the curing rate of the paint is less than 65%, so that it is easy to absorb contaminants, which may lower pollution resistance. There is a problem that cracks occur in the coating layer. The present invention can maintain a certain level of curing rate by including a multi-functional acrylate-based monomer in parts by weight of the above range to withstand thermoforming and improve stain resistance.

UV-curable matte coating composition according to the present invention comprises a photoinitiator, the photoinitiator benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosph Pinoxide, α, α-methoxy-α-hydroxyacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,2 -Dimethoxy-2-phenylacetophenone, 2, 2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) One or more selected from the group consisting of -1- [4- (4-morpholinyl) phenyl] -1-butanone and combinations thereof.

Since the UV curable matte coating composition includes a photoinitiator, the photocurable monomer may be cured at the time of light irradiation, thereby forming a cured product from the UV curable matte coating composition.

The photoinitiator may be included in an amount of about 0.1 to about 5 parts by weight based on 100 parts by weight of the UV curable matt coating composition. If it is less than the above range, even if irradiated with light does not proceed a sufficient curing reaction is left unreacted compound, there is a problem that the curing rate is difficult to control and the problem remains on the surface. By including the dispersant in the weight part of the above range, the photocuring efficiency of the UV curable matt coating composition can be maximized.

In addition, the UV-curable matte coating composition according to the present invention may further comprise an additive selected from the group consisting of dispersants, quencher, antifoaming agent and combinations thereof.

Specifically, the UV curable matte coating composition may include 5 to 20 parts by weight of an additive selected from the group consisting of a dispersant, a matting agent, an antifoaming agent, and a combination thereof, based on 100 parts by weight of the solid content. By using the dispersant, it is possible to prevent aggregation of the matting agent and to improve paint storage properties and compatibility with the paint. The matting effect may be used to provide a matting effect, thereby facilitating matting, preventing aggregation of the matting agent, improving paint storage, and preventing whitening. The antifoaming agent can be used to provide antifoaming properties, and the surface leveling property can be maintained while the strong antifoaming agent is used.

Deco Sheet

In addition, the present invention is a substrate layer; And a coating layer formed on the base layer, wherein the coating layer provides a decor sheet formed by UV curing the matte coating composition described above.

Figure 1 shows a simplified cross-sectional view of the decorative sheet according to the present invention.

As shown in FIG. 1, the decor sheet 100 according to the present invention comprises a base layer 10 and a coating layer 20 formed of the UV curable matt coating composition according to the present invention.

The base layer 10 is glass; Transparent film; Or a polymer sheet such as polyester, polycarbonate, polyolefin, polyvinyl resin, or the like. The first base layer is polyethylene terephthalate (PET), polyethylene naphthalate (PEN; polyethylene naphthalate), polycarbonate (PC), cyclic olefin polymer or copolymer (Cyclic olefin polymer or copolymer) or methylene It may be made of diphenyl diisocyanate (MDI; Methylene diphenyl diisocyanate), preferably translucent PVC (Polyvinyl chloride). The use of translucent PVC films is most preferred in terms of economics, processability, thermal stability and transparency. 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, so as to adjust 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 2 μm to about 6 μm, and specifically about 3 μm to about 4 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, when it exceeds about 6㎛, the curability for forming the coating layer 20 is lowered And, after curing, the coating layer 20 has a problem in that it is vulnerable to cracks, it can implement a coating layer 20 excellent in fouling resistance and hardness in the above range.

In addition, the curing rate of the coating layer 20 may be about 80 to about 90%. The curing rate can be adjusted by adding a polyfunctional acrylate monomer to the above UV curable matt coating composition, and in the present invention, the polyfunctional acrylate monomer, preferably pentaerythritol tri (meth) acrylate (PETIA) or dipentaerythritol hexa (meth) acrylate (DPHA) is added in an amount of about 5 to about 15 parts by weight to form a coating layer 20 that satisfies the curing rate, thereby providing excellent stain resistance and elongation characteristics. Can be implemented.

Deco Sheet  Manufacturing method

In another aspect, the present invention, (a) coating the matte coating composition according to the invention on the base layer; (b) drying the coated matt paint composition in an oven; And (c) UV curing the dried matt paint 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, and gravure coating. However, bar coating is preferably used. Bar-coating technique is to form a thin coating using a bar coater, there is an advantage that can form a coating layer of a certain thickness on the surface of the substrate with paints, coating agents.

Step (b) is a step of drying the coated matt paint composition in an oven. The drying may be performed for about 1 to about 2 minutes at a temperature of about 50 ° C to about 80 ° C. By satisfying the above temperature and time range, it is possible to produce a decor sheet having an excellent curing resistance and elongation properties by implementing an appropriate curing rate.

Step (c) is a step of UV curing the dried matt paint composition. In step (c), the dried matte paint composition may be UV cured at a light amount of about 200 to about 600 mJ / cm 2 . 200 mJ / cm 2 There is a problem that the curing rate is lowered when irradiated with UV with less light amount, there is a fear that the substrate layer is damaged by heat when irradiated with light amount of more than about 600 mJ / cm 2 .

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 thus the present invention is not limited thereto.

< Example  And Comparative example >

Example

Example  One

35 parts by weight of a first difunctional urethane acrylate oligomer having a weight average molecular weight of 15000, and a second difunctional urethane acrylate having a weight average molecular weight of 25000, based on 100 parts by weight of the UV-curable matte coating composition solid content 10 parts by weight of oligomer; 25 weight part of polyfunctional acrylate-type monomer PETIA, 4 weight part of photoinitiators, and 15 weight part of additives were mix | blended and the UV curable matte coating composition was prepared.

Then, forming a coating layer by coating with a thickness 4㎛ the matt UV curable coating composition to the BAR COATING techniques on top translucent PVC film, and dried 1-2 minutes in an oven at a temperature of 50 ~ 80 ° C. The dried specimen was UV irradiated with a light amount of 200-600 mJ / cm 2 to cure the coating layer, thereby preparing a decor sheet specimen.

Example  2

Decosheet was prepared in the same manner as in Example 1, except that 15 parts by weight of the second bifunctional urethane acrylate oligomer solid content was included.

Comparative example  One

The same method as in Example 1, except that the UV curable matt coating composition was prepared by combining 70 parts by weight of the first bifunctional urethane acrylate oligomer in which the linear polyester polyol was based, 4 parts by weight of the photoinitiator, and 15 parts by weight of the additive. Deco sheet was prepared.

Comparative example  2

Decosheet was prepared in the same manner as in Example 1 except for including 45 parts by weight of PETIA as the polyfunctional acrylate monomer.

Comparative example  3

Decosheet was prepared in the same manner as in Example 1, except that the bifunctional urethane acrylate oligomer having a weight average molecular weight of 25000 was 10 parts by weight instead of the second bifunctional urethane acrylate oligomer having a weight average molecular weight of 25000. .

Experimental Example

1) Measurement of Curing Rate

The cure rate was measured using a Vertex 70 FT-IR spectrometer (Bruker, Germany) and the results are shown in Table 2.

2) Pollution resistance evaluation

Evaluation criteria for fouling resistance (Table 1) The fouling resistance was evaluated according to DIN 68861-1: 1981-12, and the results are shown in Table 2.

evaluation Grade No change 0 Minimal changes in gloss or color One Light change in gloss or color, without surface layer change 2 Severe changes in gloss or color, without surface layer changes 3 Surface layer damage, gloss and severe changes in color 4 Peeling or breaking of surface layer 5

3) elongation measurement

Elongation was measured using UTM-Zwick / Roell Z100 and the results are shown in Table 2.

Curing rate (%) Result of contamination evaluation (washed with EtOH after 16 hours after coloring) Elongation Example 1 80-90 2 ~ 3 150% or more Example 2 80-85 3 ~ 4 150% or more Comparative Example 1 50-64 5 150% or more Comparative Example 2 92-98 1 ~ 2 Crack at 150% Comparative Example 3 92-98 1 ~ 2 Crack at 150%

Through the data of Examples 1 to 2 it can be confirmed that the decoration sheet according to the present invention than the Comparative Examples 1 to 3 has excellent pollution resistance according to the improvement of the curing rate. In particular, Example 1 shows the best result in a stain resistance evaluation result and an elongation. In Comparative Example 1, it was found that the contamination rate penetrated into the coating layer because the curing rate was not good, and the result of the contamination evaluation was not good.In Comparative Example 2, the curing rate was good, but cracks occurred in the coating layer due to excessive curing. It can be seen that it is not suitable as a coating layer of the sheet. Comparative Example 3 differs from the present invention in which a second difunctional urethane acrylate oligomer having a weight average molecular weight of 20000 to 30000 is added, and a bifunctional urethane acrylate oligomer having a small weight average molecular weight of 2000 is added. It confirmed that there was. In the case of the embodiment by maintaining an appropriate curing rate of 80 to 90 while achieving excellent pollution resistance and at the same time does not cause cracks in the coating layer is suitable for applying to the decor sheet.

Claims (15)

First difunctional urethane acrylate oligomers prepared from linear polyester polyols;
A second difunctional urethane acrylate oligomer having a larger weight average molecular weight than the first difunctional urethane acrylate oligomer;
Polyfunctional acrylate monomers; And
Photoinitiators; Including,
The weight average molecular weight of the second difunctional urethane acrylate oligomer is 20000 to 30000
UV curable matt paint composition.
The method of claim 1,
30 to 40 parts by weight of the first bifunctional urethane acrylate oligomer, 5 to 15 parts by weight of the second bifunctional urethane acrylate oligomer, and the multifunctional acrylate monomer based on 100 parts by weight of the UV-curable matte coating composition solid content 20 to 40 parts by weight
UV curable matt paint composition.
The method of claim 1,
The weight average molecular weight of the first bifunctional urethane acrylate oligomer is 10000 to 20000
UV curable matt paint composition.
delete The method of claim 1,
The polyfunctional acrylate monomer may include at least one selected from pentaerythritol tri (meth) acrylate (PETIA), dipentaerythritol hexa (meth) acrylate (DPHA), and combinations thereof.
UV curable matt paint composition.
The method of claim 1,
The photoinitiator is benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, α, α-methoxy-α-hydroxyaceto Phenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-dimeth Oxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] One or more selected from the group consisting of -1-butanone and combinations thereof
UV curable matt paint composition.
The method of claim 1,
Further comprising an additive selected from the group consisting of dispersants, quencher, antifoaming agent and combinations thereof
UV curable matt paint composition.
Base layer; And
It includes a coating layer formed on the base layer,
The coating layer is formed by UV-curing the matte coating composition according to any one of claims 1 to 3 and 5 to 7.
Deco sheet.
The method of claim 8,
The base layer is translucent PVC (polyvinyl chloride) polyethylene terephthalate (PET; polyethylene terephthalate), polyethylene naphthalate (PEN; polyethylene naphthalate), polycarbonate (PC; Polycarbonate), cyclic olefin polymer or copolymer (Cyclic olefin polymer or copolymer) or methylene diphenyl diisocyanate (MDI)
Deco sheet.
The method of claim 8,
The coating layer is a thickness of 2 to 6㎛
Deco sheet.
The method of claim 8,
Curing rate of the coating layer is 80 to 90%
Deco sheet.
(a) coating a matte coating composition according to any one of claims 1 to 3 and 5 to 7 on the base layer;
(b) drying the coated matt paint composition in an oven; And
(c) UV curing the dried matte paint composition;
Deco sheet manufacturing method.
The method of claim 12,
In the step (a), the coating is performed according to at least one method selected from bar coating, roll coating, curtain coating, and gravure coating.
Deco sheet manufacturing method.
The method of claim 12,
In the step (b) the drying is carried out for 1 to 2 minutes at a temperature of 50 to 80 ° C
Deco sheet manufacturing method.
The method of claim 12,
In the step (c) the curing is carried out with a light amount of 200 to 600mJ / cm 2
Deco sheet manufacturing method.

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