KR102468472B1 - Monochromatic ultraviolet hardening matte paint composition and matte sheet with excellent wiping property, and method for manufacturing matte sheet using the same composition - Google Patents

Abstract

A matte film manufactured by a method for manufacturing a matte sheet having excellent wiping properties using an ultraviolet monochromatic light curing type matte coating composition having excellent wiping properties according to the present invention is a solvent-free type without organic solvent and is eco-friendly, and uses monochromatic light instead of using a transfer method using a matte embossed film (PE, PP, PET), so that manufacturing is simple, is economical, and has effects of providing excellent physical properties of low gloss with a gloss of 5G or less, high wiping properties, fingerprint resistance, adhesion to substrates, surface hardness, scratch resistance, and stain resistance.

Description

Ultraviolet monochromatic light curing type matte paint composition with excellent wiping properties, matte decorative sheet using the same and method for manufacturing the same

The present invention relates to an ultraviolet monochromatic light curing type matte coating composition with excellent wiping properties and a method for manufacturing a matte decor sheet using the same, and more particularly, applied to a product having a low gloss of 5G or less, and a gloss of 60 ° or less, and the surface of the coating layer A coating film with excellent wipeability is formed on the surface, and surface hardening is performed first using the difference between surface hardening and fast hardening, and then fast hardening occurs in the subsequent process. A monochromatic light-curable matte coating composition with excellent wiping properties suitable for ultraviolet monochromatic light, which can realize ultra-matte by forming a curved shape through local surface hardening by directly irradiating ultraviolet monochromatic light, and a matte decor sheet using the same It's about manufacturing methods.

In addition, the present invention provides a non-glossy decorative sheet that is eco-friendly and has high functionality by realizing wipeability on the surface by not using a transfer method by implementing ultra-matte light using emission monochromatic light having a very narrow wavelength range, and also wiping the coated surface. UV monochromatic light-curable matte coating composition with excellent stain resistance, substrate adhesion, fingerprint resistance, hardness, stain resistance, chemical resistance, simple and economical manufacturing process, and excellent eco-friendly wiping property and method for manufacturing a matte decor sheet using the same will be.

In general, surface treatment is performed on the surface of an electronic product exterior case, architectural interior, furniture, etc. to enhance aesthetics, and the surface treatment of an article is performed in various ways depending on the use and design of the product.

In particular, matte sheets diffusely reflect external light to prevent eye fatigue and disclosure of packaged contents that occur when using glossy sheets, and can add elegance to products. Or label paper, etc. It is a trend that the use is gradually increasing.

However, UV-curable matt sheets, which have been used in the past, show a marked difference in gloss (fume phenomenon) from the surroundings as the matting agent on the surface is partially desorbed due to external impact in products with a gloss level of 5G or less, resulting in scratches. Disadvantages of appearing as if and poor wiping and stain resistance occur (Korean Patent Nos. 10-1231508, 10-1534621, and 10-2100028).

In order to solve the above problems, for example, Korean Patent No. 10-1567924 (matte paint composition and coating method using the same), Patent No. 10-2357689 (high gloss paint composition for eco-friendly sheets and sheet and sheet manufacturing method using the same) As such, although the light scratch property (transmission phenomenon) was improved by implementing a matte by using a transfer method using a PET film treated with matte embossing, it is difficult to implement a matte low gloss with fingerprint resistance and manufacturing cost by using a transfer film There is an environmental problem that the economic feasibility is reduced due to an increase in the transfer film and the transfer film must be discarded after use.

Therefore, in order to solve the above problems, the present inventors filed Korean Patent No. 10-2357693 (ultraviolet monochromatic light curing type matte coating composition and method for manufacturing matte sheet and matte sheet using the same), Patent No. 10-2357696 (ultraviolet curing type suitable for excimer emission light) It is a non-solvent type that does not contain organic solvents in the matte paint composition and the matte decor sheet using the same and its manufacturing method) by directly irradiating ultraviolet monochromatic light with a short wavelength on the coated surface without using a transfer method. A new method that is suitable for matte implementation and has excellent fingerprint resistance in terms of functionality has been introduced, but these matte sheets have poor wipeability and stains remain when contaminated with an oil-based marker or pen.

Therefore, in order to solve the above problem, a technique for maintaining a very low surface tension on the coating surface is required. There is a need for a UV monochromatic light-curable coating composition with excellent wipeability as a new coating composition with excellent wipeability, stain resistance and fingerprint resistance on the coated surface and a method for producing a matte sheet with excellent wipeability using the same.

The present invention was created by the above needs, and the object of the present invention is to provide a solvent-free, organic solvent-free, environmentally friendly coating composition with a low surface tension coating surface, and a transfer method using a PET film treated with matte embossing. It is an object of the present invention to provide an ultraviolet monochromatic light-curable coating composition having excellent wiping properties that is economical to manufacture because it is not used, and which can be applied to products having low gloss with a gloss of 5G or less.

Another object of the present invention is that it can be used for coating on sheets, films, etc., and has high residual solvent, stain resistance, surface hardness, substrate adhesion of the coating material, and excellent elongation so that microcracks do not occur during postprocessing. It is to provide an ultraviolet monochromatic light-curable coating composition with excellent wiping property, which does not generate gloss deviation after contact with nails or other objects during product processing or when used by consumers in daily life, does not leave fingerprints, and has excellent wiping properties.

Another object of the present invention is to provide a manufacturing method for realizing a matte surface with excellent fingerprint resistance through local surface curing using monochromatic light having a very narrow ultraviolet wavelength range emitted from a coated surface.

In order to solve the above problems, the present invention is a urethane-acryl acrylate copolymer represented by Formula 1, a metal oxide represented by Formula 2, and surface-treated with a fluorine or silicone compound, ethylene oxide oxide) group containing a multifunctional acrylate, an acrylate monomer, a photoinitiator and a leveling agent,

The urethane-acrylic acrylate copolymer is 5 to 40 parts by weight,

0.1 to 10 parts by weight of the metal oxide surface-treated with the fluorine or silicon compound;

5 to 50 parts by weight of the multifunctional acrylate containing the ethylene oxide group,

The acrylate monomer is 5 to 30 parts by weight,

1 to 5 parts by weight of the photoinitiator and

The leveling agent provides a coating composition comprising 0.1 to 1 part by weight.

[Formula 1]

here,

x, y, z are each less than or equal to 3, and

An integer such that x+y+z = 3

A =

In A, n = an integer less than or equal to 10

B =

in B,

R _1a, R _1b, R _1c = linear, branched or cyclic alkyl each having 1 to 10 carbon atoms

R ₂ = H or CH ₃

C =

in C,

R _1d = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms

_R3 = H or E

D =

in D,

R _1e = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms

R ₂ = H or CH ₃

E =

in E,

n = an integer less than or equal to 10

R ₄ = saturated or unsaturated hydrocarbon containing up to 30 carbon atoms, with or without oxygen or nitrogen

[Formula 2]

M _x O _y

In Formula 2,

M = Si, Ti, Al or Zr

x or y= 1, 2 or 3

Here, the fluorine or silicon compound may be represented by Formula 3-a or Formula 3-b.

[Formula 3-a]

(R ₅ ) _Q -Si-G _4-Q

R ₅ = up to 20 carbon atoms, with or without at least one fluorine (F), intramolecularly, hydrogen (H), oxygen (O), sulfur (S), chlorine (Cl), nitrogen (N), or silicon Alkyl having a saturated or unsaturated structure with or without (Si).

Q = 1 or 2

G = Cl, OH, OCH ₃ , OCH ₂ CH ₃ or OCH ₂ CH ₂ CH ₃

[Formula 3-b]

R ₆ -OH

R ₆ = 20 or less carbon atoms, contains at least one fluorine (F), contains or does not contain hydrogen (H), oxygen (O) or nitrogen (N) in the molecule, has a straight or branched chain structure, is saturated or Alkyl with an unsaturated structure.

The present application also includes a substrate layer and a coating layer formed on the substrate layer, and the coating layer provides a sheet formed by UV curing of the coating composition according to the present application.

The present application also provides (a) a coating step of forming a coating layer by applying the coating composition according to the present application to the surface of a substrate

(b) a surface curing step of irradiating ultraviolet monochromatic light to the coating layer formed in step (a), and

(c) providing a sheet manufacturing method comprising a complete curing step of irradiating the coating layer with ultraviolet rays at a wavelength greater than the wavelength of the ultraviolet monochromatic light irradiated in step (b).

The above-described means for solving the problems is only illustrative and should not be construed as limiting the present invention. In addition to the exemplary embodiments described above, there may be additional embodiments described in the drawings and detailed description.

The matte film produced by the method for producing a matte sheet having excellent wipeability using the ultraviolet monochromatic light curing matte coating composition having excellent wipeability according to the present invention having the above characteristic configuration is eco-friendly as a non-solvent type without organic solvent, and is matte embossed. It is simple and economical to manufacture by using monochromatic light without using a transfer method using a pre-treated film (PE, PP, PET), low gloss with a gloss of 5G or less, high wipeability, anti-fingerprint property, substrate adhesion , surface hardness, scratch resistance, and stain resistance have the effect of providing very excellent physical properties.

1 is a view showing a cross-section of a matte sheet structure having excellent wipeability manufactured according to an embodiment of the present invention.
Figure 2 is a SEM (Scanning Electronic Microscope) photograph taken at 150 times the surface of the matte sheet with excellent wipeability prepared according to Example 3 of the present invention.
Figure 3 is a SEM picture taken 150 times the surface of the matte sheet with excellent wipeability prepared according to Example 4 of the present invention.
Figure 4 is a SEM picture taken 150 times the surface of the matte sheet prepared according to Comparative Example 1 of the present invention.
Figure 5 is a SEM picture taken 150 times the surface of the matte sheet prepared according to Comparative Example 2 of the present invention.
6 is a 3D micrograph of the surface of the matte sheet prepared according to Example 1 of the present invention at 1,000 times magnification.
7 is a 3D micrograph of the surface of the matte sheet prepared according to Comparative Example 1 of the present invention at 1,000 times magnification.

Hereinafter, embodiments of the present application will be described in detail so that those skilled in the art can easily practice with reference to the accompanying drawings. However, the present disclosure may be implemented in many different forms and is not limited to the embodiments described herein. And in order to clearly describe the present application in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout the present specification, when a member is said to be located “on” another member, this includes not only a case where a member is in contact with another member, but also a case where another member exists between the two members.

Throughout the present specification, when a part "includes" a certain component, it means that it may further include other components without excluding other components unless otherwise stated.

As used throughout this specification, the terms "about," "substantially," and the like are used at or approximating the value when manufacturing and material tolerances inherent in the stated meaning are given, and do not convey the understanding of this application. Accurate or absolute figures are used to help prevent exploitation by unscrupulous infringers of the disclosed disclosure. The term "step of (doing)" or "step of" as used throughout the present specification does not mean "step for".

Throughout this specification, the term "combination(s) of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, It means including one or more selected from the group consisting of the above components.

Throughout this specification, reference to "A and/or B" means "A or B, or A and B".

Hereinafter, embodiments and embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. However, the disclosure may not be limited to these embodiments and examples and drawings.

Throughout this specification, the description of '~ (meth)acryl ~' means '~ methacryl ~' or '~ acryl ~'. For example, '(meth)acrylate' means 'methacrylate or acrylate'. The description of ' ~(meth)acryl ~ ' in English means ' ~ methacryl ~ ' or ' ~ acryl ~ '. For example, '(meth)acrylate' means 'methacrylate or acrylate'.

Throughout this specification, 'sheet' can be used for various decoration purposes, and specifically, it can be used in various interior or coating sectors such as furniture, exterior of home appliances, decoration of entrance doors, exterior cases of electronic products, architectural interiors, and building materials. can Representatively, it may be a 'decosheet' or 'matte sheet', but is not limited thereto.

Throughout this specification, 'matte sheet' may be defined as a film in the form of a decorative sheet treated with a matte by removing the gloss of the surface. It is defined as a case where the surface gloss (based on gloss 60°) is less than 30G.

In the present invention, by providing an ultraviolet monochromatic light curing type matte coating composition with excellent wipeability for surface protection from the matte sheet to lower the gloss to 10G or less, fingerprints caused by oily magic or handprints are not left, so the product is further advanced, In addition, it is possible to form an eco-friendly matte sheet having physical properties capable of membrane molding.

In the present invention, after coating the surface of the substrate using an ultraviolet monochromatic light curing type matte coating composition with excellent wipeability, surface curing is performed by irradiating short-wavelength monochromatic light in the ultraviolet region using an excimer during the curing process, which forms curves on the surface This results in a decrease in gloss.

The monochromatic light referred to throughout this specification refers to monochromatic light having a short wavelength range emitted using an excimer, and 'excimer' means that atoms are not bonded in the ground state (ground state) and in an excited state (excited state). refers to the chemical species to which it binds. Therefore, it is a gaseous compound that exists only in an excited state.

There are excimers in which the same element is combined in a dimer and exciplex in which different elements are combined in a heterodimer, but they are usually collectively referred to as excimers without distinction.

The characteristics of excimer are that it overcomes the problem of environmental pollution caused by the disposal of widely used mercury lamps and can efficiently convert ultraviolet radiation because strong bonding is not made in the ground state.

Advantages include high average specific power of ultraviolet radiation, high power spectral density, high energy of emitted photons, narrow spectrum, selection of ultraviolet radiation for a specific purpose, and low heating of the emitting surface.

Excimer molecules do not combine in the ground state with low energy, but when irradiated with a high voltage discharge or electron beam, atoms in the ground state combine to exist in an unstable excited state with a very short lifespan of about nanoseconds, emitting light energy of a specific wavelength range. will return to the ground state. Therefore, excimers have high photon energies of 3.5 to 11.5 eV. The half maxium of the emission band depends on excimer molecules and excitation conditions and is ultraviolet monochromatic light within 2 to 15 nm.

[Emission Mechanism of Excimer Molecules]

R _g2 ^* → R _g + R _g + hv (UV photon)

R _g X ^* → Rg + X + hv (UV photon)

R _g2 ^* : excimer molecule

R _g X ^* : Exciplex molecule

X: halogen atom

An excimer lamp is a source of ultraviolet monochromatic light produced by the spontaneous emission of excimer molecules.

Throughout this specification, gravure coating means supplying a coating liquid to a gravure roller, and rotating the gravure roller in contact with the material to be coated, but rotating in the same direction as the moving direction of the material to be coated, so that the coating liquid on the gravure roller It is a method to be applied to the material to be coated. Contrary to this, the method in which the coating liquid is buried while the gravure roller and the material to be coated rotate in the opposite direction is called reverse gravure coating.

The gravure coating method is preferred because it has the advantage of less loss of coating liquid and uniform coating compared to other coating methods.

The gravure coating method is divided into a general gravure coating method (generally using a gravure roller with a diameter of 100 mm or more) and a micro gravure coating method (using a gravure roller with a diameter of 50 mm or less). Doctor Chamber Type Gravure The method corresponds to the general gravure coating method.

Throughout this specification, 'wettability' is the ability of a liquid to maintain contact with a solid surface, and is caused by an intermolecular interaction that occurs when a liquid and a solid meet. The smaller the contact angle between the liquid and the solid, the better the wettability.

Throughout this specification, 'wiping property' refers to stain resistance and refers to a property that is easy to remove when contamination occurs.

Hereinafter, embodiments, examples and experimental examples of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention may not be limited to these embodiments and examples and drawings.

Embodiment 1. Ultraviolet monochromatic light curable matte coating composition with excellent wipeability

UV-curable matte coating composition with excellent wipeability suitable for monochromatic light according to the present invention is a urethane-acryl acrylate copolymer represented by Formula 1, represented by Formula 2, and surface treated with fluorine or silicone compound metal oxide, a multifunctional acrylate having an ethylene oxide group, an acrylate monomer, a photo initiator, and a leveling agent.

[Formula 1]

here,

x, y, z are each less than or equal to 3, and

An integer such that x+y+z = 3

A =

In A, n = an integer less than or equal to 10

B =

in B,

R _1a, R _1b, R _1c = linear, branched or cyclic alkyl each having 1 to 10 carbon atoms

R ₂ = H or CH ₃

C =

in C,

R _1d = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms

_R3 = H or E

D =

in D,

R _1e = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms

R ₂ = H or CH ₃

E =

in E,

n = an integer less than or equal to 10

R ₄ = saturated or unsaturated hydrocarbon containing up to 30 carbon atoms, with or without oxygen or nitrogen

[Formula 2]

M _x O _y

In Formula 2,

M = Si, Ti, Al or Zr

x or y= 1, 2 or 3

In Formula 1 above, each of the components A, B, C, and D should be interpreted as independent. For example, both A and E contain an integer n, but n in A and n in E may be different values. Both B and D include R ₂ , but R ₂ of B and R ₂ of D may be different substituents.

The urethane-acrylic acrylate copolymer represented by Formula 1 may be included in an amount of 5 to 40 parts by weight based on the total coating composition. The urethane-acrylic acrylate copolymer can increase the surface photocuring speed for the emitted short-wavelength ultraviolet monochromatic light, and can improve the hardness of the coated film, adhesion to substrates, weather resistance, chemical resistance, and high gloss durability. If the urethane-acrylic acrylate copolymer is less than 5 parts by weight, if the adhesion to the substrate is reduced, the hardness of the coating film is lowered and the photocuring speed for monochromatic light is slowed, making it difficult to achieve the desired matte effect, and if it is more than 40 parts by weight, the viscosity of the paint composition It is high, so it is difficult to coat and has poor weather resistance.

The urethane-acrylic acrylate copolymer represented by Chemical Formula 1 can increase the surface photocuring rate for emitted short-wavelength ultraviolet monochromatic light, and can increase the hardness of a coating film and adhesion to a substrate.

Specifically, the synthetic example of a urethane-acrylic acrylate copolymer is an acryl-alcohol compound corresponding to mark B (trade name: Dow Chemical's Tone M series and Daicel's Placcel FM series) and a diol corresponding to mark C (1, 6-Hexanediol, 1,3-pentanediol, cyclohexanedimethanol, propylene glycol, etc.) under a nitrogen stream, with an acrylic monomer having a hydroxyl group corresponding to the notation D (hydroxyethyl acrylate, 2-hydroxypropyl acryl rate, etc.) and slowly raise the temperature to 50 ° C. Here, the polymerization inhibitor methoxyhydroquinone, tin catalyst [1,1'-(dimethylstannylene) diacetate), dibutyltindilaurate, etc.] are added and the temperature is slowly raised, and triisocyanate corresponding to mark A ([2,4,6- trioxotriazine-1,3,5(2H,4H,6H)-triyl] tris(hexamethylene) isocyanate)] and acrylic monomers (pentaerythritol triacrylate, dipentaerythritol pentaacrylate) The reaction can be terminated by confirming the disappearance of the isocyanate. Formula 1 can be selectively synthesized by controlling the diol and triisocyanate contents.

The urethane-acrylic acrylate copolymer may be trifunctional or bifunctional urethane acrylate, and may have a weight average molecular weight of 1,000 to 100,000. If the weight average molecular weight is less than 1,000, sufficient elongation cannot be implemented, and if it is more than 100,000, the viscosity of the resin is very high, and solubility and coating properties may be poor.

Represented by Chemical Formula 2, the metal oxide surface treated with fluorine or silicon compound is used to maintain the wiping property of the coating layer coated on the substrate, stain resistance and uniform dispersibility in the resin, and by using the high specific gravity of the metal oxide A soft texture can be realized by controlling the surface curvature during surface curing using monochromatic light. In addition, the metal oxide can increase the reflectance of light transmitted through the coating surface, and the hardness of the coating film can be increased by using the high hardness, which is a unique physical property of the metal oxide.

Here, the fluorine or silicon compound may be represented by Formula 3-a or Formula 3-b.

[Formula 3-a]

(R ₅ ) _Q -Si-G _4-Q

R ₅ = up to 20 carbon atoms, with or without at least one fluorine (F), intramolecularly, hydrogen (H), oxygen (O), sulfur (S), chlorine (Cl), nitrogen (N), or silicon Alkyl having a saturated or unsaturated structure with or without (Si).

Q = 1 or 2

G = Cl, OH, OCH ₃ , OCH ₂ CH ₃ or OCH ₂ CH ₂ CH ₃

[Formula 3-b]

R ₆ -OH

R ₆ = 20 or less carbon atoms, contains at least one fluorine (F), contains or does not contain hydrogen (H), oxygen (O) or nitrogen (N) in the molecule, has a straight or branched chain structure, is saturated or Alkyl with an unsaturated structure.

The metal oxide may be at least one selected from among silica (SiO ₂ ), titania (TiO ₂ ), alumina (Al ₂ O ₃ ), and zirconia (ZrO ₂ ), and the surface of the metal oxide is reacted under a catalyst to form the metal oxide with fluorine. Alternatively, surface treatment with a silicon compound facilitates surface wettability using low interfacial tension to induce metal oxides to migrate to the surface, and on the other hand, increase compatibility with organic materials and form a network through a photocuring reaction. can

Comparing Examples 3 and 4 (Figs. 2, 3, and 6) with Comparative Example 1 (Figs. 4 and 7), when a metal oxide is present, a surface hardening reaction by monochromatic light is performed by the metal oxide. Curing shrinkage occurs and the roughness of the coating film shows a constant shape, but when it is composed of only organic materials, a radial curing shape is formed and the coating film shows a very irregular rough shape. It can be seen that uniform shrinkage occurs during surface curing by surface treatment of the metal oxide to cause a photocuring reaction between the organic material and the metal oxide to form an organic-inorganic hybrid.

The fluorine or silicon compound used may be included in an amount of 0.1 to 10 parts by weight compared to the metal oxide. When the fluorine or silicon compound used is less than 0.1 parts by weight compared to the metal oxide, it is difficult to implement dispersibility as well as wipeability and stain resistance, and when it is more than 10 parts by weight, economical efficiency is poor.

The average particle diameter of the metal oxide particles used is preferably 0.5 to 10 μm, but is not limited thereto. If it is less than 0.1 parts by weight compared to the paint composition, it may be difficult to implement wipeability and low gloss, and if it is more than 10 parts by weight, coating uniformity may decrease and viscosity may increase.

Fluorine compounds include hexafluoro-2-propanol, perfluoro 2-methylallyl alcohol, perfluorotriethyl carbitol, nonafluoro- nonafluoro-tert-butyl alcohol, perfluorooctyl alcohol, perfluorohexyl alcohol, perfluorobutyl alcohol, perfluorooctyl ethanol ethanol), perfluorohexyl ethanol, perfluorobutyl ethanol, fluorobenzyl alcohol, hexafluorophenylpropanol, trifluorobenzyl alcohol , chlorofluorobenzyl alcohol, fluorotelomer alcohol, and octafluoropentyl alcohol.

Silicone compounds include vinyltrichlorosilane, dimethyldichlorosilane, dimethylchlorosilane, 3,3,3-trifluoropropyltrichlorosilane, 3 ,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, 3,3,4,4,5,5,6,6,6-nonafluorohexyl methyldichlorosilane, allyltrichlorosilane, methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldichlorosilane, dimethylvinylchlorosilane, hydroxymethyl Trimethylsilane, mercaptomethyltrimethylsilane, allyldimethylchlorosilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethoxytrimethylsilane, dia diallyldichlorosilane, 3-hydroxy-1-propynyltrimethylsilane, dimethylethoxyethynylsilane, dimethoxymethyl-3,3,3-trifluoro Ropropylsilane (dimethoxymethyl-3,3,3-trifluoropropylsilane), ethoxydimethylvinylsilane, diethoxydimethylsilane (diethoxydimet hylsilane), diethoxymethylvinylsilane, 3-methacryloxypropyldichloromethylsilane, 3-trifluoroacetoxypropyltrimethoxysilane, diekoxyvinyl Dimethoxyvinylsilane, triethoxyvinylsilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, allyltriethoxysilane ), 3-glycidoxypropyltrimethoxysilane (3-glycidoxypropyltrimethoxysilane), 3-glycidoxypropyltriethoxysilane (3-glycidoxypropyltriethoxysilane), 3-glycidoxypropylmethyldiethoxysilane (3-glycidoxypropylmethyldiethoxysilane), 3-arylaminopropyltrimethoxysilane, 1,1,3,3-tetramethyl-1,3-dichlorodisiloxane , 1,2-bis(dimethylchlorosilyl)ethane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyl disiloxane (1,3-Diethoxytetramethyldisiloxane), 1,4-bis (dimethylchlorosilyl) benzene (1,4-Bis (dimethylchlorosilyl) benzene), 1,4-bis (hydroxydimethylsilyl) benzene (1,4-Bis ( hydroxydimethylsilyl)benzene), 1,3-bis(3-mercaptopropyl)tetramethyldisiloxane (1,3-Bis(3-mercaptopropyl)tetramethyldisiloxane), 1,3-bis(3-hydroxypropyl)-1, 1,3,3-tetramethyldisiloxane (1,3-Bis (3-hydroxypropyl) -1,1,3,3-tetramethyldisiloxane), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1 ,3-Bis(3-aminopropyl)tetramethyldisiloxane), 1,3-dichlorotetraisopropyldisiloxane, 1,4-bis(3-aminopropyldimethylsilyl)benzene(1,4 -Bis(3-aminopropyldimethylsilyl)benzene), 1,1,3,3,5,5,-hexamethyl-1,5-dichlorotrisiloxane (1,1,3,3,5,5,-hexamethyl -1,5-dichlorotrisiloxane), heptymethyl-3-(3-hydroxypropyl)trisiloxane (Heptamethyl-3-(3-hydroxypropyl)trisiloxane), 1,7-dichloro-1,1,3,3,5 It may contain one or more components selected from the group consisting of 5,7,7-octamethyltetrasiloxane (1,7-dichloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane) have.

In detail, an example of manufacturing a metal oxide surface-treated with fluorine or a silicon compound is described, silicon or a fluorine compound [eg, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ -Si-Cl ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ -OH, CH ₂ =CH-C(=O)-O-(CH ₂ ) ₃ -Si-(OCH ₃ ) ₃ etc.] and metal oxides (SiO ₂ or TiO ₂ , etc.) into an acrylic monomer and dispersed at high speed with a small amount of dispersant and catalyst (such as acrylic acid or tertiary amine containing a very small amount of water) to form a chemical bond between the fluorine compound and the hydroxy group on the surface of the metal oxide through a substitution reaction. It is possible to obtain a metal oxide to which a fluorine compound is bound by derivation. It can be seen that the resin dispersibility is much improved when dispersed together with a polyfunctional acrylate having an ethylene oxide group in order to increase the uniformity of dispersion.

Polyfunctional acrylate containing an ethylene oxide group can improve the leveling and coating properties of a coating film. The ethylene oxide group not only improves the wettability of the surface of the substrate, but also improves the compatibility with the metal oxide to improve the feel of the coated surface. Considering these performance and / or effects, it may be included in 5 to 50 parts by weight compared to the total coating composition. If it is less than 5 parts by weight compared to the total composition, the wettability effect of the substrate is small and the slip feeling of the coating film may be reduced. In the case of more than 50 parts by weight, a problem of lowering the surface hardness of the coating film may occur.

In consideration of the above problems, multifunctional acrylates having an ethylene oxide group include phenol (ethyleneoxy) ₂ acrylate, phenol _{(ethyleneoxy) 4 acrylate} , _and nonyl Phenol (ethyleneoxy) _{2 - 8} acrylate (nonylphenol (ethyleneoxy) _{2 - 8} acrylate), phenol (meth)acrylate, ethylene oxide (CH ₂ CH ₂ O) 2 to 10 1,6-hexanediol diacrylate with added mole, bisphenol A di(meth)acrylate with 3 to 30 mole added ethylene oxide, ethylene oxide 3 to trimethylolpropane (meth)acrylate with 15 moles added, trimethylolpropane tri(meth)acrylate with 3 moles of propylene oxide added, and ethylene At least one component selected from the group consisting of pentaerythritol tetraacrylate to which oxide is added may be included.

When the total composition of polyfunctional acrylate having an ethylene oxide group is less than 5 parts by weight, wettability of the substrate is poor and slimness of the coating film is poor. A problem of lowering may occur.

The acrylate monomer may be included in an amount of 5 to 30 parts by weight relative to the total coating composition, and may lower the viscosity of the coating composition, increase the dispersibility of the metal oxide, and increase the degree of UV curing of the coating film. The acrylate monomer may include a monofunctional acrylate compound and a bifunctional or multifunctional acrylate monomer. If the acrylate monomer composition ratio is less than 5 parts by weight, the viscosity of the entire paint composition is high, and workability may be deteriorated.

Acrylate monomer is phenol (ethyleneoxy) ₂ acrylate (phenol (ethyleneoxy) ₂ acrylate), phenol (ethyleneoxy) ₄ acrylate (phenol (ethyleneoxy) ₄ acrylate), nonylphenol (ethyleneoxy) _{2 - 8} acrylate ( nonylphenol (ethyleneoxy) _{2 - 8} acrylate), phenol (meth)acrylate, 1,6-hexanediol diacrylate, butandiol diacrylate , ethylene glycol diacrylate, isobonylacrylate, butylcyclohexyl acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate [( 5-ethyl-1,3-dioxan-5-yl)methyl acrylate], phenyl epoxy acrylate, trimethylolpropane (meth)acrylate, glycerin triacrylate), pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanate triacrylate, ditrimethylolpropane tetraacrylate (meth)acrylate (ditrimethylolpropane tetra(meth)acrylate), pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate acrylate) and dipentaerythritol hexa(meth)acrylate te) may include one or more components selected from the group consisting of 6-functional urethane acrylate, but is not limited thereto.

In the UV monochromatic light-curable matte coating composition having excellent wipeability suitable for excimer emission light according to the present invention, a photoinitiator may be used in an amount of 1 to 5 parts by weight based on the total composition of the coating composition to cure the coating film after coating. If the initiator content is less than 1 part by weight compared to the paint composition, problems may occur in curing the coating film, and if it exceeds 5 parts by weight, weather resistance may be deteriorated.

The photoinitiator is preferably a short-wavelength photoinitiator of 200 nm or less in the ultraviolet absorption region suitable for the ultraviolet monochromatic light emitted by the excimer, and long-wavelength initiators having an absorption region in the near visible ray region (350 to 400 nm) are mixed and used for complete curing. It is preferred, but not limited thereto.

Photoinitiators can be classified into chemical groups within their molecular structure. Available chemical structures include ketal series, acetophenone series, sulfide series, benzoate series, benzophenone series, spin series, benzoyl formate series. formate) series can be used.

Specific examples of photoinitiators used include 1-hydroxy-cyclohexyl-phenolketone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane- 1-one (2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one), benzyldimethylketone, 1-(4-dodecylphenyl)-2-hydroxy-2 -Methylpropan-1-one (1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one), 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy -2-methyl-1-phenylpropane-1-one), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one (1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropane-1-one), benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacet 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-propane-1-one, 4,4 '-diethylaminobenzophenone (4,4'-diethylaminobenzophenone), dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-methylthioxane 2-methylthioxanthone, 2-ethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyloxanthone It may be used, and it is preferable to use one of these alone or in combination of two or more, but is not limited thereto.

Photoinitiators are available from Ciba (Irgacure 184, 500, 2959, 754, 651, 369, 907, 1300, 819, 819DW, 2022, 2100,784, 250, Darocur 1173, MBF, TPO, 4265) or double bond chemical It is possible to mix and use one or more of the company's products (Doublecure BDK, TPO, TPO-L, 73W, 107, 173, 184, 200, 284, 560, 998, 1130, 1172, 1176, 1190, 1256), etc., but is not limited thereto. don't

The monochromatic UV-curable matte paint composition with excellent wiping property keeps the coated surface smooth during gravure or microgravure coating and increases substrate wettability and leveling property to suppress cratering of the coated surface A leveling agent may be used in the range of 0.1 to 1 part by weight.

A silicone-based leveling agent shows excellent releasability, and an acrylic-based leveling agent may be used. Leveling agents include BYK's BYK-300 series and BYK-3500 series, Teggo's RAD-2000 series, BYK's 100 series and Teggo's Dispers 600 to 700 series as dispersing agents, and BYK's Tinuvin series as antioxidants. have.

The monochromatic UV curable matte coating composition having excellent wiping properties may further include 0.1 to 1 part by weight of an adhesion promoter, 0.1 to 1 part by weight of an antifoaming agent, 0.1 to 1 part by weight of an ultraviolet stabilizer, and 0.1 to 1 part by weight of an antioxidant.

The adhesion enhancer is phosphate methacrylate or phosphor ester acrylate, which can increase the bonding strength between the substrate surface and the coating layer, the antifoaming agent can suppress bubbles in the paint composition, and the antioxidant is It is possible to improve the weather resistance of the coated decorative sheet, and the stabilizer can increase the stability of the metal oxide.

Embodiment 2. Sheet

The decorative sheet according to the present invention includes a base layer and a coating layer formed on the base layer, and the coating layer may be formed by UV curing the paint composition according to the present invention.

1 schematically shows a cross section of a decorative sheet according to the present invention.

As shown in Figure 1, the decor sheet 100 according to the present invention may be composed of a base layer 10, a back adhesive layer 30, and a coating layer 20 formed of a coating composition according to the present invention.

The base layer 10 includes crystalline and non-crystalline polyethylene terephthalate (PET, G-PET, GAG-PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) ) and at least one of polystyrene (PS), polyvinylchlorite (PVC), acrylonitrile-styrene-acrylic (Acrylonitrile, ASA), and paper.

Embodiment 3. Sheet manufacturing method

The method for producing a matte decorative sheet having excellent wipeability according to the present invention

(a) a coating step of forming a coating layer by applying the coating composition according to the present invention to the surface of a substrate;

(b) a surface curing step of irradiating ultraviolet monochromatic light to the coating layer formed in step (a) under high purity nitrogen; and

(c) a complete curing step of irradiating the coating layer with ultraviolet light at a wavelength greater than the wavelength of the monochromatic ultraviolet light irradiated in step (b);

Step (a) is a step of coating the matte paint composition according to the present invention on top of the substrate layer. Specific physical properties of the matte paint composition are shown in Table 1 of Experimental Example.

In step (a), the coating layer is bar coating, roll coating, curtain coating, gravure coating, reverse gravure coating, and microgravure coating coating) may be performed according to at least one method, but is not limited thereto, and preferably, gravure and micro gravure coating methods may be used. The micro gravure coating method is suitable when the coating appearance or precise thickness control is required, and the gravure coating method is easy to lower the production cost by increasing the production speed.

The coating layer of the coating step is preferably formed to a thickness of 5 to 20 μm, but is not limited thereto.

Step (b) is a surface curing step of irradiating the coated matte paint composition with ultraviolet monochromatic light using an excimer.

Excimer lamp (radiation wavelength, photon energy) NeF ^* (108 nm, 11.48 eV), Ar ₂ ^* (126 nm, 9.84 eV), Kr ₂ ^* (146 nm, 8.49 eV), F ₂ ^* (158 nm, 7.85 eV), ArBr ^* (165 nm, 7.52 eV), Xe ₂ ^* (172 nm, 7.21 eV), ArCl ^* (175 nm, 7.08 eV), KrI ^* (190 nm, 6.49 eV), ArF ^* (193 nm, 6.42 eV), KrBr ^* (207 nm, 5.99eV), KrCl ^* (222nm, 5.58eV), KrF ^* (248nm, 5.01eV), XeI ^* (253nm, 4.91eV), Cl2 ^* ( _259nm , 4.79eV), XeBr ^* (282nm, 4.41eV), Br ₂ ^* (289nm, 4.29eV) of any one ultraviolet monochromatic light may be used, but is not limited thereto.

In step (b), the shorter the wavelength of monochromatic ultraviolet light by the excimer, that is, the higher the energy, the greater the degree of hardening of the coated surface and the greater the surface roughness. When monochromatic ultraviolet light emitted from the excimer is irradiated, the surface hardening reaction proceeds under a certain oxygen concentration, and surface hardening may not occur as much as desired at 10 ppm or more. Therefore, when irradiation with monochromatic light emitted from excimer is used, it is preferable to carry out under high-concentration nitrogen.

Surface hardening in step (b) is a type in which only a small part of the surface is hardened because light cannot penetrate into the inside of the coating layer due to the short wavelength emitted from the excimer. A coating film of can be formed.

In addition, before irradiating ultraviolet monochromatic light by excimer, using a lamp with an emission wavelength that is smaller in energy than the monochromatic ultraviolet light used to improve the texture of the coating surface or has a larger half-maximum width of the emitted band, 190 to 280 nm in the ultraviolet UVC region wavelength can be investigated.

Step (c) is a complete curing step in which long-wavelength ultraviolet rays are irradiated to the coating layer surface-cured in step (b) with a wavelength longer than the wavelength irradiated in the surface-curing step. The longer the wavelength, the more light can pass through to the inside of the coating layer, allowing complete curing. The lamp used is not particularly limited, and metal lamps, mercury lamps, gallium lamps, etc. may be used alone or in combination.

The amount of light irradiated to the coating surface may be about 10 to about 1,000 mJ/cm ² . When irradiated with ultraviolet rays at a light amount of less than about 10 mJ/cm ² , the hardness of the coating layer may decrease due to a decrease in curing rate, and when irradiated with light at a light amount greater than about 1,000 mJ/cm ² , the substrate layer may be yellowed due to over-curing.

The substrate layer includes crystalline and non-crystalline polyethylene terephthalate (PET, G-PET, GAG-PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene. (PS), polyvinylchlorite (PVC), acrylonitrile-styrene-acrylic (Acrylonitrile, ASA), and paper.

Example 1. Synthesis of urethane-acrylic acrylate copolymer SUA-3000

200 g (1.692 mole) of Tone 100 (caprolactone acrylate, Dow Chemical Company, molecular weight 344) corresponding to mark B and 167.1 g (1.128 mole) of 1,6-hexane diol corresponding to mark C ) in 900 g of 2-hydroxyethyl acrylate corresponding to mark D under a nitrogen stream, and slowly raise the temperature to 50 ° C. In addition, 1.98 g (14.13 mole) of polymerization inhibitor methoxyhydroquinone, 7.1 g (11.24 mole) of tin catalyst dibutyltindilaurate and 2,4,6-trioxotriazine corresponding to A -1,3,5-(2H,4H,6H)-triyl] trishexamethylene isocyanate {[2,4,6-trioxotriazine-1,3,5(2H,4H,6H)-triyl] tris(hexamethylene ) isocyanate)} 93.9 g (0.186 mole) was added and the temperature was slowly raised (70 to 85 ° C) for 3 hours, and then the disappearance of isocyanate was confirmed by infrared spectroscopy (IR). If isocyanate did not disappear, the reaction was terminated by confirming disappearance of isocyanate by IR while adding a small amount of 2-hydroxyethyl acrylate. The weight average molecular weight of the urethane-acrylic acrylate copolymer corresponding to Formula 1 is 4,200.

Example 2. Metal oxide SiO surface treated with fluorine compound ₂ synthesis

10 g of spherical SiO ₂ having an average particle size of 3.5 μm, a fluorine compound corresponding to structural formula 3, 1 g of heptadecafluorodecyltrichlorosilane (Shin-Etsu, trade name: LS-3175), 0.1 g of acrylic acid, 0.5 g of dispersant BYK-110 While dispersing 50 g of multifunctional acrylate M280 (Miwon Sangsa bifunctional acrylate) having an ethylene oxide group into a mixed solution, a very small amount of water is added and stirred at high speed for 3 hours. To this, 0.1 g of polymerization inhibitor methoxyhydroquinone and 0.5 g of 3-acryloxypropyltrimethoxysilane (Shin-Etsu Co., brand name: KBM-5103) were added thereto, followed by high-speed stirring at 3,000 rpm for 5 hours to complete the surface treatment. , to obtain a metal oxide surface treated with a fluorine compound.

Example 3. Preparation of coating composition and sheet according to the present application (1)

15 parts by weight of a urethane-acrylic acrylate copolymer corresponding to Chemical Formula 1 synthesized in Example 1 (SUA-3000, weight average molecular weight 4,200) synthesized in Example 1, based on 100 parts by weight of an ultraviolet monochromatic light curable matte coating composition with excellent wiping properties part, 30 parts by weight of the SiO ₂ mixture prepared in Example 2 (4.8 parts by weight of a metal oxide content corresponding to Formula 2 and surface-treated with a fluorine compound), polyfunctional acrylate having an ethylene oxide group {Miramer M ₂ 0 ₂ ( Miwon Corporation, bifunctional acrylate with ethylene oxide added)} 25 parts by weight, acrylate monomer (25 parts by weight of pentaerythritol tetraacrylate), photoinitiator {MBF (Ciba) 2.3 parts by weight, 184 (Ciba) ) 2 parts by weight}, leveling agent (Tego RAD 2200) 0.2 parts by weight, antioxidant (Tinuvin 1130, Civas) 0.2 parts by weight, UV stabilizer (Tinuvin 531, Civas) 0.3 parts by weight UV monochromatic light with excellent wiping properties A curable matte paint composition was prepared.

Thereafter, a coating layer was formed by applying the ultraviolet monochromatic light-curable matte coating composition having excellent wiping properties to about 5 to 20 μm in a gravure method on top of a PET-GAG 400 μm film (product of Doosung Korea), and using a Xe ₂ ^* lamp 172nm ultraviolet monochromatic light (100mJ/cm ² light quantity) is irradiated under high-purity nitrogen with an oxygen concentration of 10ppm or less, and ultraviolet light is continuously irradiated (metal, etc., mercury, etc.) with a light quantity of 1,000mJ/cm ² to completely cure the coating layer, and a thermosetting adhesive is applied to the back side. was coated to prepare an ultra-matte sheet having excellent wipeability. (See Fig. 2)

Example 4. Preparation of coating composition and sheet according to the present application (2)

30 parts by weight of a urethane-acrylic acrylate copolymer corresponding to Formula 1 synthesized in Example 1 (SUA-3000, weight average molecular weight 4,200) synthesized in Example 1, based on 100 parts by weight of an ultraviolet monochromatic light curable matte coating composition with excellent wipeability Part, 20 parts by weight of the SiO ₂ mixture prepared in Example 2 (corresponding to Chemical Formula 2 and having a metal oxide content of 3.2 parts by weight surface-treated with a fluorine compound), polyfunctional acrylate having an ethylene oxide group {Miramer M ₂ 0 ₂ ( Miwon Corporation, bifunctional acrylate with ethylene oxide added)} 30 parts by weight, acrylate monomer (15 parts by weight of pentaerythritol tetraacrylate), photoinitiator {MBF (Ciba) 2 parts by weight, 184 (Ciba) ) 2 parts by weight}, leveling agent (Tego RAD 2200) 0.3 parts by weight, adhesion promoter (SC-1400, Miwon Corporation) 0.2 parts by weight, antifoaming agent (Tego-920, Civas) 0.2 parts by weight, UV stabilizer (Tinuvin 531, Civas) An ultraviolet monochromatic light curable matte coating composition having excellent wiping properties containing 0.3 parts by weight was prepared.

Then, a coating layer was formed by applying about 5 to 20 μm of the ultraviolet monochromatic light curable matte coating composition having excellent wiping properties on top of a PET-GAG 400 μm film (product of Doosung Korea) in a gravure method, and 100 mJ / cm ² of After irradiating 190 to 280 nm wavelengths in the UVC region with a low amount of light, using Xe ₂ ^* lamp 172nm ultraviolet monochromatic light (100mJ/cm ² light quantity) is irradiated under high-purity nitrogen with an oxygen concentration of 10ppm or less, and ultraviolet light is continuously irradiated (metal, etc., mercury, etc.) with a light quantity of 1,000mJ/cm ² to completely cure the coating layer, and a thermosetting adhesive is applied to the back side. was coated to prepare an ultra-matte sheet having excellent wipeability.

Comparative Example 1.

Based on 100 parts by weight of the coating composition for decorative sheets, 30 parts by weight of a urethane-acrylic acrylate copolymer (Doosung Korea, SUA-3000, weight average molecular weight 4,200) corresponding to Formula 1 synthesized in Example 1, ethylene oxide group 30 parts by weight of multifunctional acrylate {Miramer M280 (Miwon Corporation, bifunctional acrylate with 7 moles of ethylene oxide added)}, acrylate monomer (35 parts by weight of pentaerythritol tetraacrylate), photoinitiator {MBF (Cibasa) 2 parts by weight, 184 (Cibasa) 2 parts by weight}, leveling agent (Tego RAD 2200) 0.3 parts by weight, adhesion promoter (SC-1400, Miwon Corporation) 0.2 parts by weight, antifoaming agent (Tego-920, Ciba g) An ultraviolet monochromatic light-curable matte coating composition containing no metal oxide containing 0.2 parts by weight and 0.3 parts by weight of an ultraviolet stabilizer (Tinuvin 531, Ciba) was prepared.

Then, a coating layer was formed by applying the matte coating composition for the decorative sheet to a thickness of about 5 to 20 μm on top of a PET-GAG 1,000 μm film (product of Doosung Korea) in a gravure method, and using a Xe ₂ ^* lamp 172nm ultraviolet monochromatic light (100mJ/cm ² light quantity) is irradiated under high-purity nitrogen with an oxygen concentration of 10ppm or less, and ultraviolet light is continuously irradiated (metal, etc., mercury, etc.) with a light quantity of 1,000mJ/cm ² to completely cure the coating layer, and a thermosetting adhesive is applied to the back side. was coated to prepare a matte sheet.

Figure 4 is a SEM picture taken at 150 times the surface of the matte decorative sheet prepared according to Comparative Example 1 of the present invention.

Comparative Example 2.

Based on 100 parts by weight of the coating composition for decorative sheets, PN-3271 (Polynetron, bifunctional urethane acrylate) 47 parts by weight, 1,6-hexanediol diacrylate 15 parts by weight, vinylpyrrolidone 15 parts by weight, 15 parts by weight of trimethylol propane triacrylate, 2 parts by weight of RAD-2500 (Tegosa, leveling agent), 1 part by weight of antifoaming agent {DC-205S (Chemiwon)} and photoinitiator {Irgacure

184 (Cibasa, 1-hydroxy-cyclohexyl-phenol-ketone) } A coating composition for decorative sheets containing 5 parts by weight was prepared.

Thereafter, a coating layer was formed by applying the matte coating composition for the decorative sheet to a thickness of about 10 to 20 μm on top of a PET-GAG 1,000 μm film (manufactured by Doosung Korea) in a gravure method.

After surface treatment by colliding with an aluminum metal roll with a 50um metal ball (Korean Patent Nos. 10-1262723 and 10-1279521), the surface of the aluminum metal roll is transferred to transparent PET using UV resin and photo-cured matte transfer for anti-fingerprints A film was made. After laminating the prepared transfer film to the coating layer, UV irradiation with a light amount of 600mJ / cm ² to cure the coating layer and remove the matte transfer PET, and then coat the back surface with a thermosetting adhesive to prepare a matte decorative sheet. (See Fig. 5)

Experimental example

1) Gloss evaluation

The films prepared in Examples 3 and 4 and Comparative Examples 1 and 2 were measured and evaluated with a BYK-Gardner Gloss Meter (60° Gloss) (see Table 1).

2) Substrate adhesion

After making 100 squares by drawing 11 horizontal and vertical lines on the coated surface of the film at 1 mm intervals, a peel test was performed 5 times using a niche reflective tape CT-24. Three squares of 100 were tested and recorded.

The test recording result for substrate adhesion was expressed as a ratio (n/100) of the number (n) of non-peeling squares out of the total number of squares (100). For example, when it was not completely peeled off (100/100, at least 3 times), it was recorded as 'OK', and when it was peeled off, it was recorded as 'NG' (see Table 1).

3) Pencil hardness

The test was done with a pencil hardness tester. Measurements were made according to JIS K 5600-5-4, except that the tester was set so that the tip of the pencil applied a load of 200 g to the coated surface when the tester was in a horizontal position. The evaluation results are shown in Table 1 below.

4) Scratch resistance

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

In Table 1, minimal changes in the surface of the coating film were recorded as 'O', mild changes in the surface of the coating film as 'Δ', and severe changes in the surface of the coating film as 'X'.

5) Fouling resistance

Vinegar, soy sauce, coffee, and ethanol were dropped on the coating layer, and then wiped 24 hours later and inspected. The evaluation results are shown in Table 1 below.

In Table 1, the level where no traces are visible is '5', the level where traces are visible when looking closely is '4', the level where traces are visible is '3', the level where traces are visible is '2', the coating surface These varying levels were recorded as '1', respectively.

6) Chemical resistance

A sample was immersed in an aqueous acid solution obtained by diluting 100% of a commercially available hydrochloric acid (35%) stock solution in distilled water to 5%, and a 5% diluted solution of caustic soda (NaOH), washed with distilled water after 24 hours and dried, and the level of change of the coated surface was measured. It was evaluated in 5 stages and is shown in Table 1 below.

The level of change in the coating surface is from 5 to 1, no surface change is '5', the level of slight defects is '4', the level of defects is '3', the level of partial peeling is '2', The fully peeled state was recorded as '1'.

7) heat resistance

After the specimen was left for 240 hours under the test temperature (90 ± 2 ° C) conditions, it was taken out and left at room temperature for 1 hour, and then discoloration, cracking, peeling, etc. of the coating film were observed.

The evaluation results are shown in Table 1 below. The level of change in the coated surface ranges from 5 to 1, no change in the surface is '5', the level of slight defects is '4', the level of visible defects is '3', and the level of visible defects is '2' , the state of complete discoloration, cracking, and peeling was recorded as '1'.

8) wipeability

On the coating layer, Monamisa's red board marker was used to mark the coating layer, and after 30 seconds, it was wiped with a tissue and then inspected. The evaluation results are shown in Table 1 below.

In Table 1, the level where no traces are visible is '5', the level where traces are visible when looking closely is '4', the level where traces are visible is '3', the level where traces are visible is '2', the coating surface These varying levels were recorded as '1', respectively.

9) Surface roughness measurement

Using a surface roughness meter, measure the center line average roughness (Ra) value 5 times using an NR110 (product of SADT, measurement parameters: Lr 0.8mm, 0.2<Ra<2) measuring equipment, and record the average value in Table 1 did

evaluation items Example 3 Example 4 Comparative Example 1 Comparative Example 2 Polish 1.8 1.9 5.2 2.4 adhesiveness OK OK OK OK pencil hardness 2H 2H H H scratch resistance O O △ △ stain resistance 5 5 3 3 chemical resistance 5 5 4 4 heat resistance 5 5 4 4 wipeability 5 5 2 2 Surface roughness (Ra) 0.82 0.78 1.89 2.12

As can be seen from Table 1, Examples 3 and 4 show superior results than Comparative Examples 1 and 2 in all items of physical property evaluation. Through this, the organic-inorganic hybrid type UV monochromatic light-curing matte coating composition with excellent wiping property according to the present invention implements a uniform surface shape compared to the coating composition of the comparative example composed only of general organic materials, and has excellent wiping property, anti-fingerprint property, and anti-fingerprint property. It can be seen that it has scratch resistance, hardness, stain resistance, heat resistance and chemical resistance. Accordingly, it can be seen that the composition can be used by applying an economical and environmentally friendly manufacturing method to decoration sheets such as furniture and exterior interiors of buildings.

The implementations and examples described so far are merely descriptions of preferred examples of the present invention, and the scope of the present invention is not limited to the described implementations and examples, and is within the technical spirit and claims of the present invention. Various changes, modifications, or substitutions may be made by those skilled in the art, and it should be understood that such embodiments fall within the scope of the present invention.

[Assignment information]

[Assignment number] S3236342

[Name of Department] Ministry of Small and Medium Venture Business

[Research project name] Purchase-conditional new product development project (purchase-linked type)

[Name of research project] Development of decorative sheet with excellent fingerprint resistance using recycled PET

[Contribution rate] 100%

[Organizer] Doosung Korea

[Research period] 2022.04.01 ~ 2024.03.31 (24 months)

10: base layer
20: coating layer
30: adhesive layer
100: sheet

Claims (21)

A urethane-acryl acrylate copolymer represented by Formula 1;
A metal oxide represented by Formula 2 and surface-treated with fluorine or a silicon compound;
multifunctional acrylate containing an ethylene oxide group;
acrylate monomers;
photoinitiators; and
Contains a leveling agent
Based on 100 parts by weight of the total paint composition
5 to 40 parts by weight of the urethane-acrylic acrylate copolymer;
0.1 to 10 parts by weight of the metal oxide surface-treated with the fluorine or silicon compound;
5 to 50 parts by weight of the multifunctional acrylate containing an ethylene oxide group;
5 to 30 parts by weight of the acrylate monomer;
1 to 5 parts by weight of the photoinitiator; and
The leveling agent comprises 0.1 to 1 part by weight,
paint composition.
[Formula 1]

here,
x, y, z are each less than or equal to 3, and
An integer such that x+y+z = 3
A =

In A, n = an integer less than or equal to 10
B =

in B,
R _1a, R _1b, R _1c = linear, branched or cyclic alkyl each having 1 to 10 carbon atoms
R ₂ = H or CH ₃
C =

in C,
R _1d = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms
_R3 = H or E
D =

in D,
R _1e = straight chain, branched or cyclic alkyl having 1 to 10 carbon atoms
R ₂ = H or CH ₃
E =

in E,
n = an integer less than or equal to 10
R ₄ = saturated or unsaturated hydrocarbon containing up to 30 carbon atoms, with or without oxygen or nitrogen
[Formula 2]
M _x O _y
In Formula 2,
M = Si, Ti, Al or Zr
x or y= 1, 2 or 3 According to claim 1,
The fluorine or silicon compound is represented by Formula 3-a or Formula 3-b, the paint composition.
[Formula 3-a]
(R ₅ ) _Q -Si-G _4-Q
R ₅ = up to 20 carbon atoms, with or without at least one fluorine (F), intramolecularly, hydrogen (H), oxygen (O), sulfur (S), chlorine (Cl), nitrogen (N), or silicon Alkyl having a saturated or unsaturated structure with or without (Si).
Q = 1 or 2
G = Cl, OH, OCH ₃ , OCH ₂ CH ₃ or OCH ₂ CH ₂ CH ₃
[Formula 3-b]
R ₆ -OH
R ₆ = 20 or less carbon atoms, contains at least one fluorine (F), contains or does not contain hydrogen (H), oxygen (O) or nitrogen (N) in the molecule, has a straight or branched chain structure, is saturated or Alkyl with an unsaturated structure. According to claim 1,
The paint composition is
0.1 to 1 part by weight of an adhesion promoter;
0.1 to 1 part by weight of an antifoaming agent;
0.1 to 1 part by weight of an ultraviolet stabilizer; and
Further comprising 0.1 to 1 part by weight of an antioxidant,
paint composition. According to claim 1,
The urethane-acrylic acrylate copolymer is a trifunctional or bifunctional urethane acrylate, and has a weight average molecular weight of 1,000 to 100,000,
paint composition. According to claim 1,
The metal oxide surface-treated with the fluorine or silicon compound has an average particle diameter of 1 to 10 μm,
paint composition. According to claim 1,
The multifunctional acrylate having an ethylene oxide group includes phenol (ethyleneoxy) ₂ acrylate, phenol (ethyleneoxy) ₄ acrylate, _and nonylphenol (ethyleneoxy) ₄ acrylate. ) _{2 - 8} acrylate (nonylphenol (ethyleneoxy) _{2 - 8} acrylate), phenol (meth) acrylate (phenol (meth) acrylate), ethylene oxide (CH ₂ CH ₂ O) 2 to 10 moles added 1 ,6-Hexanediol diacrylate (1,6-hexanediol diacrylate), 3 to 30 mol of ethylene oxide added, bisphenol A di(meth)acrylate (bisphenol A di(meth)acrylate), 3 to 15 mol of ethylene oxide added trimethylolpropane (meth)acrylate (trimethylolpropane (meth)acrylate), trimethylolpropane tri (meth)acrylate with 3 moles of propylene oxide added, and ethylene oxide added Containing at least one component selected from the group consisting of pentaerythritol tetraacrylate,
paint composition. According to claim 1,
The acrylate monomer is
Containing monofunctional, bifunctional or multifunctional acrylate monomers,
paint composition. According to claim 1,
The acrylate monomer is
phenol(ethyleneoxy) ₂ acrylate, phenol(ethyleneoxy) ₄ acrylate, _{nonylphenol (ethyleneoxy) 2 - 8 acrylate 2 - 8} acrylate), phenol (meth)acrylate, 1,6-hexanediol diacrylate, butandiol diacrylate, ethylene glycol diacrylate ethyleneglycol diacrylate, isobonylacrylate, butylcyclohexyl acrylate, (5-ethyl-1,3-dioxan-5-yl)methyl acrylate [(5-ethyl- 1,3-dioxan-5-yl)methyl acrylate], phenyl epoxy acrylate, trimethylolpropane (meth)acrylate, glycerin triacrylate, penta Erythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanate triacrylate, ditrimethylolpropane tetra(meth)acrylate (ditrimethylolpropane tetra(meth)acrylate), pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate. In the group consisting of dipentaerythritol hexa(meth)acrylate Including one or more selected components,
paint composition. According to claim 1,
The photoinitiator
Including at least one of a short-wavelength photoinitiator or a long-wavelength photoinitiator,
paint composition. According to claim 1,
The photoinitiator
1-hydroxy-cyclohexyl-phenol-ketone (1-hydroxy-cyclohexyl-phenol-ketone), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (2- methyl-1[4-(methylthio)phenyl]-2-morpholinopropane-1-one), benzyldimethylketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1- One (1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one), 2-hydroxy-2-methyl-1-phenylpropan-1-one (2-hydroxy-2-methyl-1 -phenylpropane-1-one), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one (1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one), benzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone (2,2- diethoxy-2-phenylacetophenone), 2-hydroxy-2-methyl-1-propane-1-one, 4,4'-diethylaminobenzo Phenone (4,4 '-diethylaminobenzophenone), dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-methylthioxanthone 1 selected from the group consisting of 2-ethylthioxanthone, 2,4-dimethylthioxanthone and 2,4-diethyloxanthone containing more than one species,
paint composition. According to claim 3,
The adhesion promoter includes phosphate methacrylate or phospho ester acrylate,
paint composition. base layer; and
Including a coating layer formed on the base layer,
The coating layer is formed by UV-curing the coating composition according to any one of claims 1 to 11,
Sheet. According to claim 12,
The base layer is
Polyethylene terephthalate (PET, PET-G, PET-GAG), polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene (PP), polyethylene (PE) and polystyrene (PS), polyvinylchlorite (PVC), acrylonitrile-styrene-acrylic (Acrylonitrile, ASA) and any one selected from the group consisting of paper materials,
Sheet. (a) a coating step of forming a coating layer by applying the coating composition according to any one of claims 1 to 11 on the surface of a substrate;
(b) a surface curing step of irradiating UV monochromatic light to the coating layer formed in step (a); and
(c) a complete curing step of irradiating the coating layer with ultraviolet rays at a wavelength greater than the wavelength of the ultraviolet monochromatic light irradiated in step (b),
sheet manufacturing method. According to claim 14,
Methods for performing the coating step include bar coating, roll coating, curtain coating, gravure coating, reverse gravure coating, and microgravure coating. coating),
sheet manufacturing method. According to claim 14,
The coating layer of the coating step is formed to a thickness of 5 to 20 μm,
sheet manufacturing method. According to claim 14,
The ultraviolet monochromatic light used in the surface curing step is
NeF ^* (108 nm, 11.48 eV), Ar ₂ ^* (126 nm, 9.84 eV), Kr ₂ ^* (146 nm, 8.49 eV), F ₂ ^* (158 nm, 7.85 eV), ArBr ^* (165 nm, 7.52 eV), Xe ₂ ^* (172 nm, 7.21 eV), ArCl ^* (175 nm, 7.08 eV), KrI ^* (190 nm, 6.49 eV), ArF ^* (193 nm, 6.42 eV), KrBr ^* (207 nm, 5.99 eV), KrCl ^* (222 nm, 5.58 eV), KrF ^* (248 nm, 5.01 eV), XeI ^* (253 nm, 4.91 eV), Cl ₂ ^* (259 nm, 4.79 eV), XeBr ^* (282 nm, 4.41 eV) and Br ₂ ^* (289 nm, 4.29 eV). Which includes any one selected from the group consisting of According to claim 14,
The surface curing step is to irradiate the ultraviolet monochromatic light in a nitrogen environment to cure the surface of the coating layer, and to adjust the amount of nitrogen so that the oxygen concentration in the reaction gas is 10 ppm or less during curing,
sheet manufacturing method. According to claim 14,
Between the step (a) and the step (b),
Further comprising a surface curing step of irradiating ultraviolet rays of a UVC region (190 to 280 nm) wavelength to the coating layer formed in step (a),
sheet manufacturing method. According to claim 14,
A lamp for irradiating the ultraviolet rays to the coating layer in the complete curing step
Which includes at least one of a mercury lamp, a metal lamp and a gallium lamp,
sheet manufacturing method. According to claim 14,
The light amount of the ultraviolet rays irradiated to the coating layer in the complete curing step is 100 to 1,000 mJ / cm ² ,
sheet manufacturing method.

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