KR100840992B1 - High glossy sheet - Google Patents

Abstract

A high-glossy sheet containing spheres in a surface treatment agent is provided to secure the texture and cubic and glossy effects by mixing a surface treatment agent and spheres and to express metallic texture by irregularly reflecting the light of an evaporated layer. A high-glossy sheet containing spheres in a surface treatment agent is composed of: a base layer(11) containing PVC(Polyvinyl Chloride) or PP(Polypropylene), a plasticizer, a Ba-Zn(Barium Zinc) stabilizer, inner and outer anti-additives, and a shock reinforcing agent; an adhesive layer(12) formed on the base layer to bond the base layer and an evaporated layer(13); the evaporated layer positioned on the adhesive layer to express the metallic texture; a primer layer(14) formed on the evaporated layer to stick the evaporated layer well and to reinforce attaching power with a PET(Polyethylene Terephthalate) film layer(16), and composed of polyurethane resin, a hardening agent, and a solvent containing EA(Ethyl Acetate); a hairline layer(15) formed on the primer layer to generate mechanical scratches on the PET film in order to express natural metallic texture; the PET film layer formed on the hairline layer; and a surface treatment layer(17) formed on the PET film layer to protect the surface of a product and to increase a texture effect. The surface treatment layer contains a solvent containing at least one selected from UV(Ultraviolet) resin, a fluorine dispersing agent, MEK(Methyl Ethyl Ketone), EA, and spheres made of bead type styrene resin having a cross-linking structure suspension-polymerized from styrene monomer. Some of spheres made of bead type styrene resin are protruded on the upper surface of the surface treatment layer.

Description

High Glossy Sheet with Spherical Material in Surface Treatment

1 is a cross-sectional configuration of a conventional multi-layer decorative sheet,

Figure 2 is a cross-sectional configuration of a high gloss sheet according to an embodiment of the present invention.

<Description of the symbols for the main parts of the drawings>

11: base layer

12: adhesive layer

13: deposition layer

14: primer layer

15: hairline layer

16: PET film

17: surface treatment layer

The present invention relates to a high gloss sheet containing a spherical material and a surface treatment agent, in a high gloss sheet laminated in multiple layers on a PET film, the surface of the surface coating agent containing a variety of functionality, the degree of gloss and The effect is an important factor in the quality, characterized in that it contains 0.1 to 20% of a spherical substance made of bead-like styrene resin having a crosslinked structure suspended from styrene monomer in a weight ratio to the surface treatment layer. Since it is composed of a surface treatment agent and a spherical material, it exhibits a texture and three-dimensional appearance, and has a proper glossiness, not only to make a fantastic aesthetic sense, but also to have an anti-fingerprint effect at the same time.

Steel plates are commonly used for industrial products that require durability.In order to prevent corrosion and to improve the color and texture of the surface, a technique of laminating films to the steel plate is applied. Recently, it is applied to household appliances such as refrigerators and air conditioners. It has been applied a lot, and high glossy is popular, and the sheet applied to it is named high gloss sheet. Currently, it is divided into 4 ~ 6 kinds according to color and expression technique.

Conventionally, a method of coating UV-curable varnishes, acrylic varnishes, urethane varnishes, etc. has been used to give abrasion resistance and high gloss to the surface of the synthetic resin sheet. It was not at a level.

In addition, acrylic varnish has excellent gloss retention, but abrasion resistance does not meet the required properties, and in the case of urethane-based varnish, low-temperature polyvinyl chloride sheet having low thermal stability is used as a base material because high temperature conditions are required when drying the coating film. When there is a problem that the coating work productivity is greatly reduced.

Republic of Korea Patent Publication No. 10-2003-0063886 (name: high gloss decorative sheet consisting of a surface treatment layer by a transfer method, Applicant: Kumgang Korea Chemical Co., Ltd.) in the 'multi-layer decorative sheet in order to provide a high gloss sheet with enhanced surface hardness , High gloss decorative sheet (Claim 1) constituting the surface treatment layer by the transfer method, characterized in that the surface treatment layer is coated on the polyethylene terephthalate (PET) film and transferred to the uppermost layer of the decorative sheet. A high gloss decorative sheet (claim 2) 'comprising a surface treatment layer formed by a transfer method using a urethane isocyanate two-component surface treatment agent, a urethane one-component surface treatment agent, a urethane acrylate surface treatment agent, and an epoxy acrylate surface treatment agent is described. 1 is a cross-sectional view of a multi-layer decorative sheet including a conventional transparent film 93, a printing film 94, an easy film 96, a printing layer 95, the surface treatment layer 91.

However, such a prior art is not excellent enough to meet consumer expectations in texture, three-dimensional or aesthetic, and also has a problem that the fingerprint due to the touch remains intact, maintaining the texture, aesthetic gloss or three-dimensional according to use (that is, The prior art has no effect of preventing fingerprints from being touched).

Registered Utility Model 20-0295063 (name: High Glossy Synthetic Resin Sheet, Applicant: Hanwha General Chemical Co., Ltd.) states that the synthetic resin film layer (1), the surface coating layer (2) and the adhesive layer (3) for transfer are sequentially stacked from the bottom. The surface coating layer is made of a transfer-curable synthetic resin film (claim 1), wherein the surface coating layer is composed of a heat-curable coating film composition, and the 'heat-curable coating film composition is 15 to 30% by weight polyester resin, 5 to 15% by weight acrylic resin %, 5-10% by weight of vinyl acetate resin, 2-5% by weight of polyvinylidene chloride resin, 3-15% by weight of linear polyisocyanate resin, 1-3% by weight of cellulose ester resin, 0.2-0.8% by weight of silicone additive A transfer synthetic resin film (claim 2) 'comprising a%, 20 to 35% by weight of toluene, and 20 to 35% by weight of methyl ethyl ketone is described.

As described above, in the prior art, many surface treatment agents using silica as a gloss adjustment additive have been used. However, the surface treatment agents using silica are inexpensive and general, while they are amorphous and go down at low viscosity (1 to 50 cps). There is a sedentary property, the excessive problem of the material has a decisive problem that the surface tends to drop the overall properties of the film.

The object of the present invention is to solve the above problems, the object of the present invention is to improve the physical properties of the surface coating film, while excellent in texture and three-dimensional feeling, not only to give a proper gloss but also to prevent fingerprint formation by the touch To provide a high gloss sheet that can be.

In order to achieve the object of the present invention, the high gloss sheet containing a spherical material in the surface treatment agent according to the present invention contains PVC (polyvinyl chloride) or PP (polypropylene) in the high gloss sheet, and a plasticizer, Ba-Zn A base layer 11 containing a system stabilizer, an internal and external lubricant, and an impact modifier; An adhesive layer 12 provided on an upper layer of the substrate layer 11 and for laminating the substrate layer 11 and the deposition layer 13; A deposition layer 13 positioned on the adhesive layer 12 and expressing a metal texture; It is provided on the upper layer of the deposition layer 13 and adheres well to the deposition layer 13, and enhances the adhesion with the PET film layer 16, polyurethane resin, hardener, and ethyl acetate (Ethyl Acetate, EA) A primer layer 14 composed of a solvent including; A hairline layer 15 provided on the primer layer 14 and having a mechanical scratch on the PET film 16 to express a natural metal texture; A PET film layer 16 provided on the upper layer of the hairline layer 15; It includes a surface treatment layer 17 provided on the upper layer of the PET film layer 16 to increase the surface protection and texture effect of the product, the surface treatment layer 17 is UV resin (UV Resin), Spherical material of fluorine-based dispersant, solvent containing at least one selected from methyl ethyl ketone (MEK) and ethyl acetate (Ethyl Acetate), and bead styrene resin having a crosslinked structure suspended from styrene monomer. It includes, wherein the spherical material of the bead-like styrene resin is characterized in that a portion protrudes on the upper surface of the surface treatment layer 17.

Hereinafter, a high gloss sheet containing a spherical material in the surface treating agent according to the present invention will be described in detail according to the embodiment shown in the accompanying drawings. 2 is a cross-sectional configuration of a high gloss sheet according to an embodiment of the present invention.

As shown in Figure 2, the high gloss sheet containing the spherical material in the surface treatment agent according to an embodiment of the present invention is the base layer 11, the adhesive layer 12, the deposition layer 13, the primer layer 14, The hairline layer 15 and the PET film layer 16 are sequentially formed. The surface treatment layer prevents contamination and scratches and increases the surface protection and texture effect of the product on the upper side of the PET film layer 16. (17) is formed.

The base layer 11 contains one selected from PVC (polyvinyl chloride) or PP (polypropylene), and contains a plasticizer, a Ba-Zn-based stabilizer, internal and external lubricants, and an impact modifier. In the PVC embodiment, the substrate layer 11 uses 80 to 120 micron PVC (polyvinyl chloride) or PP (polypropylene) sheet, 100 parts by weight of PVC resin, plasticizer [Di-isononyl Phthalate (abbreviation: DINP) ), Etc.] 12-30 parts by weight, 1-8 parts by weight of Ba-Zn-based stabilizer, 0.2-3 parts by weight of internal and external lubricants. It is composed of 0.1 to 2 parts by weight of the impact modifier.

The adhesive layer 12 is provided on the upper layer of the base layer 11 and is for laminating the base layer 11 and the deposition layer 13. The adhesive layer 12 is composed of 100 parts by weight of polyurethane resin, 10 to 30 parts by weight of a curing agent, 70 to 120 parts by weight of a solvent including ethyl acetate (Ethyl Acetate, EA).

The deposition layer 13 is located on the upper layer of the adhesive layer 12 to express the metal texture, and the deposition layer 13 is generally deposited aluminum. Texture difference occurs depending on the thickness of the deposition, so limit limits are set to maintain a constant thickness.

The primer layer 14 is provided on the upper layer of the deposition layer 13 and adheres well to the deposition layer 13 and enhances adhesion with the PET film layer 16, and is a polyurethane resin, a curing agent, and ethyl acetate. It consists of a solvent containing (Ethyl Acetate, EA). The primer layer 14 is preferably composed of 1,000 to 7,000 parts by weight of a solvent containing 100 parts by weight of polyurethane resin, 10 to 30 parts by weight of a curing agent, and ethyl acetate (Ethyl Acetate, EA).

The primer layer maintains a thin thickness and obtains a desired effect (adhesion effect between the PET film layer and the aluminum deposition layer), and when the curing agent is less than 10 parts by weight, the bonding strength is weakened and the desired properties are insufficient. In the case where the hardening agent exceeds 30 parts by weight, unbound isocyanate groups may be trapped in the compound as it is and cause discoloration. The solvent in the primer layer is a means and serves as a diluent to lower the content of the resin. The content of the solvent can be controlled within the range of 1,000 to 7,000 parts by weight based on the desired strength and coating thickness. .

 The hairline layer 15 is a layer in which a mechanical scratch is generated on the PET film in order to express a natural metal texture on the upper layer of the primer layer 14, and the hairline layer 15 has no added material and is surfaced by mechanical strength. Give it a scratch like hair. That is, it is the layer which generated the mechanical scratch.

A polyethylene terephthalate (PET) film layer 16 is provided on the upper layer of the hairline layer 15. PET film layer 16 is preferably 15 to 50 microns (μ, micrometer) thick, 1,000 to 1,450mm in width.

The surface treatment layer 17 is provided on the upper layer of the PET film layer 16 to increase the surface protection and texture effect of the product.

The surface treatment layer 17 is formed from an ultraviolet resin (UV Resin), a fluorine-based dispersant, a solvent including at least one selected from methyl ethyl ketone (MEK, Methyl Ethyl Ketone) and ethyl acetate (Ethyl Acetate), and a styrene monomer. A spherical material made of bead-like styrene resin having a suspension-polymerized crosslinked structure is included, and a part of the spherical material made of bead-like styrene resin protrudes from the upper surface of the surface treatment layer 17.

Surface treatment layer 17 is 100 parts by weight of UV resin (UV Resin), 100 to 500 parts by weight of a solvent containing at least one of methyl ethyl ketone (MEK, Methyl Ethyl Ketone) and ethyl acetate (Ethyl Acetate), fluorine-based dispersant, And a spherical material made of a bead-like styrene resin having a crosslinked structure suspended from a styrene monomer, wherein the surface treatment layer 17 contains 0.01 to 1% of the total weight of the surface treatment layer 17. The spherical material of the bead-like styrene resin having a crosslinked structure suspended from the styrene monomer is preferably contained in an amount of 0.1 to 10% of the total weight of the surface treatment layer 17. If no dispersant is added, unbalance will occur in the surface gloss due to the spherical material being driven.

The spherical material (S) made of bead-like styrene resin having a crosslinked structure suspended from a styrene monomer is spherical, and preferably, the average particle diameter of the spherical material (S) is 1 to 15 µm. If the average particle diameter is too large, the surface becomes rough, rather, the fouling resistance is poor, while if the average particle diameter is too small, it is submerged without protruding from the surface to reduce the gloss effect and texture effect.

When the coating thickness of the surface treatment layer 17 in the state in which the solvent is volatilized after the coating liquid is coated to a predetermined thickness at the time of coating is 3 to 12 microns, the average particle diameter of the preferred spherical material S is 2 to 8 µm. In this range, production cost, gloss effect, texture effect, and anti-tack effect are optimized.

Fluorine-based dispersant uses 0.01 ~ 1% (based on the total amount), and fluorine-based dispersant exhibits a constant charge on the spherical materials, causing electric repulsion force between the spherical materials, preventing aggregation and facilitating dispersion. Maintaining spacing helps to maintain consistency of presentation effects. In case of excessive input, excessive surface slippage is caused, which adversely affects the processing of the next process. If no dispersant is added, unbalance will occur in the surface gloss due to the spherical material being driven.

In the case of the surface treatment agent, if the solvent is too small as a means for processing, the dispersion of the resin is difficult, the viscosity is high, and processing such as coating is difficult, and when too much is added, the viscosity is too thin and the workability such as coating becomes difficult.

The bead-like styrene resin is 100 parts by weight of a styrene monomer or another copolymerizing monomer (at least one selected from α-methylstyrene, acrylonitrile, and methyl methacrylate), 20 to 50 parts by weight of a crosslinking agent, and 0.01 to 0.01 to a polymerization catalyst. Prepared by suspension polymerization using 1 part by weight.

Ethylene glycol dimethyl acrylate, trimethylolpropane trimethacrylate, etc. are used as said crosslinking agent. The structure of the trimethylolpropane trimethacrylate is represented by the following [Formula 1].

As said polymerization catalyst, organic peroxides, such as benzoyl peroxide and tert- butyl per benzoate, and the azo compound of azobisisobutyronitrile are used.

As described above, the bead-like styrene resin is a styrene monomer; At least one crosslinking agent selected from ethylene glycol dimethyl acrylate and trimethylolpropane trimethacrylate; It is prepared by suspension polymerization using at least one polymerization catalyst selected from an azo compound of azobisisobutyronitrile and an organic peroxide selected from benzoyl peroxide and tert-butylperbenzoate. In addition, the bead-like styrene resin may be prepared by further including at least one other copolymerized monomer selected from α-methylstyrene, acrylonitrile and methylmethacrylate.

<Example>

The primer layer 14 is composed of 100 parts by weight of polyurethane resin, 16 parts by weight of hardener, and 3,000 parts by weight of ethyl acetate (Ethyl Acetate, EA) solvent, and the surface treatment layer 17 is 100 parts by weight of UV resin (UV Resin). , 300 parts by weight of solvent, 0.12% of the total weight of the fluorine-based dispersant, 0.9% of the total weight of the spherical material, the high gloss sheet excellent texture, three-dimensional, gloss, anti-fingerprint effect due to the touch of the spherical material protruding on the surface Could get

The method and operation of the high gloss sheet containing a spherical material in the surface treatment agent according to the present invention having such a configuration will be described.

The coating (surface treatment layer) thickness of the surface treatment agent is about 1 to 20 microns, and currently the 5 micron thickness is used the most. In the example of 5 microns thick, the average particle diameter is about 3 microns and the distribution degree is about 1 to 5 microns. In the preferred embodiment, the coating liquid thickness is 20 microns and the solvent is volatilized (75%). 5 microns will be coated. If the particle size is too large, the surface becomes rough, rather, the pollution resistance is poor, if too small, it is submerged without protruding to the surface to reduce the gloss effect and texture effect. If it is more than 30㎛, it is practically difficult to apply due to the cost burden.

The spherical material gives gloss while showing the texture and three-dimensional appearance of the surface, and the spherical material protruding from the surface also has the anti-fingerprint effect by the touch.

Although the present invention has been described in connection with the above-mentioned preferred embodiment, the scope of the present invention is not limited to the embodiment, various modifications and variations will be possible.

According to the high gloss sheet containing the spherical material in the surface treatment agent according to the present invention, the problem of the prior art is solved, and by mixing the surface treatment agent and the spherical material, the texture and three-dimensional appearance become glossy and make a fantastic aesthetic feeling as well as deposition. Reflects the layer's light to the upper part to make the metal texture look more three-dimensional and prevents fingerprints due to the touch. High-gloss sheet is mainly used for the exterior materials of home appliances (eg refrigerators, air conditioners, etc.). Is the main effect that is greatly improved.

Figure 3 is a photograph showing the anti-fingerprint effect by the touch, the left photo is a photograph on the high gloss sheet according to the present invention, the right photo is a photograph on the high gloss sheet of domestic woolen yarn. As shown in the figure, it can be seen that the high gloss sheet according to the present invention has an advantageous effect of anti-fingerprint by touch.

 Although the present invention has been described in connection with the above-mentioned preferred embodiments, the scope of the present invention is not limited to these embodiments, and the scope of the present invention is defined by the following claims, and equivalent scope of the present invention. It will include various modifications and variations belonging to.

The reference numerals set forth in the claims below are merely to aid the understanding of the present invention, not to affect the interpretation of the scope of the claims, and the scope of the claims should not be construed narrowly.

Claims (8)

In the high gloss sheet, A base layer 11 containing PVC (polyvinyl chloride) or PP (polypropylene) and containing a plasticizer, a Ba-Zn-based stabilizer, internal and external lubricants, and an impact modifier; An adhesive layer 12 provided on an upper layer of the substrate layer 11 and for laminating the substrate layer 11 and the deposition layer 13; A deposition layer 13 positioned on the adhesive layer 12 and expressing a metal texture; It is provided on the upper layer of the deposition layer 13 and adheres well to the deposition layer 13, and enhances the adhesion with the PET film layer 16, polyurethane resin, hardener, and ethyl acetate (Ethyl Acetate, EA) A primer layer 14 composed of a solvent including; A hairline layer 15 provided on the primer layer 14 and having a mechanical scratch on the PET film 16 to express a natural metal texture; A PET film layer 16 provided on the upper layer of the hairline layer 15; The surface of the PET film layer 16 includes a surface treatment layer 17 provided to increase the surface protection and texture effect of the product, The surface treatment layer 17 is a UV resin (UV Resin), a fluorine-based dispersant, a solvent containing at least one selected from methyl ethyl ketone (MEK, Methyl Ethyl Ketone) and ethyl acetate (Ethyl Acetate), and styrene monomer And a spherical material made of bead-like styrene resin having a cross-linked structure suspended from the above, wherein the spherical material made of bead-like styrene resin partially protrudes from the upper surface of the surface treatment layer 17. High gloss sheet containing spherical material in the treatment agent. The method of claim 1, The primer layer 14 is a spherical material in the surface treatment agent, characterized in that composed of 1,000 to 7,000 parts by weight of a solvent containing 100 parts by weight of polyurethane resin, 10 to 30 parts by weight of a curing agent, and ethyl acetate (Ethyl Acetate, EA) High gloss sheet containing this. The method according to claim 1 or 2, The surface treatment layer 17 is 100 parts by weight of UV resin (UV Resin), 100 to 500 parts by weight of a solvent containing at least one of methyl ethyl ketone (MEK, Methyl Ethyl Ketone) and ethyl acetate (Ethyl Acetate), fluorine-based dispersant And a spherical material of bead-like styrene resin having a crosslinked structure suspended from styrene monomer, The surface treatment layer 17 contains 0.01 to 1% of the fluorine-based dispersant based on the total weight of the surface treatment layer 17, and a spherical material made of a bead-like styrene resin having a crosslinked structure suspended from styrene monomer is formed on the surface. Treatment layer 17 is a high gloss sheet containing a spherical material in the surface treatment agent, characterized in that it contains 0.1 to 10% by weight. The method of claim 3, The bead-like styrene resin is a styrene monomer; At least one crosslinking agent selected from ethylene glycol dimethyl acrylate and trimethylolpropane trimethacrylate; Spherical substances in the surface treatment agent, characterized in that prepared by suspension polymerization using at least one polymerization catalyst selected from azo compounds of azobisisobutyronitrile and organic peroxide selected from benzoyl peroxide, tert- butyl perbenzoate High gloss sheet containing this. The method of claim 4, wherein A spherical material containing a spherical material in the surface treatment agent, characterized in that the spherical material of the bead-like styrene resin having a crosslinked structure suspended from the styrene monomer has an average particle diameter of 1 ~ 15㎛. The method of claim 5, The base layer 11 is 80 to 120 microns, 100 parts by weight of PVC resin, 12 to 30 parts by weight of plasticizer, 1 to 8 parts by weight of Ba-Zn-based stabilizer, 0.2 to 3 parts by weight of internal and external lubricants, and impact modifiers 0.1 to 2 parts by weight, The adhesive layer 12 contains a spherical material in the surface treatment agent, characterized in that consisting of 100 parts by weight of polyurethane resin, 10 to 30 parts by weight of a curing agent, 70 to 120 parts by weight of a solvent containing ethyl acetate (Ethyl Acetate, EA) High gloss sheet. The method of claim 4, wherein The bead-like styrene resin is a high gloss sheet containing a spherical material in the surface treatment agent, characterized in that further comprising at least one other copolymerization monomer selected from α-methylstyrene, acrylonitrile and methyl methacrylate. The method of claim 6, The bead-like styrene resin is 100 parts by weight of at least one other copolymerization monomer selected from a styrene monomer or α-methylstyrene, acrylonitrile and methyl methacrylate containing the same, 20 to 50 parts by weight of a crosslinking agent and 0.01 to 1 polymerization catalyst A high gloss sheet containing a spherical material in the surface treatment agent, characterized in that prepared by suspension polymerization using parts by weight.

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