KR101314832B1 - High-glossy decorative sheet having EVA pattern layer and the method of fabrication thereof - Google Patents

Abstract

The high gloss decoration sheet according to the present invention forms a soft EVA pattern layer between the UV curing coating layer and the decoration sheet to provide a decoration sheet excellent in scratch resistance, bending processability and interlayer adhesion.

Description

High-glossy decorative sheet having EVA pattern layer and the method of fabrication

The present invention relates to a high gloss decoration sheet and a method of manufacturing the same, and more specifically, by using a EVA hot melt resin and an environmentally friendly UV coating material to form a multi-layer coating layer containing a pattern, scratch resistance, bending processability and interlayer adhesion An improved high gloss decoration sheet and a method of manufacturing the same.

In general, furniture and interior finishes or interior materials of buildings are manufactured using vinyl chloride resin (PVC), polyolefin resin, or polyester resin, which is generally photocured in the case of high gloss products having improved surface transparency and scratch resistance. The resin is prepared by utilizing UV curing.

For example, a method of manufacturing interior sheets using UV hard coatings and UV curing adhesives has been filed (Application No. 10-2009-0054263), and an environmentally friendly polypropylene film (Application No. 10-2005-0087789) and a polyester film (Application No. 10-2007-0054644) has been applied for a technique for producing an eco-friendly interior sheet with improved surface strength by applying a UV curing coating. A technology for patterning the surface using UV-curable materials has also been published (Application No. 10-2008-0013828). In this case, a third film with a pattern is already used. It's a way to remove it.

However, the techniques disclosed in the related art improve the strength of the surface to provide the scratch resistance and the function of improving the transparency of the surface, but the hardness of the UV cured layer is so large that it does not realize the flexibility of PVC, PP or PET film. There is a disadvantage that the flexibility is too low.

In order to improve this, the modified polyethylene-based resin is used in the upper layer to improve wear resistance, scratch resistance, and stain resistance, and the mixed resin of polyurethane resin and modified polyethylene resin is used in the middle layer to improve tensile strength and elongation, and the polyurethane in the lower layer. Although a manufacturing method has been reported for a top layer film for eco-friendly decor sheet capable of heat fusion using a mixed resin of ethylene vinyl acetate resin (application number 10-2005-0043774, registration number 10-0622894), transparency and scratch resistance Not only is it lowered than using UV curable resins, but there are disadvantages in that manufacturing costs are increased due to the use of three layers of materials.

SUMMARY OF THE INVENTION An object of the present invention is to provide a decor sheet having improved surface strength and excellent bendability, including a multi-layered coating layer having a pattern.

In order to solve the above technical problem, the present invention is EVA sheet laminated on the decorative film; An EVA pattern layer formed on the EVA sheet; And it provides a high gloss decoration sheet comprising a UV hard coating layer formed on the EVA pattern layer.

According to an embodiment of the present invention, the EVA (Ethylene Vinyl Acetate copolymer) sheet may have a vinyl acetate content of 10 to 50 wt%, and a thickness of the EVA sheet may be 10 to 100 μm, but is not limited thereto. .

In addition, according to another embodiment of the present invention, the pattern may be selected from prism, stripe, lenticular, or dot type, but is not limited thereto.

The present invention (1) after coating the EVA composite resin on the EVA sheet to form a pattern and thermoset; (2) thermally compressing the decor sheet on the back of the EVA sheet; (3) coating a UV curable resin on the EVA pattern layer; And (4) aging the UV-curable resin coated sheet and then curing the UV curable resin sheet.

According to one embodiment of the present invention, the EVA composite resin of step (1) preferably comprises a thermal crosslinking agent, a photocuring initiator and a photocurable monomer.

The thermal crosslinking agents usable in the present invention are 2,2-di (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butyl-peroxyisopropylbenzene , 1,1-di (t-amylperoxy) cyclohexane, t-butyl- (2-ethylhexyl) monoperoxycarbonate, t-amyl (2-ethylhexyl) monoperoxy carbonate, t One or more selected from the group consisting of -butyl peroxy acetate, but is not limited thereto.

In addition, according to one embodiment of the present invention, the EVA composite resin may further comprise an auxiliary heat crosslinking agent, the auxiliary heat crosslinking agent, for example, t-amylperoxy-2-ethylhexanoate, 2,5- Dimethyl-2,5-di (2-ethylhexanoylperoxy) nucleic acid or t-butylperoxy-2-ethylhexanoate can be selected and used. In addition, the mixing ratio of the thermal crosslinking agent is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the EVA composite resin.

In addition, according to another embodiment of the present invention, the photocuring initiator may be used such as methyl benzoyl benzoate, benzophenone and 4-methylbenzophenone, but is not limited thereto, the content of the photocuring initiator and the photocurable monomer is EVA It is preferable that it is 0.1-3 weight part with respect to 100 weight part of composite resins.

According to another embodiment of the present invention, the photocurable monomer is, for example, 2-EHA (ethtlhexyl acrylate), ODA (octyl decyl acrylate), 2-HEA (Hydroxyethyl acrylate), BDDA (Butanediol), NPGDA ( Neopentyl Glycol Diacrylate), EGDMA (Ethylene Glycol Dimethylacrylate), TMPTA (Trimethylolpropane triacrylate), TMPTMA (Trimethylolpropane Trimethacrylate), PETA (Pentaerythritol triacrlate) can be used, but is not limited thereto.

According to one embodiment of the present invention, the coating of the EVA composite resin in step (1) is carried out in a hot melt method, the pattern formation may be performed using a pattern roll. In addition, the thermal curing of the step (2) is performed at 100 ~ 150 ℃, the aging of the (5) step may be carried out at 60 ~ 100 ℃.

The high gloss decoration sheet according to the present invention forms a soft EVA pattern layer between the UV curing coating layer and the decoration sheet to provide a deco sheet excellent in both scratch resistance and bending processing, and simply manufactured using the existing UV coating equipment There is an advantage that the manufacturing cost is not high.

1 is a process flowchart showing a manufacturing process of a high gloss decoration sheet having a composite coating layer having a prism pattern according to an embodiment of the present invention.
DESCRIPTION OF THE REFERENCE SYMBOLS
1: UV hard coating layer 2: EVA coating layer
3: EVA sheet 4: decor sheet

Hereinafter, the present invention will be described in detail.

The present invention relates to a high gloss decoration sheet, characterized by manufacturing a product having excellent surface strength and bending property by combining UV multi-layer coating and UV pattern technology. In addition, the present invention maximizes the adhesion between the layers by introducing a chemical bond by thermocompression and UV curing.

In the present invention, the multi-coating layer is formed on a conventional decor film, which is not particularly limited as a sheet on which various patterns or patterns are printed on polyvinyl chloride, polyolefin and polyester-based sheets.

In addition, the UV curable resin used for forming the UV hard coating layer in the present invention includes a UV curable oligomer, monomer and initiator, and after the coating of the liquid coating liquid in a conventional manner by irradiating ultraviolet light to initiate the reaction Curing in a short time to form a coating layer.

Epoxy acrylate, urethane acrylate and polyester acrylate are used as reactive oligomers, and epoxy acrylate and polyester acrylate have high tensile and high glass transition temperature. Although it has strength and surface hardness, there is a disadvantage in that elongation is inferior in formability of the final sheet. Urethane acrylate, on the other hand, has a relatively high elongation due to low glass transition temperature, but mechanical properties such as surface hardness and tensile strength are inferior.

On the other hand, oligomers generally have high viscosity and are difficult to use, and thus use reactive monomers to lower the viscosity. In some cases, the viscosity may be adjusted using a solvent, but there are environmental problems and physical properties are limited. Recently, a UV coating solution having a solid content of 100% using a monomer is mainly used. The monomers are classified according to the number of acrylates. In general, there are 1 to 6 acrylates.

Reactive monomers are classified into monofunctional, difunctional, trifunctional and multifunctional monomers according to the number of reactors. For monofunctional monomers, 2-EHA (ethtlhexyl acrylate), ODA (octyl decyl acrylate), 2-HEA (Hydroxyethyl acrylate), etc. Bifunctional monomers include BDDA (Butanediol), NPGDA (Neopentyl Glycol Diacrylate), and EGDMA (Ethylene Glycol Dimethylacrylate). Etc.

The final properties of the UV cured film depend on the type and compounding ratio of the oligomers and monomers. In general, when the hard monomer or oligomer having a high glass transition temperature is used and the crosslinking degree of these oligomers and monomers is increased, the elongation is increased. Is reduced, and moldability is significantly reduced. Therefore, the surface hardness and elongation can be adjusted by appropriately adjusting the amount of hard oligomer / monomer and soft oligomer / monomer according to the purpose of the final product, that is, limiting the simultaneous increase of surface hardness and elongation by changing the composition of oligomer or monomer. There is.

We tried to solve the problem by applying soft UV coating on the decor sheet and hard UV coating on it, but the soft coating layer on the lower layer reduces the surface hardness of the hard coating layer on the upper layer, and thus has no great effect.

Accordingly, the inventors of the present invention improve the surface strength and flexural formability by forming a multilayer coating layer including a pattern by using an EVA (Ethylene Vinyl Acetate Copolymer) resin and a UV curable resin that are excellent in elasticity and thermally curable and UV curable. Excellent decoration sheet has been developed.

The manufacturing method of the high gloss decoration sheet according to the present invention comprises the steps of (1) coating the EVA composite resin on the EVA sheet to form a pattern and thermoset; (2) thermally compressing the decor sheet on the back of the EVA sheet; (3) coating a UV curable resin on the EVA pattern layer; And (4) UV curing after aging. 1 is a process flowchart showing a method of manufacturing a high gloss decoration sheet having a composite coating layer having a prism pattern according to an embodiment of the present invention.

First, in step (1), the EVA composite resin including both the thermosetting initiator and the photocuring initiator is coated on the EVA sheet by a hot melt method. Then, the pattern roll is used to form a prism, stripe, lenticular, or dot-shaped pattern, and then thermally cured between 100 and 150 ° C. to increase the shape stability of the pattern. In step (2), the decor sheet is fixed by thermal compression on the back of the EVA sheet, and in step (3), a hard coating solution for UV curing is applied on the upper part of the EVA pattern. In step (4), the laminated sheet is aged between 60 to 100 ° C. for at least 1 hour, and then irradiated with UV to completely cure the EVA coating layer and the UV hard coating layer.

In the case of the composite sheet according to the present invention, since the surface is heated with a hard UV coating layer, the scratch resistance is excellent and at the same time the elongation of the final product is secured due to the soft EVA sheets in the lower layer, thereby providing excellent bending processability. . At this time, since the hard UV coating layer is formed while filling between the EVA patterns of the lower layer, it is possible to significantly reduce the phenomenon of the UV hard coating layer generated when the high gloss sheet is bent.

In the present invention, the role of the EVA pattern layer is very important, since the pattern layer is located between the EVA sheet and the UV hard coating layer, the bonding force between the upper and lower layers is very important. If the adhesive strength with the upper and lower layers is lowered, when the sheet is bent and molded over time, long-term durability is degraded such as gaps between sheets or UV hard coating layers are broken or peeled off. Another problem is that the pattern can be deformed in a two-step process of thermally compressing the decor sheet.

In order to solve the above problems, in the present invention, an EVA pattern was formed using an EVA composite resin capable of thermal curing and photocuring. First, the thermosetting agent, crosslinking aid, UV initiator and photocurable monomer are added to the EVA composite resin, followed by hot melt mixing, and then the composite resin is pattern coated on the EVA sheet and heat cured to increase the stability of the EVA pattern. The deformation of the pattern does not occur in the process of thermal compression.

On the other hand, when the UV curable hard coating layer is applied to the EVA pattern coating layer and then aged between 60 and 100 ° C., and then irradiated with UV, partial crosslinking is generated between the UV hard coating layer and the EVA coating layer. The adhesion between the coating layers is rapidly increased.

The EVA sheet used in the present invention may be a general EVA having a vinyl acetate (VA) content of 10 to 50% by weight and a thickness of 10 to 100 μm. Meanwhile, in the case of the composite EVA used for pattern coating, a thermal crosslinking agent, a photoinitiator and a photocuring monomer are added to the EVA composite resin.

Examples of the thermal crosslinking agent that can be used in the present invention include 2,2-di (t-butylperoxy) butane and n-butyl-4,4-bis (t-butylperoxy) having a half-life of about 140 to 170 ° C. Valerate, t-butyl-peroxyisopropylbenzene, 1,1-di (t-amylperoxy) cyclohexane, t-butyl- (2-ethylhexyl) monoperoxycarbonate, t-amyl (2 -Ethylhexyl) monoperoxycarbonate, t-butylperoxyacetate, etc. can be used, and as an auxiliary heat crosslinker, t-amylperoxy-2-ethylhexanoe is an auxiliary radical peroxide having a half-life of 120 to 150 ° C. Ate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) nucleic acid, t-butylperoxy-2-ethylhexanoate and the like can be used.

It is effective to mix | blend the mixing ratio of a crosslinking agent in the ratio of 0.1-5 weight part, especially 0.5-3 weight part with respect to 100 weight part of EVA composite resins. If the content of the crosslinking agent is too low, the crosslinking of EVA may be insufficient, resulting in deformation of the pattern upon thermocompression bonding with the decor sheet. On the other hand, if the content of the crosslinking agent is too high, the compatibility with the EVA composite resin may be degraded and unreacted. The crosslinking agent remains in the module, causing side reactions, and the durability of the pattern layer becomes poor.

In addition, the photocuring initiators include methyl benzoylbenzoate, benzophenone, 4-methylbenzophenone, and 4-mrthylbenzophenone. One or a combination of functional or trifunctional monomers may be used. In the case of the content of the photoinitiator and the photocurable monomer, it is effective to mix 0.1 to 3 parts by weight based on 100 parts by weight of the EVA composite resin, but is not particularly limited.

In addition, the pattern of the soft UV coating layer according to the present invention is possible without limitation as long as it is a three-dimensional shape, it is usually selected from prism, stripe, lenticular, or dot form. In the case of a pattern, a pattern of various forms can be formed using the pattern roll like a conventional method.

Through the following examples will be described in more detail the present invention. The present embodiment is for illustrative purposes only, and the scope of the present invention is not limited to these examples.

Example  One

First, EVA (trade name PV-1650 manufactured by Mitsui Dupont) resin was processed in a milling apparatus to prepare an EVA sheet having a thickness of 100 nm. To 100 parts by weight of the EVA composite resin, 1.5 parts by weight of a thermal crosslinking agent (trade name CHEMEX-EC, t-butylperoxy-2-ethylhexyl carbonate), photocuring initiator (MBB, methyl-o-benzoylbenzoate from Sang Hing Hong) ) 1.0 parts by weight, and 2.0 parts by weight of a photocurable monomer (Additek's EGDMA, Ethylene Glycol Dimethylacrylate) were mixed at 160 ° C. and coated directly on the EVA sheet. At the time of coating, the pattern layer of the prism form was formed using the pattern roll, At this time, the prism height was set to 10 micrometers, and the area was 1 mm <^2> .

The oak-colored PVC decorative sheet printed on the back of the EVA composite sheet was bonded by thermocompression bonding, and then directly coated on the EVA coating layer using a UV curable resin (Aekyung Chemical, RS-1657). The composite sheet was aged at 80 ° C. for 1 hour and then photocured using a mercury lamp. At this time, the UV irradiation amount was adjusted to 800 mJ / cm ² .

Comparative Example  One

It is the same as Example 1 except the EVA coating layer without a pattern was formed. At this time, the thickness of the coating layer was adjusted to 10 ㎛.

Comparative Example  2

It is the same as Example 1 except the EVA coating layer does not contain a thermal crosslinking agent.

Comparative Example  3

It is the same as Example 1 except the EVA coating layer does not contain a photocuring initiator and a photocuring monomer.

The surface gloss, scratch resistance and V-cutting and bending workability of the sheet according to the Examples and Comparative Examples were evaluated based on the following evaluation method, and the results are shown in Table 1.

[Assessment Methods]

1. Surface glossiness

The high gloss decoration sheet was placed on black paper, and a 1m fluorescent lamp was installed to classify the film into three grades by observing the glossiness of the film.

○: The surface is smooth and the film finish is constant

Δ: surface is somewhat smooth but unstable

×: almost no surface gloss and poor thickness

2. Scratch resistance

After the scratch test (1kg load, 10 round trips) for # 000 steel wool, the results were classified into 3 grades.

○: No surface damage

Δ: slight surface damage

X: much surface damage

3. V-shaped cutting and bending workability

After forming the V-shaped cutting groove on the upper surface of the high-gloss decoration sheet, check whether it is possible to restore the original flat state by bending and unfolding, and if it is bent without cutting grooves, observe the degree of discoloration of the bent portion and classify it into 3 grades. Classified by.

○: When the V-shaped cutting groove is formed, it is bent and straightened. If there is no cutting groove, there is no discoloration of the bent portion.

Δ: When the V-shaped cutting groove is formed, it is bent and unfolded, but when there is no cutting groove, the discoloration of the bent portion is somewhat observed.

X: When the V-shaped cutting groove is formed, it is not bent and unfolded. If there is no cutting groove, the bent portion discolors to white.

Structure and Composition of EVA Coating Layer Product Specifications Heat curing agent Photoinitiators and Monomers pattern Surface gloss Scratch resistance Bending workability Example 1 U U U O O O Comparative Example 1 U U radish O O X Comparative Example 2 radish U U X O D Comparative Example 3 U radish U O O D

As can be seen in the above examples and comparative examples, when the pattern is formed by using the EVA composite resin containing a thermosetting and photocuring initiator it can be produced a composite sheet excellent in both scratch resistance and bending processability Able to know. On the other hand, it can be seen that the bending processability is poor when simply forming an EVA coating layer without a pattern or a coating layer without a photocuring initiator and monomer. In addition, when the EVA coating layer is formed without the thermosetting initiator, it can be seen that the surface gloss is deteriorated due to the deformation of the prism shape during the thermocompression bonding with the decor sheet.

Claims (18)

delete delete delete delete (1) coating the EVA composite resin on the EVA sheet to form a pattern and thermosetting;
(2) thermally compressing the decor sheet on the back of the EVA sheet;
(3) coating a UV curable resin on the EVA pattern layer; And
(4) a method of manufacturing a high gloss decor sheet comprising the step of aging the UV-curable resin-coated sheet (UV) and then UV curing. The method of claim 5,
EVA composite resin of step (1) is a method of producing a high gloss decoration sheet, characterized in that it comprises a thermal crosslinking agent, a photocuring initiator and a photocurable oligomer or monomer. The method of claim 5,
The EVA sheet has a vinyl acetate content of 10 to 50% by weight of the manufacturing method of the high gloss decoration sheet. The method according to claim 6,
The thermal crosslinking agent is 2,2-di (t-butylperoxy) butane, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butyl-peroxyisopropylbenzene, 1,1 -Di (t-amylperoxy) cyclohexane, t-butyl- (2-ethylhexyl) monoperoxycarbonate, t-amyl (2-ethylhexyl) monoperoxy carbonate, t-butylperoxy Method for producing a high gloss decoration sheet, characterized in that at least one selected from the group consisting of acetate. The method according to claim 6,
The EVA composite resin further comprises an auxiliary heat crosslinking agent. 10. The method of claim 9,
The auxiliary thermal crosslinking agent is t-amylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) nucleic acid, t-butylperoxy-2-ethylhexahexa Method for producing a high gloss decoration sheet, characterized in that selected from noate. The method according to claim 6,
The mixing ratio of the thermal crosslinking agent is a method for producing a high gloss decoration sheet, characterized in that 0.1 to 5 parts by weight with respect to 100 parts by weight of EVA composite resin. The method according to claim 6,
Wherein the photocuring initiator is selected from methyl benzoylbenzoate, benzophenone and 4-methylbenzophenone. The method according to claim 6,
The content of the photocuring initiator and the photocurable monomer is a method for producing a high gloss decoration sheet, characterized in that 0.1 to 3 parts by weight based on 100 parts by weight of the EVA composite resin. The method according to claim 6,
The photocurable monomer is 2-ethhaxyl acrylate (EDA), octyl decyl acrylate (ODA), 2-hydroxy (Hydroxyethyl acrylate), BDDA (butanediol), NPGDA (Neopentyl Glycol Diacrylate), EGDMA (Ethylene Glycol Dimethylacrylate), TMPTA (Trimethylolpropane) triacrylate), TMPTMA (Trimethylolpropane Trimethacrylate), PETA (Pentaerythritol triacrlate) A method for producing a hygroscopic decor sheet, characterized in that at least one selected. The method of claim 5,
The coating of the EVA composite resin in the step (1) is a method of manufacturing a high gloss decoration sheet, characterized in that carried out in a hot melt method. The method of claim 5,
Forming the pattern of the step (2) is a method for producing a high gloss decoration sheet, characterized in that performed using a pattern roll. The method of claim 5,
Heat curing of the step (2) is a method for producing a high gloss decoration sheet, characterized in that carried out at 100 ~ 150 ℃. The method of claim 5,
Aging of the step (4) is a method for producing a high gloss decoration sheet, characterized in that carried out at 60 ~ 100 ℃.

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