KR20220067827A - Acrylic sheet laminate and method of preparing the same - Google Patents

Abstract

According to one embodiment of the present application, provided are an acrylic sheet laminate for furniture capable of implementing various colors and appearances using a co-extruded sheet and a method of preparing the same. The sheet laminate includes: a styrene-based resin layer; an acryl-based resin layer; an adhesive layer; and a hard coating layer.

Description

Acrylic sheet laminate and manufacturing method thereof

The present application relates to an acrylic sheet laminate and a manufacturing method thereof, and to an acrylic sheet laminate capable of implementing various designs and appearances, and a manufacturing method thereof.

The decoration sheet (decor sheet) is applied as an exterior material for home appliances such as TVs, refrigerators, and air conditioners or electronic devices such as smartphones and tablets to realize desired colors and patterns.

A decoration sheet is generally based on a film such as PET, and consists of a pattern layer that implements various patterns, a print layer that implements colors, a multi-deposition layer that implements colors and metal effects, and an adhesive layer, and is laminated according to the purpose. The structure may be variously deformed in terms of order, manufacturing method, or material.

In the case of using a co-extruded sheet laminate, there is a limit to realizing various patterns, various colors, and complex appearances in addition to a simple solid appearance, so research for implementing this is necessary.

According to an embodiment of the present application, an object of the present application is to provide an acrylic sheet laminate for furniture capable of implementing various colors and appearances using a co-extruded sheet, and a method for manufacturing the same.

One aspect of the present application relates to a sheet laminate.

As an example, the sheet laminate includes a styrene-based resin layer; an acrylic resin layer positioned on the styrene-based resin layer; It may include an adhesive layer positioned on the acrylic resin layer and a hard coating layer positioned on the adhesive layer.

As an example, the styrene-based resin layer and the acrylic resin layer may be manufactured by co-extrusion.

As an example, the hard coating layer may include a pattern or embossing on the surface.

As an example, the sheet laminate includes a styrene-based resin layer; an acrylic resin layer positioned on the styrene-based resin layer; and a hard coating layer positioned on the acrylic resin layer.

As an example, the styrene-based resin layer and the acrylic resin layer may be manufactured by co-extrusion.

As an example, the glossiness may be 10 or less.

One aspect of the present application relates to a method of manufacturing a sheet laminate.

As an example, the method for manufacturing a sheet laminate includes the steps of: forming a styrene-based resin and an acrylic resin being extruded at the same time as the styrene-based resin is extruded, forming a co-extruded styrene-based resin layer and an acrylic-based resin layer positioned on the styrene-based resin layer; laminating an adhesive layer of a transfer film in which an adhesive layer, a hard coating layer, and a carrier film are sequentially stacked and the acrylic resin layer; and removing the carrier film.

As an example, the melt index of the styrene-based resin measured at 230° C./3.8 kg according to ASTM D1238 may be 2 to 4 g/10 min.

As an example, the melt index of the acrylic resin measured at 230° C./3.8 kg according to ASTM D1238 may be 1 to 3 g/10 min.

As an example, the thickness ratio of the styrene-based resin layer and the acrylic resin layer may be 1: 3 to 5.

As an example, the sheet laminate is extruded at the same time as the styrene-based resin is extruded, forming a co-extruded styrene-based resin layer and an acrylic resin layer positioned on the styrene-based resin layer; and locating a hard coating layer on the acrylic resin layer.

According to an embodiment of the present application, it is possible to provide a sheet laminate capable of implementing various appearances.

According to an embodiment of the present application, it is possible to provide a sheet laminate capable of implementing excellent surface durability.

According to an embodiment of the present application, it is possible to provide a sheet laminate capable of realizing a desired embossing or pattern.

1 is a schematic cross-sectional view of a sheet laminate according to an embodiment of the present application.
2 is a schematic cross-sectional view of a sheet laminate according to an embodiment of the present application.
3 is a flowchart illustrating a method of manufacturing a sheet laminate according to an exemplary embodiment of the present application.
4 is a schematic diagram for explaining a method of manufacturing a sheet laminate according to an embodiment of the present application.
5 is a flowchart illustrating a method of manufacturing a sheet laminate according to an exemplary embodiment of the present application.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that the features, components, etc. described in the specification are present, and one or more other features or components may not be present or may be added. Doesn't mean there isn't.

Throughout the specification, when “A and/or B” is used, it means A, B or A and B, unless otherwise stated, and when “C to D” is used, it means that there is no specific opposite description. Unless otherwise specified, it means that it is greater than or equal to C and less than or equal to D.

Reference to an element or layer “on” or “on” another element or layer includes not only directly on the other element or layer, but also with other layers or other elements intervening. include all On the other hand, reference to an element "directly on" or "directly on" indicates that no intervening element or layer is interposed.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

The manufacturing of the co-extruded sheet laminate is a single process that can extract a sheet having a thickness of about 2T from a double-layer ultra-thin layer. Although the pre-preparation process is long and complicated, once the conditions are confirmed, it is possible to produce a larger lot size at once compared to dry lamina or nib lamina.

In addition, when using a co-extruded sheet laminate, there is a limitation in implementing various patterns, various colors, and complex appearance in addition to a simple solid appearance. By laminating the embossed hard coating layer, various colors and appearances can be realized.

Hereinafter, the sheet laminate of the present application and a manufacturing method thereof will be described in detail with reference to the accompanying drawings. However, the accompanying drawings are exemplary, and the scope of the sheet laminate and the manufacturing method thereof of the present application is not limited by the accompanying drawings.

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

1, the sheet laminate 10 is a styrene-based resin layer 11; an acrylic resin layer 13 positioned on the styrene-based resin layer 11; It may include an adhesive layer 15 positioned on the acrylic resin layer 13 and a hard coating layer 17 positioned on the adhesive layer 15 .

Styrene-based resin layer

The styrene-based resin layer includes a styrene resin composed of three components: acrylonitrile, butadiene, and styrene. It is called ABS resin (acrylonitrile butadiene styrene copolymer), and as described above, it is a styrene resin composed of three components: acrylonitrile, butadiene, and styrene. It has excellent impact resistance, chemical resistance, and weather resistance. In particular, it has excellent moldability such as injection molding and extrusion molding and secondary processability such as coloring.

Acrylic resin layer

The acrylic resin layer includes polymethyl methacrylate resin. It is called PMMA resin (Polymethly Methacrylate) and has excellent transparency, good weather resistance, high hardness, and excellent surface gloss.

As an example, the styrene-based resin layer and the acrylic resin layer may be manufactured by co-extrusion. Put PMMA resin in the main extruder and ABS resin in the sub extruder, and co-extruded to a thickness of 1.6T / 0.4T. In the present invention, as an example in consideration of workability, the melt index of the styrene-based resin measured at 230 ° C / 3.8 kg according to ASTM D1238 may be 2 to 4 g/10 min, and as an example, 230 according to ASTM D1238 The melt index of the acrylic resin measured at ℃/3.8kg may be 1 to 3 g/10 min. Preferably, the MI (230° C./3.8 kg) value is controlled at a level of 3.0 g/10 min for ABS and 2.1 g/10 min for PMMA.

Here, the melt index (MI) is an index that determines the amount of resin discharged under a given temperature and force condition during extrusion. It becomes difficult to control the thickness, and the co-extrusion operation may not be smooth.

In particular, ABS is responsible for the basic color as a toning layer, and the transparent PMMA layer gives a sense of depth to the exterior, giving it a glass-like feeling with high thickness. .

adhesive layer

As will be described later, the sheet laminate according to an embodiment of the present application may be manufactured by a transfer method. In this case, an adhesive layer is required for adhesion of the acrylic resin layer and the hard coating layer during the transfer process.

In addition, the adhesive layer preferably includes a polyester-based ink for color toning for color toning.

The adhesive layer serves to bond the transfer film to the decoration material, and specifically serves to bond the transfer film to the decoration material. The material constituting the adhesive layer may be used without limitation as long as it can secure sufficient adhesion between the decorative film and the decorative material, and may include, for example, a polyester-based resin and a curing agent.

The thickness of the adhesive layer is preferably 1 to 3 μm.

hard coating layer

Various patterns of hard coating appearance can be given. As an example, the hard coating layer may include a pattern or embossing on the surface.

A pattern formed on the carrier film or a pattern transferred by embossing is formed on the hard coating layer.

In the present invention, the hard coating layer may include a polymer formed by combining a polyacrylic polyol and a polyester polyol with an isocyanate compound and a urethane bond.

The hard coating layer may include the polyacrylic polyol and the polyester polyol. It may be included in the form of a polymer blend of the polyacrylic polyol and the polyester polyol. In addition, the polyacrylic polyol and the polyester polyol may be a thermosetting resin. For example, the inclusion content ratio of the polyacrylic polyol and the polyester polyol may be 95:5 to 50:50 by weight, preferably 90:10 to 60:40, and more preferably 80 :20 to 70:30. When the polyacrylic polyol is included in more than the above range, there is a problem in that room temperature processability is deteriorated as the content of the polyacrylic polyol having a high glass transition temperature is too high, and when the polyester polyol is included in more than the above range, hardness or tensile strength There is a problem with the decrease in strength.

The polyacrylic polyol may include an acrylate repeating unit. The polyacrylic polyol may be included in an amount of 40 wt% to 80 wt% based on the total content of the transparent resin layer.

The polyacrylic polyol may have a weight average molecular weight of 10,000 to 150,000, and a hydroxyl value (OH value) of 20 KOH mg/g to 200 KOH mg/g (on solid basis). When the weight average molecular weight of the polyacrylic polyol exceeds 150,000, the viscosity of the polyacrylic polyol is remarkably increased, and coating defects may occur when the coating solution is applied. When the weight average molecular weight of the polyacrylic polyol is 10,000 or less, the chemical resistance of the polyacrylic polyol may be lowered and solvent resistance to a solvent such as MEK may be deteriorated. In consideration of the coating properties and chemical resistance of the polyacrylic polyol, preferably, the weight average molecular weight of the polyacrylic polyol may be 50,000 to 100,000.

In addition, when the hydroxyl value of the polyacrylic polyol is lower than 20 KOH mg/g, it does not participate in the curing reaction, so there is a problem as long as the degree of surface hardening is low and solvent resistance and stain resistance are weak, and the hydroxyl value of the polyacrylic polyol is If it is greater than 200 KOH mg/g, there is a problem in that it is difficult to apply the product due to the change in appearance in moisture resistance due to the hydroxyl functional group that does not participate in the curing reaction.

The polyester polyol may include an ester repeating unit. The polyester polyol may be included in an amount of 2 wt% to 20 wt% based on the total content of the transparent resin layer. The polyester polyol may have a hydroxyl value (OH value) of 10 KOH mg/g to 600 KOH mg/g.

In addition, when the hydroxyl value of the polyester polyol is lower than 10 KOH mg/g, the OH equivalent of the polyester polyol is very low and even if a coating film is formed, the surface of the coating film is sticky or does not harden, so it sticks to the substrate in the roll-to-roll process There is a problem that the line application becomes difficult due to the discarding phenomenon, and when the hydroxyl value of the polyester polyol is greater than 600 KOH mg/g, the compatibility deteriorates and the coating film becomes opaque after coating occurs, and a curing agent is added due to the high hydroxyl value After the viscosity rises very quickly, there is a problem in that the appearance of the coating is not good due to the occurrence of streaks during coating.

2 is a schematic cross-sectional view of a sheet laminate according to an embodiment of the present application.

As shown in Figure 2, the sheet laminate 20 is a styrene-based resin layer (21); an acrylic resin layer 23 positioned on the styrene-based resin layer 21; and a hard coating layer 27 positioned on the acrylic resin layer 23 .

Styrene-based resin layer

The styrene-based resin layer includes a styrene resin composed of three components: acrylonitrile, butadiene, and styrene. It is called ABS resin (acrylonitrile butadiene styrene copolymer), and as described above, it is a styrene resin composed of three components: acrylonitrile, butadiene, and styrene. It has excellent impact resistance, chemical resistance, and weather resistance. In particular, it has excellent moldability such as injection molding and extrusion molding and secondary processability such as coloring.

Acrylic resin layer

The acrylic resin layer includes polymethyl methacrylate resin. It is called PMMA resin (Polymethly Methacrylate) and has excellent transparency, good weather resistance, high hardness, and excellent surface gloss.

As an example, the styrene-based resin layer and the acrylic resin layer may be manufactured by co-extrusion. Put PMMA resin in the main extruder and ABS resin in the sub extruder, and co-extruded to a thickness of 1.6T / 0.4T. In the present invention, as an example in consideration of workability, the melt index of the styrene-based resin measured at 230 ° C / 3.8 kg according to ASTM D1238 may be 2 to 4 g/10 min, and as an example, 230 according to ASTM D1238 The melt index of the acrylic resin measured at ℃/3.8kg may be 1 to 3 g/10 min. Preferably, the MI (230° C./3.8 kg) value is controlled at a level of 3.0 g/10 min for ABS and 2.1 g/10 min for PMMA.

Here, the melt index (MI) is an index that determines the amount of resin discharged under a given temperature and force condition during extrusion. It becomes difficult to control the thickness, and the co-extrusion operation may not be smooth.

In particular, ABS is responsible for the basic color as a toning layer, and the transparent PMMA layer gives a sense of depth to the exterior, giving it a glass-like feeling with high thickness. .

hard coating layer

Durability may be provided through the hard coating layer. However, in this embodiment, the hard coating layer exhibits a matte characteristic.

In order to exhibit matte properties, the hard coating layer may include polyurethane resin.

As an example, the glossiness may be 10 or less.

In the present application, "60° gloss (G)" can be measured using a gloss meter according to ASTM D2457, and is a numerical value expressing the degree of glossiness of the surface (GU: gloss unit). It can be seen that the lower the gloss, the closer to matte.

The 60 ° glossiness (G) of the wrinkled surface of the coating layer may be, for example, 5.9 or less, 5.8 or less, 5.6 or less, 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, or 5.0 or less. When the surface of the coating layer of the film has a gloss (G) of 60° in the above range, it is possible to provide a user with a beautiful matte property.

3 is a flowchart illustrating a method of manufacturing a sheet laminate according to an exemplary embodiment of the present application.

4 is a schematic diagram for explaining a method of manufacturing a sheet laminate according to an embodiment of the present application.

3 and 4, in the method for manufacturing a sheet laminate, the styrene-based resin is extruded and the acrylic resin is extruded at the same time, the co-extruded styrene-based resin layer and the acrylic-based resin positioned on the styrene-based resin layer forming a stratum (S11); laminating the adhesive layer of the transfer film in which the adhesive layer, the hard coating layer, and the carrier film are sequentially stacked and the acrylic resin layer (S13); and removing the carrier film (S15).

The manufacturing method will be described in more detail for each step.

First, the styrene-based resin is extruded and the acrylic resin is extruded at the same time to form a co-extruded styrene-based resin layer and an acrylic-based resin layer positioned on the styrene-based resin layer (S11).

Since the hard coating using the transfer film is applied using the heat remaining on the sheet immediately after the co-extrusion sheet is produced, hard coating with embossing can be applied, unlike the existing general co-extrusion and hard-coated sheets. It may proceed as a single process, not a heavy process.

Then, the adhesive layer of the transfer film in which the adhesive layer, the hard coating layer, and the carrier film are sequentially laminated and the acrylic resin layer are laminated (S13).

Carrier films include polyester-based resin film, polyolefin-based resin film, polyamide-based resin film, polyacrylate-based resin film, thermoplastic polyurethane-based resin film, polycarbonate-based resin film, ABS (Acrylonitrile-Butadiene-Styrene) resin film, etc. can be heard

Examples of the polyester-based resin film include a polyethylene terephthalate (PET) resin film, examples of the polyamide-based resin film include a nylon resin film, and examples of the polyolefin-based resin film include a polyethylene resin film or A polypropylene resin film etc. are mentioned.

In the present invention, the thickness of the carrier film may be, for example, about 10 μm or more and less than about 100 μm. When the thickness of the carrier film is less than about 10 μm, processability and handleability of the transfer film are disadvantageous, and when the thickness of the carrier film is about 100 μm or more, price competitiveness of the transfer film may be lowered. For this reason, the thickness of the carrier film may be, for example, about 20 μm to about 80 μm.

Then, the carrier film is removed (S15).

By removing the carrier film, the outermost layer of the sheet laminate becomes a hard coat layer, and an appearance such as a pattern or embossing of the hard coat layer appears on the surface of the sheet laminate.

5 is a flowchart illustrating a method of manufacturing a sheet laminate according to an exemplary embodiment of the present application.

As shown in FIG. 5, the acrylic resin is extruded at the same time as the tyrene-based resin is extruded, forming a co-extruded styrene-based resin layer and an acrylic resin layer positioned on the styrene-based resin layer (S21); and locating the hard coating layer on the acrylic resin layer (S23).

Hereinafter, the present application will be described in more detail through experimental examples.

[Experimental example]

[Example 1]

After preparing ABS and PMMA by co-extrusion, a matte hard coating layer was laminated.

[Example 2]

After preparing ABS and PMMA by co-extrusion, an adhesive primer and a hard coating layer were laminated on a patterned release PET, and then transferred onto an ABS/PMMA co-extrusion sheet.

[Comparative Example 1]

A sheet laminate of AM1800TopX commercially available from SENOSAN was purchased and used as a sample for Comparative Example 1.

[Comparative Example 2]

A sheet laminate of Rauvisio Crystal commercially available from REHAU was purchased and used as a sample for Comparative Example 1.

[evaluation]

For Examples 1 and 2 and Comparative Examples 1 and 2, stain resistance was measured as follows.

Specifically, the stain resistance according to DIN 68861:2011, part 1 was evaluated, and mustard, wine, coffee, tea, acetic acid, and ethanol were each tested. After exposure to contaminants, the degree of damage to the surface was visually checked and graded from grade 1 (severe damage) to grade 5 (no change).

mustard wine coffee car acetic acid ethanol Example 1 5 5 5 5 5 5 Example 2 5 5 5 5 5 5 Comparative Example 1 3 5 5 5 5 5 Comparative Example 2 4 5 5 5 5 5

As shown in Table 1, compared to Comparative Example 1, Examples 1 to 3 exhibited a pollution degree ranging from 4 grades (occurrence of minimal change in gloss or color) to 5 grades, and through this, the cured product according to the present application It can be seen that the silver has excellent stain resistance.

Although the above has been described with reference to preferred embodiments of the present application, those skilled in the art can variously modify and change the present application without departing from the spirit and scope of the present invention as set forth in the claims below. You will understand that you can.

10: sheet laminate
11: Styrene-based resin layer
13: acrylic resin layer
15: adhesive layer
17: hard coating layer
19: carrier film
20: sheet laminate
21: styrene-based resin layer
23: acrylic resin layer
27: hard coating layer

Claims (14)

styrene-based resin layer;
an acrylic resin layer positioned on the styrene-based resin layer;
an adhesive layer positioned on the acrylic resin layer; and
A sheet laminate comprising a hard coating layer positioned on the adhesive layer.
The method of claim 1,
The styrene-based resin layer and the acrylic resin layer is a sheet laminate manufactured by co-extrusion.
The method of claim 1,
The hard coating layer is a sheet laminate including a pattern or embossing on the surface.
styrene-based resin layer;
an acrylic resin layer positioned on the styrene-based resin layer; and
An acrylic sheet laminate comprising a hard coating layer positioned on the acrylic resin layer.
The method of claim 1,
The styrene-based resin layer and the acrylic resin layer is a sheet laminate manufactured by co-extrusion.
The method of claim 1,
A sheet laminate having a glossiness of 10 or less.
The styrene-based resin is extruded and the acrylic resin is extruded at the same time to form a co-extruded styrene-based resin layer and an acrylic resin layer positioned on the styrene-based resin layer;
laminating an adhesive layer of a transfer film in which an adhesive layer, a hard coating layer, and a carrier film are sequentially stacked and the acrylic resin layer; and
and removing the carrier film.
8. The method of claim 7,
The melt index of the styrene-based resin measured at 230 °C / 3.8 kg according to ASTM D1238 is 2 to 4 g/10 min. A method of manufacturing a sheet laminate.
8. The method of claim 7,
According to ASTM D1238, the melt index of the acrylic resin measured at 230°C/3.8kg is 1 to 3 g/10 min.
8. The method of claim 7,
The thickness ratio of the styrene-based resin layer and the acrylic resin layer is 1: 3 to 5. A method for producing a sheet laminate.
The styrene-based resin is extruded and the acrylic resin is extruded at the same time to form a co-extruded styrene-based resin layer and an acrylic resin layer positioned on the styrene-based resin layer; and
A method of manufacturing a sheet laminate comprising the step of locating a hard coating layer on an acrylic resin layer.
12. The method of claim 11,
The melt index of the styrene-based resin measured at 230 °C / 3.8 kg according to ASTM D1238 is 2 to 4 g/10 min. A method of manufacturing a sheet laminate.
12. The method of claim 11,
According to ASTM D1238, the melt index of the acrylic resin measured at 230°C/3.8kg is 1 to 3 g/10 min. A method for producing a sheet laminate.
12. The method of claim 11,
The thickness ratio of the styrene-based resin layer and the acrylic resin layer is 1: 3 to 5, a method for producing a sheet laminate.

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