WO2020071633A1 - Adhesive composition and deco sheet comprising same - Google Patents

Abstract

The present invention relates to an adhesive composition and a deco sheet comprising same, and the adhesive composition includes, together with an epoxy resin, an organic acid, an aromatic alcohol, and/or a polar aprotic solvent, and thus has good compatibility and high adhesion to a metal layer. In addition, an adhesive layer formed using the adhesive composition exhibits high adhesion to a metal layer and high elongation even under a condition where a primer layer is excluded, and thus a deco sheet comprising same has high durability and high formability.

Description

Adhesive composition and decorative sheet comprising the same

The present invention relates to an adhesive composition comprising an organic acid, an aromatic alcohol and / or a polar aprotic solvent together with an epoxy resin, and a decor sheet comprising the same.

In general, the decor sheet for home appliances is mainly used to finish the surface of home appliances, and it protects the home appliances from external environmental changes and prints beautiful patterns of various colors to change the appearance of home appliances according to customer preference. It also has a design effect.

Recently, more and more consumers prefer a silver color, which gives a metallic feel, rather than white, which gives a clean image when selecting home appliances. Accordingly, in order to express the appearance of a silver-colored home appliance, research on a decorative sheet for household appliances including a metal layer (aluminum layer) on which an aluminum is deposited on an adhesive layer has been actively conducted. In addition, research is being actively conducted on a decorative sheet for household appliances to further improve the adhesion between the metal layer and the adhesive layer by further including a primer layer between the metal layer and the adhesive layer.

However, like the existing decor sheet for home appliances, the adhesive sheet, the primer layer, the aluminum layer, the polyethylene terephthalate (PET) base layer and the top coating layer are sequentially stacked, and the decor sheet is composed of several layers, so that the corrosion resistance is not good and the manufacturing method There is a drawback to this complexity.

Accordingly, there is an urgent need for the development of a home appliance deco sheet material that exhibits a metallic texture including aluminum but does not include several layers, and exhibits excellent adhesion and durability.

An object of the present invention is to provide an adhesive layer composition having good compatibility and excellent adhesion to a metal layer and a decor sheet comprising the same.

Thus, the present invention in one embodiment,

Epoxy resins; And

Contains at least one component selected from the group consisting of organic acids, aromatic alcohols and polar aprotic solvents,

The organic acid, aromatic alcohol, and polar aprotic solvent independently provide an adhesive composition comprising 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the total adhesive composition.

In addition, the present invention in one embodiment,

Base layer; Metal layer; And the adhesive layer containing the adhesive composition is sequentially laminated,

The metal layer includes voids,

The pores have an average depth of 1 nm to 15 nm, providing a decorative sheet.

The adhesive composition according to the present invention has an advantage of good compatibility and excellent adhesion to a metal layer, including an organic acid, an aromatic alcohol, and / or a polar aprotic solvent together with an epoxy resin. In addition, since the adhesive layer formed using the adhesive composition exhibits high adhesiveness and elongation with the metal layer even under the condition that the primer layer is excluded, the decorative sheet containing the same has the advantage of excellent durability and moldability.

1 is a scanning electron microscope (SEM) analysis of a cross-section of a decorative sheet according to the present invention.

The present invention can be applied to various changes and may have various embodiments, and specific embodiments will be illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, terms such as “comprises” or “have” are intended to indicate that there are features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other features. It should be understood that the existence or addition possibilities of fields or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

In addition, the accompanying drawings in the present invention should be understood to be shown enlarged or reduced for convenience of description.

Hereinafter, the present invention will be described in detail with reference to the drawings, and the same or corresponding components will be given the same reference numbers regardless of the reference numerals, and redundant descriptions thereof will be omitted.

The present invention relates to an adhesive composition film and a decor sheet comprising the same.

In general, the decor sheet for home appliances is mainly used to finish the surface of home appliances, and it protects the home appliances from external environmental changes and prints beautiful patterns of various colors to change the appearance of home appliances according to customer preference. It also has a design effect.

Recently, more and more consumers prefer a silver color, which gives a metallic feel, rather than white, which gives a clean image when selecting home appliances. Accordingly, in order to express the appearance of a silver-colored home appliance, research on a decorative sheet for household appliances including a metal layer (aluminum layer) on which an aluminum is deposited on an adhesive layer has been actively conducted. In addition, research is being actively conducted on a decorative sheet for household appliances to further improve the adhesion between the metal layer and the adhesive layer by further including a primer layer between the metal layer and the adhesive layer. However, like the existing decor sheet for home appliances, the adhesive sheet, the primer layer, the aluminum layer, the polyethylene terephthalate (PET) base layer and the top coating layer are sequentially stacked, and the decor sheet is composed of several layers, so that the corrosion resistance is not good and the manufacturing method There is a drawback to this complexity.

Accordingly, the present invention provides an adhesive composition and a decorative sheet comprising the same.

The adhesive composition according to the present invention has an advantage of good compatibility and excellent adhesion to a metal layer, including an organic acid, an aromatic alcohol, and / or a polar aprotic solvent together with an epoxy resin. In addition, since the adhesive layer formed using the adhesive composition exhibits high adhesiveness and elongation with the metal layer even under the condition that the primer layer is excluded, the decorative sheet containing the same has the advantage of excellent durability and moldability.

Hereinafter, the present invention will be described in more detail.

Adhesive composition

The present invention in one embodiment,

Epoxy resins; And

Contains at least one component selected from the group consisting of organic acids, aromatic alcohols and polar aprotic solvents,

The organic acid, aromatic alcohol, and polar aprotic solvent independently provide an adhesive composition comprising 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the total adhesive composition.

The adhesive composition according to the present invention may induce an organic resin, an aromatic alcohol, and / or a polar aprotic solvent together with an epoxy resin, thereby inducing deformation of an interface structure of an adhesive surface to which the composition contacts the adhesive composition. The adhesive strength of the adhesive composition can be significantly improved.

Here, the adhesive composition according to the present invention may include one or more components selected from the group consisting of an epoxy resin, an organic acid, an aromatic alcohol, and a polar aprotic solvent, and may specifically have the following composition:

(1) epoxy resins and organic acids;

(2) epoxy resins and aromatic alcohols;

(3) epoxy resin and polar aprotic solvent;

(4) epoxy resins, organic acids and aromatic alcohols; or

(5) Epoxy resin, organic acid, aromatic alcohol and polar aprotic solvent.

More specifically, the adhesive composition may have the following composition:

(1) epoxy resins and organic acids;

(2) epoxy resins and aromatic alcohols;

(3) epoxy resin and polar aprotic solvent; or

(4) Epoxy resins, organic acids and aromatic alcohols.

The adhesive composition according to the present invention comprises an epoxy resin as a main component. The epoxy resin has the advantage of realizing excellent compatibility while exhibiting good adhesion unlike resins such as polyester and polyacrylic used in the conventional adhesive composition. Here, the term "consisting of the main component" means that 70 parts by weight or more, 75 parts by weight or more, 80 parts by weight or more, 85 parts by weight or more, 90 parts by weight or more, or 95 parts by weight or more based on 100 parts by weight of the adhesive composition is included. More specifically, the content of the epoxy resin may be 70 to 99.9 parts by weight relative to the total 100 parts by weight of the adhesive composition, specifically 70 to 99 parts by weight, 80 to 90 parts by weight, 90 to 90 parts by weight relative to the total 100 parts by weight of the adhesive composition 95 parts by weight or 85 to 95 parts by weight. For example, the adhesive composition comprises 93 parts by weight of an epoxy resin and 7 parts by weight of an organic acid, or 88 parts by weight of an epoxy resin; 6 parts by weight of organic acid; And 6 parts by weight of an aromatic alcohol.

In addition, the epoxy resin is a polyfunctional epoxy resin, bisphenol-based epoxy resin, novolak-type epoxy resin, naphthalene-type epoxy resin, trisphenol methane-type epoxy resin and one selected from the group consisting of glycidyl amine-type epoxy resin It may include the above. In the present invention, by including the epoxy resin as described above, the cured product prepared from the adhesive composition can be thermally cured, and high temperature durability and strength of the cured product can be improved. In addition, when the epoxy resin contains any one or more of an organic acid, an aromatic alcohol and an aprotic solvent as an additive, there is an advantage of excellent compatibility with them. In the present invention, "compatibility" refers to the affinity between each component mixed in the composition. When compatibility is low, it is difficult to uniformly mix the composition, and there is a problem in that physical properties such as adhesion or moldability of the deco sheet are deteriorated. have. The present invention can significantly improve the adhesiveness and moldability of the decor sheet by including an epoxy resin having high compatibility with an organic acid, an aromatic alcohol, and an aprotic solvent as a resin constituting the main component of the adhesive composition.

In addition, the adhesive composition according to the present invention may include any one or more of an organic acid, an aromatic alcohol, and an aprotic solvent together with an epoxy resin.

At this time, the organic acid may include one or more selected from the group consisting of maleic acid, fumaric acid, itaconic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, acrylic acid, methacrylic acid and stearic acid. Specifically, the organic acid may include maleic acid, fumaric acid, phthalic acid or isophthalic acid. More specifically, the organic acid may be maleic acid.

In addition, the content of the organic acid may be 0.1 to 10 parts by weight based on 100 parts by weight of the total adhesive composition, specifically 0.1 to 10 parts by weight, 0.1 to 8 parts by weight, 0.1 to 6 parts by weight based on 100 parts by weight of the total adhesive composition Parts, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, 1 to 6 parts by weight, 1 to 5 parts by weight, 2 to 4 parts by weight, 3 to 5 parts by weight, 3 to 7 parts by weight, 5 to 8 parts by weight, It may be 7 to 10 parts by weight, 0.2 to 5 parts by weight, 0.2 to 1 part by weight, 0.8 to 1.5 parts by weight, or 0.3 to 1.5 parts by weight.

In addition, the aromatic alcohol may include one or more selected from the group consisting of phenol, hydroquinone, catechol, benzenediol, and naphthol. Specifically, the aromatic alcohol may be phenol, hydroquinone or benzenediol. More specifically, the aromatic alcohol may be phenol or hydroquinone.

At this time, the content of the aromatic alcohol may be 0.1 to 10 parts by weight relative to the total 100 parts by weight of the adhesive composition, specifically 0.1 to 10 parts by weight, 0.1 to 8 parts by weight, 0.1 to 6 parts by weight relative to the total 100 parts by weight of the adhesive composition Parts by weight, 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, 1 to 6 parts by weight, 1 to 5 parts by weight, 2 to 4 parts by weight, 3 to 5 parts by weight, 3 to 7 parts by weight, 5 to 8 parts by weight , 7 to 10 parts by weight, 0.2 to 5 parts by weight, 0.2 to 1 part by weight, 0.8 to 1.5 parts by weight or 0.3 to 1.5 parts by weight.

Furthermore, the polar aprotic solvent may include one or more selected from the group consisting of dimethyl sulfoxide (DMSO), dimethyl formamide (DMF) and acetonitrile. Specifically, the polar aprotic solvent may be dimethyl sulfoxide (DMSO) or dimethyl formamide. More specifically, the polar aprotic solvent may be dimethyl sulfoxide (DMSO).

At this time, the content of the polar aprotic solvent may be 0.1 to 10 parts by weight relative to the total 100 parts by weight of the adhesive composition, specifically 0.1 to 10 parts by weight, 0.1 to 8 parts by weight, 0.1 to 0.1 parts by weight to the total 100 parts by weight of the adhesive composition 6 parts by weight, 0.1-5 parts by weight, 0.1-3 parts by weight, 1-6 parts by weight, 1-5 parts by weight, 2-4 parts by weight, 3-5 parts by weight, 3-7 parts by weight, 5-8 parts by weight Parts, 7 to 10 parts by weight, 0.2 to 5 parts by weight, 0.2 to 1 part by weight, 0.8 to 1.5 parts by weight or 0.3 to 1.5 parts by weight. However, the polar aprotic solvent is preferably included in an amount of 1 part by weight or less based on 100 parts by weight of the total adhesive composition for compatibility of the adhesive composition when used in combination with an organic acid and an aromatic alcohol.

The adhesive composition according to the present invention increases the depth of voids provided in the metal layer when the adhesive composition is applied on the metal layer by controlling the organic acid, aromatic alcohol and / or the polar aprotic solvent to the above-described configuration, thereby increasing the surface roughness and / or The specific surface area can be optimized to improve the wettability of the adhesive composition.

Deco sheet

In addition, the present invention in one embodiment,

Base layer; Metal layer; And the adhesive layer prepared from the adhesive composition according to the present invention described above are sequentially stacked,

The metal layer includes voids,

The pores have an average depth of 1 nm to 15 nm, providing a decorative sheet.

The adhesive layer included in the decor sheet according to the present invention is formed from the adhesive composition according to the present invention described above and serves to increase the depth of voids included in the metal layer, thereby improving the adhesion to the metal layer. In addition, since the adhesive layer formed from the adhesive composition exhibits high elongation, the decor sheet containing the same exhibits excellent durability and formability.

As an example, when evaluating adhesiveness according to the evaluation method of ASTM D3359, the decorative sheet may be peeled off with an area of 5% or less of the total area. More specifically, when decorating the decor sheet according to ASTM D3359 A evaluation method, an area of about 5% or less or 3% or less of the total area may be peeled or removed, which may be 4 or more when converted to a grade. have. In addition, the deco sheet is excellent in adhesiveness, and in some cases, peeling or damage of the adhesive layer and / or the metal layer may not occur at all in the evaluation of the adhesiveness (damage area: ≒ 0%, grade 5).

In addition, the decorative sheet has an improved elongation and may be 1% to 15% when elongated after heating to 70 ° C for 1 ± 0.2 minutes. Specifically, the average elongation of the decor sheet is 1 to 15%, 1 to 12%, 1 to 10%, 1 to 5%, 5 to 10%, 10 to 12%, 10 to 15%, 2 to 4%, 2 to 8%, 6 to 10%, 7 to 12%, 12 to 15%, 6 to 11%, or 9 to 12%.

Hereinafter, each configuration of the decor sheet according to the present invention will be described in more detail.

First, the decor sheet according to the present invention includes a base layer as a base substrate, wherein the base layer may be a transparent base layer. Specifically, the base layer may include at least one selected from the group consisting of polyvinyl chloride (PVC) and polyethylene terephthalate (PET). More specifically, the base layer may be polyethylene terephthalate (PET). In addition, the substrate layer may have a hairline pattern formed on one surface.

Next, the decor sheet according to the present invention includes a metal layer on one surface of the base layer, and when a hairline pattern is formed on the base layer, a metal layer may be included on the surface of the base layer on which the hairline pattern is formed. Here, the metal layer is formed to a certain thickness on the surface of the substrate layer to realize a metal texture, thereby improving the aesthetic effect of the decor sheet. The metal layer may include various types of metals, but specifically, at least one of aluminum (Al), stainless steel (SUS), nickel (Ni), copper (Cu), chromium (Cr), and molybdenum (Mo). It may include, and more specifically, may include aluminum (Al), nickel (Ni), copper (Cu) or molybdenum (Mo). As one example, the metal layer may include aluminum (Al) or nickel (Ni).

In addition, the average thickness of the metal layer may have an average thickness of 10 nm to 20 nm. Specifically, the average thickness of the metal layer is 10 nm to 18 nm, 10 nm to 15 nm, 11 nm to 13 nm, 14 nm to 19 nm, 12 nm to 16 nm, 14 nm to 18 nm, or 16 nm to 20 nm Can be More specifically, the average thickness of the metal layer may be 15 nm to 17 nm.

In addition, the metal layer may be formed by a conventional method of forming a metal layer on a transparent substrate layer in the art. For example, the metal layer may be formed by an ion plating method, a sputtering method, a high frequency plasma method, an arc method, a plasma deposition method, or a chemical vapor deposition method such as plasma assisted chemical vapor deposition (PACVD).

In addition, the metal layer has pores on the surface, and the pores may have an average depth in the range of 1 nm to 15 nm. Specifically, the average depth of voids included in the surface of the metal layer is 1 nm to 5 nm, 3 nm to 8 nm, 3 nm to 13 nm, 5 nm to 13 nm, 8 nm to 12 nm, 4 to 7 nm, 6 nm To 9 nm, 11 nm to 14 nm, or 5 nm to 10 nm. More specifically, the average depth of the pores may be 4 nm to 6 nm. Deco sheet of the present invention by including the above-mentioned pores on the surface of the metal layer, the surface area of the metal layer is increased to improve the adhesion between the metal layer and the adhesive layer, thereby exhibiting an excellent effect of durability of the decor sheet.

Next, the decor sheet according to the present invention includes an adhesive layer formed from the adhesive composition according to the present invention on the metal layer. The adhesive layer has a form that penetrates into the pores formed on the surface of the metal layer, and thus can physically and mechanically impart high adhesion to the metal layer, and thus the surface (2D) plated with the deco sheet, as well as curved or curved surfaces (3D) High adhesion and elongation can be achieved when bonding to.

Hereinafter, the present invention will be described in more detail by examples and experimental examples.

However, the following examples and experimental examples are merely illustrative of the present invention, and the contents of the present invention are not limited to the following examples and experimental examples.

Example  1 to 5.

An epoxy resin (bisphenol A, weight average molecular weight (Mw): 500 to 150000), maleic acid, phenol, and dimethyl sulfoxide were compounded as shown in Table 1 below to prepare an adhesive composition. In addition, the compatibility of the prepared adhesive composition was evaluated. Specifically, the compatibility of the composition was observed by visually observing the prepared adhesive composition to confirm the presence or absence of clouding and gelling phenomenon. When all components are uniformly mixed and turbidity and gelation are not confirmed, ○, cloudiness and / or gelation If confirmed, it is marked with X.

Unit: parts by weight	Preparation Example 1	Preparation Example 2	Preparation Example 3	Preparation Example 4	Preparation Example 5
Epoxy resin	100	100	100	100	100
Maleic acid	One	-	-	0.5	0.5
phenol	-	10	-	7	5
DMSO	-	-	One	-	0.5
Compatibility	○	○	○	○	○

Example  6 to 10.

A polyethylene terephthalate (PET, average thickness: 200 ± 10 μm) film was prepared, and aluminum was deposited on the polyethylene terephthalate film to form a metal layer (average thickness: 15 ± 1 nm). The adhesive compositions prepared in Examples 1 to 5 were applied and thermally cured to form an adhesive layer (average thickness: 150 ± 10 μm) to prepare a decor sheet.

	Adhesive composition used
Example 6	Adhesive composition of Example 1
Example 7	Adhesive composition of Example 2
Example 8	Adhesive composition of Example 3
Example 9	Adhesive composition of Example 4
Example 10	Adhesive composition of Example 5

Comparative example  One.

An adhesive composition was prepared in the same manner as in Example 1, except that the polyester resin was used instead of the epoxy resin in Example 1.

As a result of visually observing the prepared adhesive composition, it was confirmed that the whitening phenomenon occurred because the polyester resin and maleic acid were not uniformly mixed.

Comparative example  2.

An adhesive composition comprising only the epoxy resin used in Example 1 as an adhesive composition was prepared.

Comparative example  3 to 6.

Epoxy resin, maleic acid, phenol and dimethylsulfoxide (DMSO) were compounded as shown in Table 3 below to prepare an adhesive composition. In addition, the compatibility of the prepared adhesive composition was evaluated. Specifically, the compatibility of the composition was observed by visually observing the prepared adhesive composition to confirm the presence or absence of clouding and gelling phenomenon. When all components are uniformly mixed and turbidity and gelation are not confirmed, ○, cloudiness and / or gelation If confirmed, it is marked with X.

Unit: parts by weight	Comparative Example 3	Comparative Example 4	Comparative Example 5	Comparative Example 6
Epoxy resin	100	100	100	100
Maleic acid	5	-	0.1	20
phenol	-	5	-	-
DMSO	5	5	-	-
Compatibility	X	○	○	X

Comparative example  7 to 11.

A polyethylene terephthalate (PET, average thickness: 200 ± 10 μm) film was prepared, and aluminum was deposited on the polyethylene terephthalate film to form a metal layer (average thickness: 15 ± 1 nm). The adhesive compositions prepared in Comparative Examples 2 to 6 were applied and thermally cured to form an adhesive layer (average thickness: 150 ± 10 μm) to prepare a decor sheet.

	Adhesive composition used
Comparative Example 7	Adhesive composition of Comparative Example 2
Comparative Example 8	Adhesive composition of Comparative Example 3
Comparative Example 9	Adhesive composition of Comparative Example 4
Comparative Example 10	Adhesive composition of Comparative Example 5
Comparative Example 11	Adhesive composition of Comparative Example 6

Experimental example  One.

In order to confirm the structure of the decor sheet according to the present invention, a specimen was formed by depositing aluminum on a polyethylene terephthalate (PET, average thickness: 200 ± 10 μm) film to form an Al metal layer (average thickness: 15 ± 1 nm). . Scanning electron microscopy (SEM) analysis was performed on the prepared specimens and the decor sheets prepared in Examples 6 and 7, and the results are shown in FIG. 1.

As shown in Fig. 1, in the decorative sheet of Example 6 according to the present invention, it was confirmed that a metal layer and an adhesive layer were sequentially stacked on a polyethylene terephthalate film as a base layer, and the adhesive layer penetrated into the pores formed on the surface of the metal layer and cured. have.

In addition, the specimen having only the Al metal layer formed on the polyethylene terephthalate film and the decor sheet of Comparative Example 7 had an average thickness of about 0.5 to 1 nm and an average depth of about 2 to 4 nm of pores formed on the surface of the metal layer. The decor sheet of 6 was found to have an average thickness of about 1.2 to 1.8 nm and an average depth of about 5 to 8 nm in the metal layer pores.

This means that the depth of the pores on the surface of the metal layer is increased by the organic acid, aromatic alcohol and / or polar aprotic solvent contained in the adhesive composition penetrating the pores formed in the metal layer and etching the pores.

Experimental example  2.

In order to evaluate the properties of the film of the decorative sheet according to the present invention, adhesiveness and moldability were evaluated for the decorative sheets prepared in Examples 6 to 10 and Comparative Examples 8 to 11. The specific evaluation method is as follows, and the results are shown in Table 5 below:

A) Adhesion evaluation

In accordance with the evaluation method of ASTM D3359, the surface of the decor sheet was cut with a cross hatch cutter with an angle of 30 to 45 °, a length of about 40 mm (1.5 inch) and a spacing of 1 mm. Then, the tape (Nichiban's Tape) was firmly attached along the grid to the cut surface and quickly peeled off to check the peeling state of the cut grid. It was given according to the confirmed peeling state, and the criteria are as follows:

Grade 0: grid area completely peeled off,

Grade 1: Peeling was confirmed within about 35% to 65% of the total area,

Grade 2: Peeling was confirmed within 15% to 35% of the total area,

Grade 3: Peeling was confirmed within 5% to 15% of the total area,

Grade 4: Peeling of about 5% of the total area was confirmed.

Grade 5: Peeling of the cut surface was not observed.

B) Evaluation of formability

Decosheets of Examples and Comparative Examples were cut to 70 cm in width and 150 cm in length to prepare specimens, and the prepared specimens were fixed to an Ericsson Test machine, followed by polishing the center of the specimens (average thickness: 10 When it was pushed to ± 0.5 cm), cracks and / or cracks were observed. At this time, the evaluation result was measured by the depth at which the specimen was pushed when cracks and / or cracks occurred.

	Adhesiveness	Formability
Example 6	5 ratings	9 mm
Example 7	5 ratings	9 mm
Example 8	4 Ratings	10 mm
Example 9	5 ratings	9 mm
Example 10	5 ratings	9 mm
Comparative Example 8	-	-
Comparative Example 9	3 ratings	8 mm
Comparative Example 10	3 ratings	7 mm
Comparative Example 11	-	-

It can be seen that the decorative sheet according to the present invention has excellent adhesiveness and formability.

Specifically, referring to Table 5, it was shown that the decorative sheet of the embodiment exhibits an adhesive strength of 4 or higher when evaluating adhesiveness, and in particular, when an adhesive composition containing an organic acid and / or aromatic alcohol together with an epoxy resin is used, the 5th grade It can be seen that it has a high adhesion. In addition, the decorative sheet of the example was improved in elongation, it was found that when the specimen was fixed to the Ericsson test machine and then pushed for evaluation of formability, it was pushed over 9 mm without damaging the decorative sheet.

On the other hand, the decor sheets of Comparative Examples 8 and 11 prepared using the adhesive composition in which cloudiness and / or gelation was observed with the naked eye were markedly deteriorated in both adhesiveness and moldability, and it was found that accurate evaluation was difficult. In addition, the decor sheets of Comparative Examples 9 and 10 have good compatibility, but the composition shows an adhesiveness of 3 grades or less using an adhesive composition different from the present invention, and the elongation is not high. When the specimen was pushed over mm, damage to the deco sheet was confirmed.

From these results, the decor sheet according to the present invention includes a coating layer formed from an adhesive composition containing a specific composition and content of an organic acid, an aromatic alcohol, and / or a polar aprotic solvent together with an epoxy resin, thereby providing 2D and 3D adhesion and elongation. Since it is very excellent, it can be seen that it has excellent durability and moldability.

The adhesive composition according to the present invention comprises an organic acid, an aromatic alcohol and / or a polar aprotic solvent together with an epoxy resin, so that the adhesive layer formed using the adhesive composition has high adhesion to the metal layer even under conditions where the primer layer is excluded. Since it exhibits good properties and high elongation and is excellent in durability and formability, it can be usefully used as a teco sheet.

Claims (11)

1. Epoxy resins; And

   Contains at least one component selected from the group consisting of organic acids, aromatic alcohols and polar aprotic solvents,

   The organic acid, the aromatic alcohol and the polar aprotic solvent are independently an adhesive composition comprising 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the total adhesive composition.
2. According to claim 1,

   The adhesive composition,

   (1) epoxy resins and organic acids;

   (2) epoxy resins and aromatic alcohols;

   (3) epoxy resin and polar aprotic solvent;

   (4) epoxy resins, organic acids and aromatic alcohols; or

   (5) An adhesive composition comprising an epoxy resin, an organic acid, an aromatic alcohol, and a polar aprotic solvent.
3. According to claim 1,

   The organic acid is an adhesive composition, characterized in that at least one member selected from the group consisting of maleic acid, fumaric acid, itaconic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, acrylic acid, methacrylic acid and stearic acid.
4. According to claim 1,

   Aromatic alcohol is an adhesive composition, characterized in that at least one selected from the group consisting of phenol, hydroquinone, catechol, benzenediol and naphthol.
5. According to claim 1,

   The polar aprotic solvent is at least one selected from the group consisting of dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and acetonitrile (acetonitrile).
6. Base layer; Metal layer; And the adhesive layer comprising the adhesive composition according to claim 1 is sequentially stacked,

   The metal layer includes voids,

   Deco sheet having an average depth of the pores of 1 nm to 15 nm.
7. The method of claim 6,

   Deco sheet, characterized in that the average thickness of the metal layer is 10 ㎚ to 20 ㎚.
8. The method of claim 6,

   The metal layer is a decorative sheet comprising at least one of aluminum (Al), stainless steel (SUS), nickel (Ni), copper (Cu), chromium (Cr), and molybdenum (Mo).
9. The method of claim 6,

   The base layer is a decor sheet comprising at least one selected from the group consisting of polyvinyl chloride (PVC) and polyethylene terephthalate (PET).
10. The method of claim 6,

    Deco sheet, when evaluating adhesiveness according to ASTM D3359 A evaluation method, characterized in that the area of less than 5% of the total area is peeled off.
11. The method of claim 6,

    Deco sheet is a deco sheet, characterized in that the average elongation at 1% to 15% upon heating after heating to 70 ° C. for 1 ± 0.2 minutes.

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