KR19990053828A - A decorative sheet - Google Patents

Abstract

A polyester base film, a primer coating layer formed on at least one surface of the polyester base film, a printing layer formed on the primer coating layer, an adhesive layer formed on the printing layer and polyvinyl laminated on the adhesive layer In a decorative sheet comprising a chloride sheet, the primer coating layer comprises a dicarboxylic acid component consisting of at least 85 mol% of aromatic dicarboxylic acid and up to 15 mol% of sulfonic acid alkali metal salt containing dicarboxylic acid. The present invention is formed of a composition comprising a water-soluble polyester resin having an average molecular weight of 3,000 to 8,000 and a glass transition temperature of 52 to 67 ° C., a thermosetting urethane prepolymer having a hydrophilic group, and colloidal silica having a particle size of 50 to 200 nm. The decorative plate sheet by the base film and the base material It is excellent in the interlayer adhesion and durability between sheets, and can be used as a decorative sheet sheet for various purposes.

Description

A decorative sheet

The present invention relates to a decorative plate sheet, and more particularly, to a decorative plate sheet having excellent interlayer adhesion and durability between the printing layer and the base film.

The decorative sheet is usually printed on a polyester film with a desired pattern to form a printing layer, and coated with an adhesive on the printing layer to form an adhesive layer, and the polyester film coated with the ink and the adhesive is coated with a base sheet. It is produced by lamination. Such a smooth sheet sheet has excellent smoothness and high print sharpness, high gloss, temperature resistance, and weather resistance of polyester film, so it can be used for interior products such as furniture, steel sheets, walls, etc. as well as advertisement sheets for outdoor vehicles. It can be used extensively.

In the production of the decorative sheet, in particular, the problem of firmly adhering the print layer onto the polyester film is very important, because the stretched polyester film is generally hydrophobic and is commonly used in the flexo or gravure ink. This is because it is very difficult to coat the printed layer using an or the like. If the interlayer adhesion between the printing layer and the polyester film is weak, the durability of the decorative sheet produced using the same cannot be ensured.

Therefore, in order to solve these drawbacks, a method of coating a special ink on the surface of the polyester film has been devised, but since these special inks mostly use organic solvents, various resin combinations, and expensive blends as substrates, the actual production line There was a problem that it was inappropriate and dangerous to use. Therefore, first, a primer layer is coated with at least one surface of the polyester film with an adhesive material to the film, and then the ink is printed to alleviate the hydrophobicity of the polyester film to form a printed layer on the film. This has been disclosed. However, as the material for forming the primer layer, organic materials including phenolic materials have been generally used. These materials have disadvantages of being inadequate in terms of environmental protection and harmful to the health of workers.

Examples of the prior art for coating the primer layer on the film surface include US Pat. Nos. 4,486,483 and 4,544,200. The patent provides a technique for imparting ink adhesion to a film by primer coating a film surface with a composition comprising an alkali metal salt of an unsaturated fatty acid and an alkali metal salt of an alkyl sulfate as a non-toxic coating. However, in the case of manufacturing the decorative sheet after coating the primer layer by the method according to the patent, the adhesion between the primer layer and the printing layer is not sufficient as the level required for the decorative sheet. In addition, in the case of a biaxially stretched polyester film, a high coefficient of friction causes appearance defects such as blocking and wrinkling, so that the problem of imparting slip properties to the film is also very prerequisite in the manufacturing process of the cosmetic sheet. It is an important task.

The technical problem to be achieved by the present invention is to overcome the above problems, to provide a decorative sheet sheet excellent in the interlayer adhesion between the printing layer and the base film and durability.

1 is a cross-sectional view showing an embodiment of a decorative plate sheet according to the present invention.

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

11: polyester base film

12: primer coating layer

13: printed layer

14: adhesive layer

15: polyvinylchloride sheet

In order to achieve the above technical problem, in the present invention, a polyester base film, a primer coating layer formed on at least one surface of the polyester base film, a printing layer formed on the primer coating layer, is formed on the printing layer In the decorative sheet comprising an adhesive layer and a polyvinyl chloride sheet laminated on the adhesive layer, the primer coating layer is 85 mol% or more aromatic dicarboxylic acid and 15 mol% or less sulfonic acid alkali metal salt-containing dicarboxylic acid It comprises a dicarboxylic acid component consisting of a water-soluble polyester resin having a number average molecular weight of 3,000 to 8,000 and a glass transition temperature of 52 to 67 ℃, a thermosetting urethane prepolymer having a hydrophilic group and colloidal silica having a particle size of 50 to 200nm Characterized in that the composition is formed A decorative sheet is provided.

Here, as the urethane prepolymer, a compound represented by the following Chemical Formula 1 is preferable.

In Chemical Formula 1,

R represents a body portion to which the hydroxyl group of the polymer polyol compound is connected,

B is SO ₃ X (where X is H ⁺ , Na ⁺ or K ⁺ ), NaNO ₂ , NaNO ₃ or NaHCO ₃ .

In addition, the total solid concentration in the composition is preferably 20% by weight or less, and the viscosity of the composition is preferably adjusted to 100cps. On the other hand, the content of the urethane prepolymer and colloidal silica is preferably adjusted to 1 to 30% by weight and 0.01 to 20% by weight, respectively, based on the polyester resin solid content.

In the present invention, the thickness of the primer coating layer is appropriate about 0.001 to 0.5㎛. In addition, it is preferable that the thickness of the said polyvinyl chloride sheet is 1-1000 micrometers.

On the other hand, in the decorative sheet of the present invention, the total thickness of the printed layer and the adhesive layer is preferably adjusted to 0.1 to 100 m.

Hereinafter, the decorative plate sheet according to the present invention will be described in detail.

In the decorative sheet according to the present invention, the polyester resin for the base film is prepared by polycondensing a polyhydric organic acid component and a polyhydric alcohol component, and the organic acid component is preferably a carboxylic acid, particularly an aromatic dicarboxylic acid, As said alcohol component, glycol, especially alkylene glycol is preferable.

Specific examples of the aromatic dicarboxylic acid include dimethyl terephthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl dicarboxylic acid and diphenyl ether. Dicarboxylic acid, anthracene dicarboxylic acid or α, β-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and the like, among which dimethyl terephthalic acid or terephthalic acid is particularly preferred. .

Specific examples of the alkylene glycol include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol or hexylene glycol, and among these, ethylene glycol is particularly preferable.

In the present invention, the method for producing the polyester film is not particularly limited as long as it is a conventional method known in the art, and the apparatus for use thereof is also not limited. For example, a cast sheet of the polymer is prepared by melting the polyester polymer obtained by transesterification and polycondensation reaction and extruding it into an amorphous sheet on a shiny rotary casting drum. Subsequently, the sheet is uniaxially stretched in one of the extrusion direction (the longitudinal direction) or the direction perpendicular to the extrusion direction (the transverse direction) or biaxially stretched in both directions to produce a uniaxial or biaxially stretched film. do. Suitable draw ratios for imparting strength and toughness to the film are about 3 to 5 times, preferably about 3.2 to 4.2 times, in both the longitudinal and transverse directions.

The stretching process is preferably carried out at a temperature near the secondary transition temperature to below the temperature at which the polymer softens and melts. In some cases, the polyester film is crystallized by performing a heat treatment process for a predetermined time, for example, a time required for crystallization of the film, to impart stability and tensile properties to the finished film. The heat treatment temperature is typically maintained at about 190 to 250 ℃, preferably about 215 to 245 ℃.

The polyester resin used in the preparation of the resin composition of the present invention is a water-soluble or water-dispersible high molecular compound having an ester bond in the molecular backbone obtained by transesterification and polycondensation of dicarboxylic acid and diol, and at least 85 mol% of aromatic dica A dicarboxylic acid consisting of a carboxylic acid and dicarboxylic acid containing up to 15 mol% of sulfonic acid alkali metal salt, having a number average molecular weight of about 50,000 or less, preferably 25,000 or less, and having a glass transition temperature of 80 ° C. or less. Resin which has is preferable.

As the dicarboxylic acid component used in the polyester copolymer resin, terephthalic acid, isophthalic acid, adipic acid, 5-sodium sulfoisophthalic acid, trimellilic acid, phthalic anhydride, sebacic acid, succinic acid and the like are used as the diol component. Specific examples include ethylene glycol, 1,4-butanediol, propylene glycol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polypropylene glycol, cyclohexane dimethanol, and the like.

On the other hand, examples of the prior art using a sulfomonomer component containing a metal sulfonate group bonded to an aromatic nucleus in order to aqueousize the polymer compound as described above, US Pat. A technique is disclosed in which sodium sulfophthalic acid, 5-sodium sulfoisophthalic acid, 5-sulfopropoxy isophthalic acid and the like are added in an amount of 2 to 20 mol% with respect to an aromatic or dibasic acid derivative as a monomer component. Adhesives using polyester or copolyester coatings derived from sulfoisophthalic acid (see US Pat. No. 4,252,885) or coatings consisting of isophthalic acid, sulfoisophthalic acid and terephthalic acid (see EP-A-0,029,629). Techniques for producing photographic films with excellent properties have been known, and also terephthalic acid and / or isophthalate. , Aqueous dispersion of polymer consisting of saturated aliphatic dicarboxylic acid and sulfonate monomers (U.S. Patent No. 3,563,942) and similar materials (U.S. Patent No. 3,779,993) are known to be useful as hot melt adhesives.

As the composition of the present invention, a mixture of a urethane resin and colloidal silica is used in a polyester copolymer resin containing a sulfonate component as described above.

The urethane resin used in the present invention is a thermosetting urethane prepolymer represented by Chemical Formula 1 having a urethane bond obtained by polycondensing a polyol and a polyisocyanate, which is an active hydrogen compound, in the molecular chain and having a hydrophilic block group at the molecular end thereof. Dissolves well in water without water.

The polyol component of the urethane prepolymer may be a polyester polyol containing an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid, a block copolymer of propylene oxide and ethylene oxide or a block copolymer of alkylene oxide and ethylene oxide Or alkylene oxides and active hydrogen compounds (eg alcohols, fatty acids, amines, etc.) can be obtained from polymerized polyether polyols and other known polyols.

As the polyisocyanate component of the urethane prepolymer, diisocyanate such as 5-isocyanate-1-isocyanatemethyl-1,3,3-trimethyl cyclohexane and the like is preferable. In general, the isocyanate group has a property of rapidly reacting with a compound such as alcohol or water having an active hydrogen atom, and thus, when the urethane prepolymer having an isocyanate group as a terminal group is brought into contact with water, foaming and gelation is accompanied by decarbonation reaction. cause. Therefore, in order to stabilize the highly reactive isocyanate compound in water, it is necessary to protect the isocyanate group by using a blocking agent to block the reaction of water and isocyanate. In the present invention, a block group B is used to form a strong hydrophilic group carbamoyl group (-NHCO-B) at the end of the urethane prepolymer molecule so that the prepolymer is well dissolved in water without using an emulsifier. The block group is released again under certain conditions.

In one embodiment of the decorative sheet according to the present invention, the urethane prepolymer is a block copolymer of propylene oxide and ethylene oxide or a polyether polyol polymerized with an alkylene oxide and a polyisocyanate polymerized to bond an ether to a molecular backbone. Preference is given to anionic thermosetting urethane prepolymers having an anionic type having a carbamoyl sulfonate group at the molecular end thereof.

The total solids concentration in the composition is suitably 20% by weight or less, preferably 1 to 10% by weight, and the viscosity is preferably 100cps or less, but particularly suitable for a coating process having a viscosity of 20cps or less. . In some cases, in order to promote the reaction, a catalyst known in the art may be added to the resin composition by about 2 to 3% by weight based on the solids content of the composition, and the amount of heat required for the reaction during drying may be insufficient or 2 When coating the resin composition on the axially stretched film serves to increase the coating efficiency. In addition, hardening agents, such as aqueous melamine or urea / formaldehyde condensation products, may also be added in order to further modify the properties of the coating material. In addition to the catalyst or hardener, the resin composition of the present invention does not inhibit the effects of the present invention by known additives known in the art, such as antistatic agents, wetting agents, pH adjusting agents, antioxidants, dyes or pigments. It may contain within the range which does not.

In the present invention, the content of the thermosetting urethane prepolymer in the composition is adjusted to 1 to 30% by weight, preferably 10 to 20% by weight, based on the polyester copolymer resin solids. If the content is less than 1% by weight, the effect is inferior. If the content is more than 30% by weight, there is a problem that the surface layer of the film becomes cloudy and physical properties such as ink adhesion are lowered.

In the present invention, the colloidal silica added to improve the slip properties of the film is a silica containing 40 to 60% by weight of SiO ₂ and 0.05 to 0.2% by weight of Na ₂ O, the particle diameter is 50 to 200nm desirable. The amount of the colloidal silica added is preferably 0.01 to 10% by weight based on the polyester copolymer resin solids. If more colloidal silica is added than 20% by weight, the coefficient of friction of the film is improved, but the problem that the transparency and ink adhesion of the coating film are lowered is inevitable.

In the present invention, the process of coating the resin composition on the polyester base film is not particularly limited as long as it is a conventional method known in the art, such as a preliminary process between the casting process of the amorphous sheet and the first stretching process. Direct to one or both surfaces of the film in the pre-draw stage (UK Patent No. 1,411,564) or in the inter-draw stage (U.S. Patent No. 3,214,035) after uniaxial stretching and before biaxial stretching. It is a coating method using a roll, a reverse roll, a reverse gravure roll, a spray, a rod bar or an air knife. The primer coating layer formed on the surface of the film as described above is typically dried by heat applied to the film during the stretching step or the final adjustment step of the film.

As shown in FIG. 1, the decorative plate sheet according to the present invention has a printing layer 13 made of ink and an adhesive layer 14 made of an adhesive on the primer coating layer 12 of the polyester film 11 prepared as described above. Is sequentially coated, and then polyvinyl chloride sheet 15 is laminated on the adhesive layer.

In the production of the decorative sheet according to the present invention, the method of laminating the polyvinyl chloride sheet on the polyester film is not particularly limited as long as it is a conventional method known in the art.

The thickness of the polyvinyl chloride sheet is preferably adjusted to 1 to 1000㎛. In the present invention, the polychloride sheet is difficult to be manufactured to a thickness of less than 10 μm, and if the thickness exceeds 1000 μm, the winding property during the manufacturing process of the decorative sheet is inferior and causes a cost increase.

According to a preferred embodiment of the present invention, the total thickness of the printed layer and the adhesive layer is appropriately adjusted to 0.1 to 100㎛.

Since the composition used in the manufacture of the decorative sheet of the present invention imparts excellent thermal stability to the film, any film fragments coated with the composition are mixed with a new polymer such as a polyester polymer to remelt and re-melted in the film forming extruder. It can also supply and manufacture an oriented film. Films prepared in this manner and containing up to about 50% by weight of the coated film piece reclaimed material are commercially advantageous due to their excellent quality, coloration and appearance.

As described above, the composition may be coated on one or both surfaces of the film, and may be coated on only one side of the film and then coated with a thermosetting acrylic or methacrylic coating on the other side. Since the biaxially stretched polyester film surface-coated with the composition as described above is excellent in ink adhesion and slip properties, it is very useful for producing a decorative sheet sheet having improved physical properties.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it goes without saying that the scope of the present invention is not limited to the scope of the following examples. In the following Examples and Comparative Examples, various performance evaluations of the manufactured decorative sheet were performed in the following manner. In the following examples and comparative examples, the evaluation of ink adhesion, friction coefficient, and surface appearance characteristics was performed on a polyester film coated with a primer layer, which is an indirect measure of the physical properties of the decorative sheet.

(1) Lamination Adhesion of Polyvinyl Chloride Sheet

The laminate of the polyester film and the polyvinyl chloride sheet was cut into 25 mm pieces, and the peel force between the two layers was measured while peeling the T-type at a constant speed using an Instron tensile tester (ASTM D882). . The measured peel force is shown in Table 1.

(2) ink adhesion

The printing layer is coated on the surface of the polyester film on which the primer coating layer is formed by using ink (please specify the ink used in detail), and then dried at 100 ° C. for 1 minute. Then, the cellophane tape (manufactured by Daeilsa Co., Ltd.) was well adhered to the coated ink print layer, and then peeled off instantaneously, followed by attaching the cellophane tape to the same portion again and then peeling it off three times. The ink adhesion is evaluated according to the following criteria.

○ (excellent): when the coated colored ink layer remains to the base film to some extent after three peelings

△ (normal): When the coated ink layer does not remain on the base film after peeling twice or three times

X (poor): when the coated colored ink layer does not remain on the base film after one peeling

(3) coefficient of friction

At a load of 200 g, static and dynamic coefficients of friction were measured, respectively, using a surface tester ASTM D 1894 (Heidon-14) from Heydon.

(4) surface appearance

The appearance of the film surface was evaluated by the following criteria by visually measuring the frequency of occurrence of fish eye.

○: When no fish eye occurs

△: 2 to 4 fish eyes per unit area

×: 5 or more fisheye per unit area

<Example 1>

A mixture of 49.5 mol% of dimethyl terephthalate, 49.5 mol% of dimethylisophthalate and 8.5 mol% of sodium 5-sulfoisophthalate as a dicarboxylic acid component was transesterified and polycondensed with ethylene glycol and diethylene glycol to 70 ° C. A polyester copolymer resin having a glass transition temperature of was prepared. 100 g of the polyester resin was added to 1 L of ionized water maintained at about 95 DEG C in a 2 L stainless steel vessel with vigorous stirring to allow it to solubilize. The water-soluble polyester copolymer resin was then cooled to room temperature and filtered to adjust the solids content to 5% by weight, and then the water-soluble polyurethane prepolymer containing ether bonds in the molecular backbone was determined based on the polyester copolymer resin. 0.1 g of colloidal silica having a weight percentage and a particle size of 50 to 200 nm was added and mixed to prepare a composition having a final solid concentration of 5 wt%.

Subsequently, a slot die on a casting drum was melted from a dimethyl terephthalate and ethylene glycol through a transesterification reaction and a polycondensation reaction by a conventional method and kept at a temperature of about 20 ° C. After extrusion through, cooling to prepare a cast sheet. After the longitudinal stretching was performed at a draw ratio of about 3.5 times while maintaining the sheet at about 80 ° C., the dry weight of the coating composition was approximately 0.05 by reverse gravure printing without corona discharge treatment on one surface of the stretched film. g / cm 2, and after coating, the coating was coated to have a thickness of about 0.05 μm.

Subsequently, after drying at about 100 DEG C, a biaxially stretched film having a thickness of about 25 mu m was prepared by transverse stretching at a draw ratio of 3.5 times and heat-treated at 210 DEG C. Next, after coating the polyester-based ink to a coating layer of the polyester film prepared as described above with a thickness of 3㎛, dried for 1 minute at 100 ℃, and coated with a polyurethane-based two-component adhesive to a thickness of 6㎛, 60 It dried at 1 degreeC. By laminating the film coated with the printing layer and the adhesive layer by the above method by a conventional dry lamination method, and then leaving the sheet at 60 ° C. for 48 hours for aging to prepare a decorative sheet according to the present invention. .

The physical properties of the manufactured plate sheets were measured by the above-described method, and the results are shown in Table 1.

<Example 2>

Except for adding 10% by weight of the urethane prepolymer to the composition on the basis of the polyester copolymer resin solid content, after preparing the sheet plate in the same manner as in Example 1, the physical properties were evaluated and the results are shown in Table 1. .

<Example 3>

Except for adding 15% by weight of the urethane prepolymer to the composition on the basis of the polyester copolymer resin solid content, after preparing the sheet plate in the same manner as in Example 1, the physical properties were evaluated and the results are shown in Table 1. .

<Example 4>

Except for adding 20% by weight of the urethane prepolymer to the composition on the basis of the polyester copolymer resin solid content, after preparing the sheet plate in the same manner as in Example 1, the physical properties were evaluated and the results are shown in Table 1. .

Example 5

Except for adding 0.01% by weight of colloidal silica to the composition on the basis of the polyester copolymer resin solid content, after preparing the decorative sheet in the same manner as in Example 1, the physical properties were evaluated and the results are shown in Table 1. It was.

<Example 6>

Except for adding 0.5% by weight of colloidal silica to the composition on the basis of the polyester copolymer resin solids, after preparing the sheet plate in the same manner as in Example 2, the physical properties were evaluated and the results are shown in Table 1. It was.

<Example 7>

Except for adding 1% by weight of colloidal silica to the composition based on the polyester copolymer resin solid content, after preparing the sheet plate in the same manner as in Example 3, the physical properties were evaluated and the results are shown in Table 1. It was.

<Example 8>

Except for adding 5% by weight of colloidal silica to the composition on the basis of the polyester copolymer resin solid content, after preparing the sheet sheet in the same manner as in Example 4, the physical properties were evaluated and the results are shown in Table 1. It was.

Comparative Example 1

Except that urethane prepolymer and colloidal silica were not added to the composition, after preparing the sheet plate in the same manner as in Example 1, the physical properties were evaluated and the results are shown in Table 1.

Comparative Example 2

The cosmetic plate sheet was prepared in the same manner as in Example 1 except that WR961 polyester resin manufactured by Japanese Synthesis Inc. was used instead of the water-soluble copolyester resin and no urethane prepolymer and colloidal silica were added. The results are shown in Table 1 below.

Lamination Adhesion of Polyvinyl Chloride Sheet (g / inch) Ink adhesive Coefficient of friction (static / dynamic) Surface appearance Example 1 1300 ○ 0.55 / 0.51 ○ Example 2 1200 ○ 0.50 / 0.46 ○ Example 3 1100 ○ 0.48 / 0.45 ○ Example 4 800 ○ 0.45 / 0.41 ○ Example 5 1000 ○ 0.60 / 0.55 ○ Example 6 900 ○ 0.45 / 0.43 ○ Example 7 800 ○ 0.38 / 0.35 ○ Example 8 700 ○ 0.33 / 0.31 ○ Comparative Example 1 1000 △ 0.70 / 0.65 △ Comparative Example 2 500 × 0.66 / 0.64 ×

As can be seen from the results of Table 1, the decorative sheet produced by the method of Example was generally excellent in the interlayer adhesion between the polyester base film and the polyvinyl chloride sheet compared to the case of the comparative example, the film used In the case of ink adhesion, friction coefficient characteristics and surface appearance properties can be confirmed excellent.

A primer layer is formed on the polyester substrate film by using a composition comprising a water-soluble polyester resin, a thermosetting urethane prepolymer, and colloidal silica, and then the printing layer and the adhesive layer are sequentially coated, and then the polyvinyl chloride sheet and The decorative sheet of the present invention produced by laminating is excellent in the interlayer adhesion between the polyester base film and the polyvinyl chloride sheet, and can be used as a decorative sheet for various purposes.

Claims (9)

Polyester base film; A primer coating layer formed on at least one surface of the polyester base film; A printing layer formed on the primer coating layer; An adhesive layer formed on the printing layer; And In the decorative sheet comprising a polyvinyl chloride sheet laminated on the adhesive layer, The primer coating layer, A dicarboxylic acid component consisting of at least 85 mol% of aromatic dicarboxylic acid and up to 15 mol% of sulfonic acid alkali metal salt-containing dicarboxylic acid, having a number average molecular weight of 3,000 to 8,000, and a glass transition temperature of 52 to 67 ° C. Water-soluble polyester resin which is the following; Thermosetting urethane prepolymers having hydrophilic groups; And A decorative plate sheet formed from a composition containing colloidal silica having a particle diameter of 50 to 200 nm. The cosmetic sheet according to claim 1, wherein the urethane prepolymer is a compound represented by the following Chemical Formula 1. <Formula 1> In Chemical Formula 1, R represents a body portion to which the hydroxyl group of the polymer polyol compound is connected, B is SO ₃ X (where X is H ⁺ , Na ⁺ or K ⁺ ), NaNO ₂ , NaNO ₃ or NaHCO ₃ . The cosmetic sheet according to claim 1, wherein the total solid concentration in the composition is 20% by weight or less. The plate of claim 1, wherein the composition has a viscosity of 100 cps. The cosmetic sheet according to claim 1, wherein the content of the urethane prepolymer is 1 to 30% by weight based on the polyester resin solid content. The cosmetic sheet according to claim 1, wherein the content of the colloidal silica is 0.01 to 20% by weight based on the solid content of the polyester resin. The decorative sheet according to claim 1, wherein the primer coating layer has a thickness of 0.001 to 0.5 µm. The decorative sheet according to claim 1, wherein the polyvinyl chloride sheet has a thickness of 1 to 1000 mu m. The decorative sheet according to claim 1, wherein the total thickness of the printed layer and the adhesive layer is 0.1 to 100 µm.