KR20000059284A - Sheet and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A decorative lamination sheet is to have a good adhesive capability between the base film and the printing layer and a good resistance to heat and water and is to be applied with a water-based coating liquid for economical cost and environment friendliness. CONSTITUTION: The decorative lamination sheet comprises a polyester base film, a primer layer, a print layer, an adhesive layer, and a polyvinylchloride sheet layered in the order of mentioning, the primer layer being composed of an ester group polyurethane resin including 35-35mole% carboxylic acid, 35-55mole% glycol and 5-15mole% di-isocyanate.

Description

Cosmetic plate sheet and manufacturing method thereof

The present invention relates to a decorative plate sheet and a method of manufacturing the same, and more particularly, by using a decorative plate sheet and a water-based coating liquid excellent in the interlayer adhesion between the substrate film and the printing layer and the like. The present invention relates to a method for manufacturing a decorative plate sheet capable of producing a decorative sheet sheet having the above characteristics in an environmentally friendly manner.

The decorative plate sheet typically prints ink on a polyester film in a desired pattern to form a printing layer, and then forms an adhesive layer by applying an adhesive on the printing layer, and the polyester film coated with the ink and the adhesive is polyvinyl chloride. It is produced by laminating with a sheet. This sheet is not only excellent in smoothness, but also has high print sharpness, high gloss, temperature resistance, and weather resistance of polyester film. It can be used extensively.

In the production of the decorative plate sheet, in particular, the problem of firmly adhering the printing layer onto the polyester film is very important. This is because the stretched polyester film is generally hydrophobic, and it is very difficult to apply the printing layer using a commercially available flexo or gravure ink. In order to solve these drawbacks, a method of applying a special ink to the surface of the polyester film has been devised, but since these special inks are mostly used as a substrate using organic solvents, various resin combinations, and expensive blends, they are used in actual production lines. There was a problem of being inappropriate and dangerous. Therefore, a technique of first applying a primer layer with a material that is adhesive to the film on at least one surface of the polyester film, and then printing the ink to relieve the hydrophobicity of the polyester film to form a printed layer firmly 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, and these materials are not appropriate in terms of environmental protection, and have problems that adversely affect the health of workers.

Examples of the prior art for applying the primer layer to 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 comprising 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 applying the primer layer by the method according to the patent, the adhesive force between the primer layer and the printing layer is not sufficient as the level required for the decorative sheet sheet, in particular the sheet laminated in the presence of water The problem that the adhesive force of the liver falls is inevitable.

On the other hand, as a film having excellent adhesion even in the presence of water is required, various methods for imparting hot water resistance to the film have been proposed. For example, Japanese Unexamined Patent Application Publication No. 4-51424 has an effect of improving the hot water resistance by dissolving a coating liquid in an organic solvent and applying it onto a base film. However, since a composition based on an organic solvent is used as a coating liquid, There was a risk of ignition when applied, a bad smell, and a problem of causing environmental pollution.

Accordingly, the technical problem to be achieved by the present invention is to overcome the above problems, to provide a decorative sheet sheet with improved interlayer adhesion between the printed layer and the base film and hot water resistance.

Another technical problem to be achieved by the present invention is to provide a manufacturing method of a decorative plate sheet which can produce a decorative plate sheet having the above characteristics economically and environmentally by using a water-based coating liquid.

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

<Explanation of symbols for main parts of drawing>

11: polyester base film 12: primer layer

13: printed layer 14: adhesive layer

15: polyvinylchloride sheet

In order to achieve the above technical problem, the present invention is a polyester substrate film; A primer layer formed on at least one surface of the polyester base film; A printing layer formed on the primer layer; An adhesive layer formed on the printing layer; And a polyvinyl chloride sheet laminated on the adhesive layer, wherein the primer layer has a dicarboxylic acid component of 35 to 55 mol%, a glycol component of 35 to 55 mol%, and a diisocyanate component To prepare a decorative plate sheet, characterized in that consisting of 5 to 15 mol% ester-based polyurethane resin.

In the cosmetic sheet according to the present invention, the dicarboxylic acid component of the polyurethane resin is 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 to 40 mol of isophthalic acid component It is preferably made of%.

In the decorative sheet sheet according to the present invention, the softening point of the polyurethane resin is preferably 70 ~ 90 ℃.

In the cosmetic sheet according to the present invention, the primer layer is an ester-based polyurethane resin crosslinked by at least one crosslinking agent selected from the group consisting of melamine-formaldehyde resin, urea-formaldehyde resin, and water-soluble blocked diisocyanate resin. Can be done.

In order to achieve the above technical problem, the present invention also provides an ester-based polyurethane resin comprising 35 to 55 mol% of dicarboxylic acid component, 35 to 55 mol% of glycol component, and 5 to 15 mol% of diisocyanate component. Applying a composition consisting of 1 to 10% by weight, 0.01 to 0.5% by weight of surfactant, and the remaining amount of water on one or more surfaces on the polyester base film, and then heat-treating to form a primer layer comprising the step of forming a primer layer Provided is a method for producing a sheet.

In the manufacturing method of the decorative sheet according to the present invention, the dicarboxylic acid component of the polyurethane resin is 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 isophthalic acid component It is preferable that it consists of-40 mol%.

In the manufacturing method of the decorative sheet sheet which concerns on this invention, it is preferable that the softening point of the said polyurethane resin is 70-90 degreeC.

In the method for producing a decorative sheet according to the present invention, the composition further comprises 1 to 5% by weight of at least one crosslinking agent selected from the group consisting of melamine-formaldehyde resin, urea-formaldehyde resin, and water-soluble blocked diisocyanate resin. It is desirable to do it.

In the manufacturing method of the decorative sheet sheet according to the present invention, the composition preferably further comprises 0.1 to 0.5% by weight of the silica-based additive.

Hereinafter, the decorative plate sheet according to the present invention and a manufacturing method thereof will be described in detail.

1 is a cross-sectional view for explaining the structure of a decorative plate sheet according to an embodiment of the present invention. Referring to Figure 1, the decorative plate sheet according to an embodiment of the present invention is a polyester base film 11, a primer layer 12, the printing layer 13 of the ink and the adhesive layer 14 of the adhesive, and The polyvinyl chloride sheet 15 (hereinafter, referred to as PVC sheet) is laminated in this order.

The polyester base film is made of a conventional polyester film such as PET, the thickness is preferably 12 ~ 200㎛. If the thickness is less than 12㎛, there is a problem that the productivity of the manufacturing process of the polyester film is lowered and the possibility of delamination of the decorative plate sheet is increased, and if the thickness exceeds 200㎛, the manufacturing cost increases.

The primer layer 12 laminated in order to firmly adhere the printing layer 13 on the hydrophobic polyester base film 11 is 35 to 55 mol% dicarboxylic acid component, 35 to 55 mol% glycol component , And an ester-based polyurethane resin having a diisocyanate component of 5 to 15 mol%, in particular, the dicarboxylic acid component is 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 to 20 isophthalic acid component. It consists of a coating film which consists of ester-type polyurethane resin which consists of 40 mol%.

The ester-based polyurethane resin is preferably crosslinked by a crosslinking agent such as melamine-formaldehyde resin, urea-formaldehyde resin, or water-soluble blocked diisocyanate resin to increase the coating film strength.

The thickness of the primer layer 12 is preferably adjusted to 0.001 ~ 1㎛. If the thickness is less than 0.001 μm, there is a problem that it is difficult to form the coating layer. If the thickness exceeds 1 μm, there is a problem that the adhesive strength with the ink is lowered.

As the ink of the printing layer 13, any ink can be used as long as the adhesive strength with the polyester base film 11 is not reduced. Of these, polyvinylchloride-based or polyester-based inks are particularly preferable in that they have excellent adhesive strength after lamination.

As the adhesive layer 14, any adhesive may be used as long as the adhesion between the printing layer 13 and the polyvinyl chloride sheet 15 is good. Conventional one-component or two-component curable adhesives may be used. For example, a urethane two-component curable adhesive may be used.

As the PVC sheet, a sheet made of a vinyl chloride polymer, copolymer, or a mixture thereof may be used. The degree of polymerization of PVC is preferably 500 to 1400, more preferably 600 to 800. If the degree of polymerization is less than 500, there is a problem in the mechanical properties, if the degree of polymerization exceeds 800 there is a problem that the moldability is lowered. The PVC sheet may include a plasticizer. For example, phthalic ester, polyester, epoxy and adipic ester plasticizers can be used. Of these, phthalic ester plasticizers such as di- (2-ethylhexyl) phthalic acid ester, which have little migration to the interface with the adhesive layer 14, are preferable.

It is preferable that the thickness of the said PVC sheet is 1-500 micrometers. In order to manufacture the thickness of the PVC sheet to less than 1㎛ there is a problem that the productivity is lowered, if the thickness exceeds 500㎛ there is a problem that the windingability is lowered and the manufacturing cost rises.

Next, the method of manufacturing the decorative plate sheet according to the present invention will be described.

In the present invention, the intrinsic viscosity of the polyester resin used to produce the base film is preferably 0.4 to 0.9 dl / g, preferably 0.5 to 0.8 dl / g. If the intrinsic viscosity is less than 0.4 dl / g, the breakage during stretching in the manufacturing process of the film is frequent and the productivity is greatly reduced, and the physical viscosity such as mechanical strength of the final film is not preferable, whereas the intrinsic viscosity is 0.9 dl / g If it exceeds g, the melt viscosity is very high and the extrusion process becomes unstable during the film forming process, and the productivity in the post process is greatly reduced due to difficulties in the manufacturing process.

The polyester resin is prepared by polycondensing a polyhydric organic acid component and a polyhydric alcohol component. The organic acid component is preferably a carboxylic acid, particularly an aromatic dicarboxylic acid, and preferably the glycol component, particularly an alkylene glycol. .

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 this invention, the method of manufacturing a polyester base film is not specifically limited. For example, the base film is melt-extruded by a conventional method to form a sheet by electrostatic application on a cooling roll of 20 ~ 30 ℃. The unstretched sheet is stretched 2 to 5 times, preferably 3 to 4 times in the longitudinal direction at 70 to 100 ° C, and then 2 to 5 times in the transverse direction at 100 to 120 ° C, preferably 3 to 4 times The polyester base film is completed by stretching and then heat setting at 200 to 260 ° C, preferably 220 to 240 ° C.

Next, the method of apply | coating a primer layer to any one or more surfaces on the said polyester base film is demonstrated. The primer layer may be applied at any time when the base film is unstretched, uniaxially stretched, or biaxially stretched during the manufacturing process of the base film. The method of applying the primer layer is not particularly limited as long as it is a conventional method known in the art. The coating method of the system can be used. As described above, the thickness of the primer layer is adjusted to 0.001 to 1 µm, and the coating density of the primer layer is adjusted to be 0.01 to 0.5 g / m ² .

The composition for applying the primer layer is one in which an ester-based polyurethane is dispersed in water, and the polyurethane resin is a copolymer of a dicarboxylic acid component, a glycol component, and a diisocyanate component.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,5-methyl terephthalic acid or dimethyl isophthalic acid. , Cycloaliphatic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid or 1,4-cyclohexane dicarboxylic acid Acids or aliphatic dicarboxylic acids such as adipic acid and sebacic acid may be used. Among these, terephthalic acid, isophthalic acid and adipic acid are particularly preferable. Terephthalic acid has a function to keep the coating film hard when forming the coating film, and isophthalic acid and adipic acid increase adhesion to the ink.

On the other hand, when the temperature of the roll is higher than the softening point of the primer layer when the PVC sheet and the printed polyester film are laminated, the primer layer turns into a rubber state, and the printing layer penetrates into the primer layer, and between the polyester film and the printing layer. The adhesive force of the becomes high. In consideration of the usual lamination process, it is preferable that the softening point of the ester type polyurethane of a primer layer is 70-90 degreeC. When the ratio of the isophthalic acid component and the adipic acid component is high, the softening point of the polyurethane resin is lowered, thereby increasing the adhesive force to the ink. Therefore, it is very important to copolymerize these three dicarboxylic acid components in combination in appropriate amounts. When the content of terephthalic acid is high, the film strength is excellent, but the ink adhesion is not satisfactory. When the content of isophthalic acid and adipic acid is too high, the ink adhesion is good, but the film strength is low. Problems such as a roll pattern appearing on the coating film during the film manufacturing process occurs. In view of these points, it is preferable that the dicarboxylic acid component of the polyurethane resin is composed of 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 to 40 mol% of isophthalic acid component. Do.

As said glycol component, a C2-C8 aliphatic glycol or a C6-C12 alicyclic glycol is preferable. For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexane dimethanol, 1,3 -Cyclohexane dimethanol, 1,4-cyclohexane dimethanol, p-xylene glycol and the like are preferable. In addition, diethylene glycol, triethylene glycol, polyether glycol, polyethylene glycol or polytetramethylene glycol may be used.

Examples of the diisocyanate component include 2,4-hexamethylene diisocyanate, 2,6-hexamethylene diisocyanate, 5-isocyanate-1-isocyanate methyl-1,3,3-trimethyl cyclohexane represented by the following formula (1), and the like. Derivatives thereof can be used, among which 5-isocyanate-1-isocyanatemethyl-1,3,3-trimethyl cyclohexane is preferable.

The composition of the ester-based polyurethane resin is 35 to 55 mol% dicarboxylic acid component, 35 to 55 mol% glycol component, and 5 to 15 mol% diisocyanate component copolymerized to maximize the effect of the present invention It is preferable.

It is preferable that the composition for laminating | stacking the said primer layer contains the crosslinking agent which can form bridge | crosslinking with a dicarboxylic acid component, a glycol component, and a diisocyanate component. When crosslinking is introduced in the structure of the polyurethane resin by the crosslinking agent, the coating film strength is increased to decrease the adhesiveness of the coating film and to make the coating film hard.

As such a crosslinking agent, it is preferable to contain at least two of an alkoxy group, a hydroxyl group, an amine group, an amide group, and a water-soluble blocked diisocyanate group per molecular structure. Among these, at least one selected from the group consisting of melamine-formaldehyde resins, urea-formaldehyde resins, and water-soluble blocked diisocyanate resins is preferable. Melamine-formaldehyde resins not only dissolve well in water, but also react with ester-based polyurethane resins to form good crosslinked structures.

In the composition, the content of the crosslinking agent should be appropriately adjusted according to the molecular weight and the number of functional groups of the crosslinking agent. In the case of melamine-formaldehyde, 5 to 45% by weight based on the weight of the polyurethane resin, and 20 to 35% by weight More preferred.

The content of the polyurethane resin in the composition is preferably adjusted to 1 to 10% by weight. If the content of the polyurethane resin is less than 1% by weight, there is a problem in the wetting (wetting) when applied to the polyester film, there is a problem that the adhesive strength with the ink may be lowered if it exceeds 10% by weight.

The content of the crosslinking agent in the composition is preferably adjusted to 1 to 5% by weight.

In addition to the composition, it is preferable that the surfactant further comprises 0.01 to 0.5% by weight, silica-based additives 0.1 to 0.5% by weight. The surfactant and / or the silica-based additive serves to lower the surface friction coefficient of the film to improve slip resistance and blocking resistance.

On the other hand, the composition is an additive known in the art, such as antistatic agents, wetting agents, pH adjusting agents, antioxidants, dyes, pigments or slip agents such as colloidal silica and the like does not lower the adhesion to the printing layer It can contain in a range.

After the application of the primer layer on the polyester base film is completed, the printing layer, the adhesive layer, and the PVC sheet are sequentially laminated in accordance with a conventional method. For example, a conventional dry lamination method well known in the art may be used as a method of laminating a PVC sheet on a polyester film in which a printing layer and an adhesive layer are laminated.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. In Examples and Comparative Examples of the present invention, various performance evaluations of the manufactured decorative sheet were performed by the following method.

(1) Peeling force (adhesiveness)

The laminate of the polyester film and the PVC sheet was cut into 25 mm pieces and peeled between the two layers while being T-shaped peeled at a constant speed according to ASTM D 882 using a peel tester (Heiden-17) of Shindong Science Co., Ltd. Force was measured.

(2) hot water resistance

The laminate of the polyester film and the PVC sheet was cut into 25 mm pieces and immersed in water at 100 ° C. for 1 hour, which was then subjected to ASTM D 882 using a peel tester (Heiden-17) of Shindong Science Co., Ltd. The peeling between the two layers was measured while peeling the T-type at a constant speed.

(3) coating film strength

The coating film strength of the polyester film in which the primer layer was laminated by the pencil hardness test (JIS-K5400) was measured.

Examples 1 to 8, Comparative Examples 1 to 4

<Synthesis of polyurethane resin a>

Adipic acid, terephthalic acid and isophthalic acid as the dicarboxylic acid component, ethylene glycol as the glycol component, diethylene glycol and triethylene glycol and 5-isocyanate-1-isocyanatemethyl-1,3,3-trimethyl cyclo as diisocyanate components Hexanes were mixed at a molar ratio of 8: 5: 5: 8: 8: 4: 4, to which dibutyltindilaurate (DBTDL) was added as catalyst and copolymerized by conventional polymerization methods. The softening point of the polyurethane resin a obtained in this way was 70-80 degreeC.

<Synthesis of polyurethane resin b>

Terephthalic acid and isophthalic acid as the dicarboxylic acid component, ethylene glycol as the glycol component, diethylene glycol and triethylene glycol, and 5-isocyanate-1-isocyanatemethyl-1,3,3-trimethylcyclohexane as the diisocyanate 9: The mixture was mixed at a molar ratio of 9: 8: 8: 4: 4, to which dibutyltindilaurate (DBTDL) was added as a catalyst and copolymerized by a conventional polymerization method. The softening point of the polyurethane resin b obtained in this way was 110-115 degreeC.

Example 1

A composition for forming a primer layer was prepared by dispersing 6% by weight of polyurethane resin a, 1.5% by weight of partially methylated melamine-formaldehyde resin crosslinker and 0.05% by weight of anionic hydrocarbon in water.

Next, a polyester sheet or film obtained by melt extrusion of a polyester resin obtained through a transesterification reaction and a polycondensation reaction from dimethyl terephthalate and ethylene glycol by a conventional method, and then stretched 3.5 times in one direction at 85 ° C. On at least one side, apply the above composition so that the thickness of the coating layer before drying is 5 µm, and then simultaneously dry the applied composition while stretching 3.5 times in the other direction at 230 ° C. again to form a biaxially stretched poly-laminated primer layer. An ester film was prepared.

Subsequently, polyvinyl chloride ink (polyvinyl chloride resin: methyl ethyl ketone: toluene = 20:40:40) was applied to the primer layer thus laminated to a thickness of 3 μm, and dried at 100 ° C. for 1 minute. Next, a polyurethane two-component adhesive was applied to a thickness of 6 mu m and dried at 60 DEG C for 1 minute. Thus, after laminating | stacking a PVC sheet by the normal dry lamination method on the film on which the printing layer and the adhesive layer were apply | coated, it was left to stand at 60 degreeC for 48 hours, and the decorative plate sheet which concerns on this invention was completed. The physical properties of the manufactured decorative sheet were measured by the above-described method, and the results are shown in Table 1.

Example 2

Except not adding a melamine crosslinking agent in the composition for forming a primer layer, after producing a decorative sheet in the same manner as in Example 1, the physical properties were measured and the results are shown in Table 1.

Example 3

After preparing the decorative plate sheet in the same manner as in Example 1, except that the amount of the polyurethane resin a was changed to 4% by weight and the amount of the melamine-based crosslinking agent was changed to 1% by weight in the composition for forming the primer layer. Physical properties were measured and the results are shown in Table 1.

Example 4

After preparing the decorative plate sheet in the same manner as in Example 1, except that the amount of the polyurethane resin a was changed to 2% by weight and the amount of the melamine-based crosslinking agent was changed to 0.5% by weight in the composition for forming the primer layer. Physical properties were measured and the results are shown in Table 1.

Example 5

After the addition of 0.2% by weight of an anionic clodal silicate having an average particle diameter of 80 nm and a pH value of 9.5 in the primer layer-forming composition, a cosmetic plate sheet was prepared in the same manner as in Example 1 It measured and showed the result in Table 1.

Example 6

After the addition of 0.2% by weight of an anionic clodal silicate having an average particle diameter of 80 nm and a pH value of 9.5 in the composition for forming a primer layer, a cosmetic plate sheet was prepared in the same manner as in Example 2. It measured and showed the result in Table 1.

Example 7

After the addition of 0.2% by weight of anionic clodal silicate having an average particle diameter of 80 nm and a pH value of 9.5 in the composition for forming a primer layer, a cosmetic plate sheet was prepared in the same manner as in Example 3 It measured and showed the result in Table 1.

Example 8

After the addition of 0.2% by weight of an anionic clodal silicate having an average particle diameter of 80 nm and a pH value of 9.5 in the composition for forming a primer layer, a cosmetic plate sheet was prepared in the same manner as in Example 4 It measured and showed the result in Table 1.

Comparative Example 1

Except not forming a primer layer, after producing a decorative plate sheet in the same manner as in Example 1, the physical properties were measured and the results are shown in Table 1.

Comparative Example 2

Except for using a polyurethane resin b in place of the polyurethane resin a in the composition for forming a primer layer, after producing a decorative sheet sheet in the same manner as in Example 1, the physical properties were measured and the results are shown in Table 1.

Comparative Example 3

Except for using polyurethane 503 as a water-dispersible acrylic resin instead of polyurethane resin a in the composition for forming a primer layer, a cosmetic plate sheet was prepared in the same manner as in Example 1, and then the physical properties were measured. Is shown in Table 1.

Comparative Example 4

A cosmetic plate sheet was prepared in the same manner as in Example 1, except that WR-961 manufactured by Japanese Synthetic Co., Ltd. was used as the water-soluble polyester resin instead of the polyurethane resin a in the primer layer-forming composition. Is shown in Table 1.

Peel force (g / in.) Peeling after immersion in water at 100 ℃ for 1 hour (Heat resistant) Coating strength Example One 1400 radish B 2 1300 radish 2B 3 1300 radish B 4 1200 radish B 5 1350 radish B 6 1250 radish 2B 7 1250 radish B 8 1150 radish B Comparative example One 700 U B 2 1000 radish B 3 900 radish B 4 800 U B

Referring to Table 1, the decorative plate sheet produced by the method of the embodiment is compared with the decorative plate sheet prepared by the comparative example, the interlayer adhesiveness and hot water resistance between each layer of the polyester base film and the printed layer, PVC sheet, etc. This is generally good.

As described above, the decorative plate sheet according to the present invention can be usefully used as a decorative plate sheet for various purposes because of excellent interlayer adhesion and hot water resistance between the base film and the printing layer and the PVC sheet. In addition, in the present invention, the composition for forming the primer layer is economical because water is used as a solvent or a dispersion medium, rather than using an organic solvent as a solvent or a dispersion medium, and does not adversely affect the health of workers, and there is a fear of ignition during work. There is no.

Claims (9)

Polyester base film; A primer layer formed on at least one surface of the polyester base film; A printing layer formed on the primer layer; An adhesive layer formed on the printing layer; And a polyvinyl chloride sheet laminated on the adhesive layer. The primer layer is 35 to 55 mol% of dicarboxylic acid component, 35 to 55 mol% of glycol component, and 5 to 15 mol% ester-based polyurethane resin having a diisocyanate component. . According to claim 1, wherein the dicarboxylic acid component of the polyurethane resin is 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 to 40 mol% of isophthalic acid component A decorative plate sheet characterized by the above. The softening point of the said polyurethane resin is 70-90 degreeC, The decorative plate sheet of Claim 1 or 2 characterized by the above-mentioned. The method of claim 1, wherein the primer layer is characterized in that the ester-based polyurethane resin crosslinked by at least one crosslinking agent selected from the group consisting of melamine-formaldehyde resin, urea-formaldehyde resin, and water-soluble blocked diisocyanate resin. Board sheet. 1-10 wt% of ester-based polyurethane resin consisting of 35 to 55 mol% of dicarboxylic acid component, 35 to 55 mol% of glycol component, and 5 to 15 mol% of diisocyanate component, 0.01 to 0.5 weight of surfactant %, And applying a composition consisting of the remaining amount of water to at least one surface on the polyester base film and then heat-treating to form a primer layer. The dicarboxylic acid component of the polyurethane resin is 30 to 50 mol% of adipic acid component, 20 to 40 mol% of terephthalic acid component, and 20 to 40 mol% of isophthalic acid component. A decorative plate sheet characterized by the above. The softening point of the said polyurethane resin is 70-90 degreeC, The decorative plate sheet of Claim 5 or 6 characterized by the above-mentioned. The method according to claim 5, wherein the composition further comprises 1 to 5% by weight of at least one crosslinking agent selected from the group consisting of melamine-formaldehyde resin, urea-formaldehyde resin, and water-soluble blocked diisocyanate resin. Method for producing a sheet of sheet. The method of claim 5, 6, or 8, wherein the composition further comprises 0.1 to 0.5% by weight of a silica-based additive.