KR20090120079A - Polyseter film for decoration sheet and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A polyester film for decoration sheet and manufacturing method thereof are provided to put pigments into a co-polymerized polyester layer to improve thickness uniformity, adhesion force, moldability, shielding property, and coloring capability. CONSTITUTION: A polyester film for decoration sheet comprises a polyester layer(B) and copolymerized polyester layer(A). The polyester layer(B) comprises a first component consisting of repeat units of dicarbonic acid and diol, and a 95mol% second component selected from dicarbonic acid and diol. The copolymerized polyester layer(A) contains pigments, the first component consisting of repeat units of dicarbonic acid and diol, and the 95mol% second component selected from dicarbonic acid and diol. The polyester layer(B) and copolymerized polyester layer(A) are laminated.

Description

Polyester film for decoration sheet and manufacturing method thereof {POLYSETER FILM FOR DECORATION SHEET AND MANUFACTURING METHOD THEREOF}

The present invention relates to a polyester film for decorating sheet and a method for manufacturing the same, and more particularly, at least one side of the copolyester polyester layer (B) has a copolyester polyester layer (A) having shielding property and colorability and adhesiveness. As a laminated structure, the raw material composition is optimized, and the pigment is contained in the copolymerized polyester layer (A), and thus the polyester film for decorating sheet having excellent adhesiveness, moldability, shielding property, coloring property, and cost reduction effect, and its manufacture It is about a method.

Conventionally, plasticized polyvinyl chloride material, which is used as a material for decor sheet, has excellent physical properties and moldability, but since a plasticizer is added to the vinyl chloride resin to give plasticity, toxic gases such as dioxins are generated during incineration. Hazard issues are always raised.

Deco sheets using polyolefin resins, which are emerging as alternative materials, have been disclosed. However, calendar molding is difficult and appearance quality is poor.

On the other hand, polyester films are used for packaging, electronic materials, laminates, graphic arts, windows, mold release, carriers, etc., but are not widely known for decoration sheets such as vinyl chloride.

Korean Patent No. 662817 discloses glycol-modified polyethylene terephthalate (PET-G), lubricants, antioxidants, UV stabilizers, and white pigments in gel-barrier mixers, and then added to a calender roll to a thickness of 0.1 mm (100 μm). The glycol-modified polyethylene terephthalate (PET-G) sheet was produced, but the above technique is a method of mixing the modified polyethylene terephthalate and various additives in a short-barrier mixer, gelling them, and then injecting them into a calender roll to produce sheets. There is a problem that foreign matter such as or gel is generated.

In addition, since the Montan lubricant is used, not only the adhesiveness to the printing layer is lowered, but also the glycol-modified polyethylene terephthalate (PET-G) monolayer film is used.

Therefore, the present invention is a two-layer or three-layer that is excellent in uniformity of thickness and excellent adhesion to the printing layer while using a polyester-based resin, and at the same time excellent in moldability, shielding and coloring, and can reduce the cost burden To provide a polyester film for decor sheet of.

An object of the present invention is to provide a polyester film for decorating sheet having excellent adhesiveness, moldability, shielding property and coloring properties suitable for decorating sheet.

Another object of the present invention is to provide a method for producing a laminated co-polyester film suitable for decor sheet.

In order to achieve the above object, the present invention provides a polyester film for decor sheet, wherein at least one side of the copolyester layer (B) is laminated with a copolyester layer (A) further containing a pigment in the copolyester raw material. to provide.

The raw material of the copolyester layer (B) and the copolyester layer (A) may be a single or mixed form selected from dicarboxylic acid or diol in a polyester first component consisting of repeating units of dicarboxylic acid and diol. 5 to 95 mol% of two components are contained. Thus, the polyester film for decoration sheet of the present invention has a tensile elongation of 170% or more to implement excellent moldability.

The pigment may be contained in an amount of 0.1 to 40% by weight based on the weight of the copolyester raw material, and preferred pigments include a white pigment, a black pigment, a red pigment, a yellow pigment, a green pigment, a blue pigment, and a purple pigment. It is to use one or more selected from the group consisting of. Thus, the polyester film for decorating sheet of the present invention, the total light transmittance is 50% or less, can be utilized for decorating sheet.

The polyester film for decor sheets of this invention is 40-1200 micrometers in total thickness, and the thickness of a co-polyester layer (A) 1-500 micrometers is preferable.

More preferably, as a first embodiment for the preferred embodiment of the present invention, a structure in which a copolyester polyester layer (A) is laminated on both sides of the copolyester polyester layer (B) (layer (A) / layer (B) / layer) (A)), wherein the thickness ratio between the layers is 1: 1: 1 to 1: 50: 1.

In addition, as a second embodiment for a preferred embodiment of the present invention, a structure (layer (A) / layer (B)) in which a copolymerized polyester layer (A) is laminated on one surface of a copolymer polyester layer (B), wherein , The thickness ratio between the layers satisfies 1: 1 to 1:50.

In addition, the polyester film for decoration sheet of the present invention can implement a cost reduction by adding a recycled raw material to the copolyester layer (A) or copolyester layer (B).

One example that can be used as the dicarboxylic acid second component in the present invention is isophthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, adipic acid, diphenyldicarboxylic acid, 5-tert-butyl butyl iso Phthalic acid, 2,2,6,6-tetramethyldiphenyl-4,4-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindan-4,5-dicarboxylic acid, 5-sodium sulfoiso Phthalic acid, trimellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimeric acid, azelaic acid, pyromellitic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and At least one selected from the group consisting of dimethyl-1,4-cyclohexanedicarboxylic acid.

In addition, the diol second component usable in the present invention is diethylene glycol, triethylene glycol, hexanediol, pentanediol, diol of 2,2- (4-oxyphenol) propane derivative, xylene glycol, 1,4-butanediol , 1,3-butanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, polytetramethylene glycol, polyethylene glycol, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol At least one selected from the group consisting of.

The present invention provides a method for producing a polyester film suitable for decor sheet. More specifically, a copolyester layer containing 5 to 95 mol% of the second component in a single or mixed form selected from dicarboxylic acid or diol in the polyester first component consisting of repeating units of dicarboxylic acid and diol. The raw material of (B) and the copolyester layer (A) is put into another extruder, and it melt-extrudes, manufactures a melt sheet by a multilayer laminated structure, and manufactures the said melt sheet by adhering to a cold rolling roll. .

At least one pigment selected from the group consisting of a white pigment, a black pigment, a red pigment, a yellow pigment, a green pigment, a blue pigment, and a purple pigment is added to the copolymer polyester raw material layer (A), It is characterized by containing 0.1 to 40% by weight.

In addition, during the manufacturing process of the present invention, the melt extrusion process is carried out at 160 to 280 ℃ in order to prevent the uniformity of the film thickness and foreign substances such as gel.

After the melt extrusion process, when the multilayered structure is formed, the laminated structure is a structure in which a copolymerized polyester layer (A) is laminated on both sides of the copolymerized polyester layer (B) (layer (A) / layer (B)). / Layer (A)), and the thickness ratio of each layer satisfies 1: 1: 1 to 1: 50: 1.

Moreover, as another laminated structure, the structure (layer (A) / layer (B)) by which the copolymerization polyester layer (A) was laminated | stacked on one surface of the copolymerization polyester layer (B), and the thickness ratio of each layer is 1: 1. To 1:50.

The unstretched laminated co-polyester film produced by the production method of the present invention can be usefully used for decor sheet.

According to the present invention, it is possible to provide a polyester film for decor sheet that is excellent in thickness uniformity and excellent in adhesiveness with a printing layer and also excellent in adhesiveness, moldability, shielding property and colorability.

Specifically, at least one side of the copolyester polyester layer (B) is a polyester film for decorating sheet, wherein the copolyester polyester layer (A) in which the copolyester raw material further contains a pigment is laminated, through optimization of the raw material composition. , Adhesiveness and moldability are imparted.

In addition, by including the pigment in the copolyester layer (A), the shielding and coloring properties of the final film is imparted, and the expensive pigment is contained only on the outermost side of the film, thereby reducing the cost.

Further, as a raw material composition of the polyester film for decorating sheet of the present invention, by using a recycled raw material, it is possible to implement a cost reduction effect.

The polyester film for decorating sheet of the present invention can be usefully applied to overlay, lapping, member lane, high gloss, interior sheet paper and the like.

Hereinafter, the present invention will be described in detail.

The present invention relates to a copolymer polyester layer (B) containing 5 to 95 mol% of a second component in a single or mixed form selected from dicarboxylic acids or diols in a polyester first component comprising a repeating unit of dicarboxylic acid and diol. On at least one side,

Pigment is further contained in the copolyester raw material containing 5 to 95 mol% of the second component in a single or mixed form selected from dicarboxylic acid or diol in the polyester first component consisting of dicarboxylic acid and diol repeating units. Provided is a polyester film for decorating sheet having a laminated structure of a co-polyester layer (A).

In the laminated copolyester film of the present invention, the polyester used as a raw material for the copolyester layer (A) and / or the copolyester layer (B) is dicarboxylic acid and ethylene glycol selected from terephthalic acid or dimethyl terephthalate. 5 to 95 mol% of the second component selected from dicarboxylic acid and / or diol, more preferably 10 to 90 mol%, even more preferably to the polyester first component comprising a repeating unit of a diol containing It contains 15-85 mol%.

At this time, if less than 5 mol% of the second component selected from dicarboxylic acid and / or diol is contained, the cohesive polyester layer (A) may have low printing adhesive strength, and the copolyester layer (B) may have low moldability. Can be. Moreover, when 95 mol% of 2nd components chosen from dicarboxylic acid and / or diol are contained, printing adhesive force and moldability will fall. That is, the polyester first component and the second component of the present invention should be uniformly well mixed, but if the ratio of any one component is too large, crystallization may occur and print adhesion and moldability may be deteriorated.

In particular, as an essential item for applying to the decor sheet, if the moldability is poor, turbidity may occur. This can be known by measuring the tensile elongation as a means for predicting such formability. That is, when the tensile elongation of the polyester film for decoration sheet of the present invention is 170% or more, preferably 200% or more, more preferably 300% or more, the desired moldability can be realized. At this time, when the tensile elongation is less than 170%, the moldability is insufficient, in particular, when the tensile elongation is low as about 10%, breakage of the film occurs in the post-process, such as printing process, secondary cutting process.

In the polyester film for decor sheets of the present invention, the preferred dicarboxylic acid second component is isophthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, adipic acid, diphenyldicarboxylic acid, 5-agent. Tert-butyl isophthalic acid, 2,2,6,6-tetramethyldiphenyl-4,4-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindan-4,5-dicarboxylic acid, 5- Sodium sulfoisophthalic acid, trimellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimeric acid, azelaic acid, pyromellitic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedica At least one selected from the group consisting of carboxylic acid, dimethyl-1,4-cyclohexanedicarboxylic acid.

In addition, the diol second component is diethylene glycol, triethylene glycol, hexanediol, pentanediol, diol of 2,2- (4-oxyphenol) propane derivative, xylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-bis (4-hydroxy Phenyl) propane, bis (4-hydroxyphenyl) sulfone, polytetramethylene glycol, polyethyleneglycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol More choices are available.

In the polyester film for decorating sheet of the present invention, in order to impart printing adhesion, it can be implemented by using 5 to 95 mol% of the second component of the dicarboxylic acid and / or diol, In order to impart colorability, it further contains one or more pigments selected from the group consisting of white pigments, black pigments, red pigments, yellow pigments, green pigments, blue pigments and purple pigments.

Pigments usable in the present invention can be used without limitation inorganic pigments or organic pigments known to those skilled in the art as long as the pigments can be decomposed when producing the pigment masterbatch chip, and a phenomenon such as poor coloration and poor appearance may occur.

As one example, a conventional white pigment may use inorganic particles such as titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, kaolin, silica, clay, calcium terephthalate, aluminum oxide, calcium phosphate, and melted with a copolyester resin. Insoluble high-melting organic compound fine particles, cross-linked polymer fine particles, and metal compound catalysts used for synthesizing polyester, for example, internal particles formed inside the polymer when preparing copolyester by alkali metal compound, alkaline earth metal compound, etc. Can be mentioned.

In addition, as a black pigment, carbon black is used a lot. In addition, Munsell color wheel base index red pigments, yellow pigments, green pigments, blue pigments or purple pigments can be selected and used within the range of pigments well known to those skilled in the art.

In addition, the preferred content of the pigment for imparting shielding and coloring properties to the film is 0.1 to 40% by weight, preferably 1 to 40% by weight, and more, based on the weight of the copolyester raw material used for the copolyester layer (A). Preferably 5 to 40% by weight is used. At this time, if the content of the pigment is less than 0.1% by weight, the desired shielding properties or coloring properties are not expressed, while if the content of the pigment is more than 40% by weight, the strength of the film is lowered and the possibility of breakage is increased.

When prepared by containing the pigments in the present invention, the total light transmittance of the prepared polyester sheet for decor sheet is 50% or less, preferably 40% or less, more preferably 30% or less, excellent shielding properties.

Moreover, in addition to the said pigment, resin incompatible with polyester can also be used for the polyester film for decorative sheets of this invention in the range which does not interfere with shielding property or coloring property. For example, polystyrene resin, polyolefin resin, polyacrylic resin, polycarbonate resin, polysulfone resin, cellulose resin and the like can be used.

Moreover, the cost burden of a final film can be reduced by using recycled raw material as a raw material of the copolyester layer (A) and / or copolyester layer (B) of this invention. In the case of using the recycled raw material, the copolymerized polyester layer (B) may also contain inorganic pigment particles such as titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, kaolin, silica, clay, terephthalate, aluminum oxide, calcium phosphate, and the like. have.

The present invention provides a method for producing the polyester film for decoration sheet.

The copolymerized polyester layer (B) constituting the polyester film for decorating sheet of the present invention and the copolymerized polyester layer (A) having shielding properties and adhesiveness are copolymerized or several copolymerized poly-polymers which make a laminate directly from the copolymerized polyester resin. It can be prepared by a blending method using a mixture of esters and / or homopolyesters. Thus, looking at the manufacturing method of the polyester film of the present invention in detail,

1) Copolyester layer (B) containing 5 to 95 mol% of second components in a single or mixed form selected from dicarboxylic acids or diols in a polyester first component consisting of a repeating unit of dicarboxylic acid and diol. And the raw material of the copolyester polyester layer (A) is put into a separate extruder and melt-extruded,

2) manufacturing a molten sheet in a multilayered laminated structure,

3) The molten sheet is brought into close contact with a cold rolling roll, and is made into an unstretched sheet.

In the manufacturing process, the polyester raw material used for the copolyester layer (A) and the copolyester layer (B) in step 1) is the same as described in the laminated copolyester film for decoration sheet, Description of the one component and the second component is omitted.

Print adhesiveness and moldability are provided to a film by containing 5 to 95 mol% of polyester second components of dicarboxylic acid and / or diol in the said polyester raw material. That is, the laminated co-polyester film prepared by the production method of the present invention exhibits a tensile elongation of 170% or more, preferably 200% or more, more preferably 300% or more, thereby fulfilling the essential requirements for use as a decor sheet. do.

Further, in the manufacturing process, in step 1), the copolymerized polyester layer (A) is selected from the group consisting of white pigment, black pigment, red pigment, yellow pigment, green pigment, blue pigment and purple pigment. It is characterized in that it contains 0.1 to 40% by weight based on the weight of the polyester raw material at least one pigment.

By containing the said pigment in a copolyester layer (A), shielding property and coloring property can be provided to a film. At this time, if the content of the pigment is less than 0.1% by weight, the desired shielding properties or coloring properties are not expressed, while if the content of the pigment is more than 40% by weight, the strength of the film is lowered and the possibility of breakage is increased.

That is, the laminated copolyester film produced by the production method of the present invention exhibits a total light transmittance of 50% or less, preferably 40% or less, and more preferably 30% or less, and thus has excellent shielding properties. In addition, by containing the pigment in the copolyester layer (A), it is possible to implement a cost-saving effect.

In addition, the production method of the present invention can realize the cost reduction of the final film by using a recycled (recycle) raw material as the raw material composition used in step 1). That is, in the film manufacturing process, the outermost edge portion may be thick, in which case the grinding is performed while cutting the edges. In the case of using such a pulverized product (regenerated raw material) again as a raw material, the copolyester layer (B) also contains titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, kaolin, silica, clay, terephthalate, aluminum oxide, calcium phosphate, and the like. It may contain inorganic pigment particles of. At this time, the content of the pigment is the same as the range contained in the copolyester layer (A).

In addition, when producing co-polyesters with high-melting-point organic compound fine particles, cross-linked polymer fine particles and metal compound catalysts used for synthesizing polyester, such as alkali metal compounds, alkaline earth metal compounds, etc., which are insoluble during melt mixing with the copolyester resin. Internal particles formed in the polymer may also be contained, and incompatible resins for polyester may be used within a range that does not interfere with shielding or coloring. For example, polystyrene resin, polyolefin resin, polyacrylic resin, polycarbonate resin, polysulfone resin, cellulose resin and the like can be contained.

Therefore, by further using recycled raw materials in the copolyester layer (A) and / or copolyester layer (B) of the present invention, the cost burden can be further reduced.

Furthermore, the polyester film for decorating sheet of the present invention, if necessary, further input other additives such as heat stabilizer, antioxidant, pinning improver, sunscreen, antibacterial agent, antistatic agent, flame retardant, colorant (pigment), etc. The additives may be selected and used within the range commonly used by those skilled in the art according to the purpose of use.

For example, an additive may be further used in the copolyester layer (A) and / or copolyester layer (B) having the shielding properties and adhesiveness of the present invention in order to prevent blocking property or runability between films.

At this time, examples of additives used for the purpose of preventing blocking or improving runability include silica, calcium carbonate, kaolin, alumina, zirconia, zeolite, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, and hydroxide. Inorganic fine particles such as aluminum, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, carbon black, and molybdenum disulfide; Or organic fine particles such as an acrylic crosslinked polymer, a styrene crosslinked polymer, a crosslinked silicone resin, a fluorine resin, a benzoguanamine resin, a phenol resin, or a nylon resin.

The inorganic fine particles or the organic fine particles used for the purpose of preventing the blocking property or improving the running property are required to control the particle size so that they can be differentiated from the inorganic fine particles used in the copolyester polyester layer (A) having shielding properties and adhesiveness. For example, when the average particle diameter of the inorganic fine particles used in the copolyester polyester layer (A) having shielding properties and adhesiveness is 0.5 μm, the average particle diameter of the particles used for preventing blocking property is larger than 0.5 μm (0.5 μm). Micrometers or more).

In addition, during the manufacturing process, the melt extrusion process of step 1) is preferably performed at 160 to 280 ° C, more preferably at 200 to 280 ° C, in order to prevent film uniformity and foreign matter generation such as gel. It is. At this time, when the temperature during the melt extrusion process is less than 160 ° C, unmelted copolyester may be generated to generate foreign substances such as gel. In addition, when the temperature exceeds 280 ° C. during the melt extrusion process, a large amount of black foreign matter due to pyrolysis may occur in the case of melt extrusion. When the film is continuously produced in a state in which a large amount of the gel or black foreign material is generated, the thickness uniformity of the film is reduced due to the hunting of the filter pressure.

In addition, in the case of external foreign matter and unmelted gel, an appropriate filter can be selected and removed. In other words, all foreign matters or unmelted gels larger than the pore size of the filter can be removed. Therefore, the laminated co-polyester film of the present invention is uniform in thickness, foreign matters due to external foreign matter and unmelted gel is prevented, it is preferable for decor sheet applications.

In the melt extrusion, a single screw extruder, a twin screw extruder, or the like may be used.

In the manufacturing process of the present invention, step 2) is a step of manufacturing a melted sheet of a melted laminate in the above step, the first embodiment for the preferred embodiment of the polyester film for decoration sheet of the present invention is the copolyester It is a structure (layer (A) / layer (B) / layer (A)) by which the copolyester polyester layer (A) was laminated | stacked on both surfaces of the layer (B), and the thickness ratio between the said layers is 1: 1: 1- 1: 50: 1.

In addition, in the polyester film for decorating sheet of the present invention, the second embodiment for the preferred embodiment is a structure in which the copolyester polyester layer (A) is laminated on one surface of the copolyester polyester layer (B) (layer (A) / Layer (B)), wherein the thickness ratio between the layers satisfies 1: 1 to 1:50.

The total thickness of the polyester film for decorating sheet of the present invention is preferably in the range of 40 to 1200 µm. At this time, when the thickness is less than 40 µm, the strength of the film is weak, so that breakage is likely to occur during film processing, and when the thickness exceeds 1200 µm, roll winding of the film becomes difficult.

In addition, in the polyester film for decorating sheet of the present invention, by further comprising a pigment in the copolyester layer (A), while imparting the shielding and coloring properties, while implementing a function to obtain while minimizing expensive pigment content In addition, there is a cost reduction effect in the final film production.

At this time, the preferable thickness of a copolyester layer (A) is 1-500 micrometers, Preferably it is 1-200 micrometers, More preferably, it is 1-100 micrometers.

In the manufacturing process of the present invention, step 3) is to prepare the unstretched laminated film by closely contacting the molten sheet prepared in step 2) with a cold rolling roll through a feed block and a tea die.

At this time, the method of closely contacting the molten sheet prepared in step 2) to a cold rotating roll (casting drum), by applying the electrostatic application method or calendaring method, it is possible to produce a film in a cooling solidified state.

The electrostatic application method is a method of manufacturing a sheet in a molten state in a casting drum (cooling roll) by inserting an appropriate pinning enhancer into the copolyester resin itself.

In the method of uniformly forming the thickness by the electrostatic application method, the phosphorus-containing compound is contained in the alkali metal compound or the alkaline earth metal compound as a pinning-enhancing agent in the raw material to be used in order to lower the melting bead value of the molten sheet. In addition, the thickness uniformity can be realized by constant extrusion amount, constant pressure management, and die bolt adjustment of the t-shaped die. This thickness uniformity can be adjusted to those skilled in the art to control the process, to produce an optimal film.

The calendaring method is a method of producing a sheet in a cooling solidified state using a backup roll in order to closely adhere the sheet in a molten state to a casting drum.

Factors that can form the thickness uniformly by the calendaring method include uniform bank formation, constant spacing between the casting drum and the backup roll, die bolt adjustment to adjust the local spacing of the T-shaped die, constant extrusion amount, A sheet of uniform thickness can be produced by constant pressure control or the like.

The unstretched laminated co-polyester film produced by the production method of the present invention can be usefully used as a decor sheet.

Hereinafter, the present invention will be described in more detail with reference to Examples.

This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

< Production Example  1> Cyclohexanedimethanol  Copolyester ( PETG Manufacturing

1,000 kg of dimethyl terephthalate, 600 kg of ethylene glycol and 240 kg of 1,4-cyclohexanedimethanol were added to the reaction tube, and 0.08% by weight of manganese acetate and 0.01% by weight of acetic acid were prepared in comparison to the dimethyl terephthalate. Sodium was added.

The methanol is distilled out while gradually raising the temperature to 240 ° C., and after completion of the transesterification reaction, trimethyl phosphate is added 0.03 wt% to the dimethyl terephthalate as a heat stabilizer, and after 5 minutes, the antimony trioxide is added to the dimethyl terephthalate. 0.04% by weight of the prepared solution was added, and after 5 minutes, 0.03% by weight of the silica particles having an average particle diameter of 2 μm were added to the dimethyl terephthalate, and the stirring was continued for 5 minutes.

The oligomeric mixture was transferred to another reactor equipped with vacuum equipment, and then cyclohexanedimethanol copolyester (cyclohexanedimethanol concentration: 32 mol%) was prepared while heating up from 250 ° C to 280 ° C. The intrinsic viscosity of the copolyester is 0.72 dl / g.

< Production Example  2> Isophthalic acid  Copolyester ( PETI Manufacturing

1,000 kg of dimethyl terephthalate, 720 kg of ethylene glycol and 110 kg of dimethyl isophthalate were added to the reaction tube, and 0.08 wt% manganese acetate and 0.01 wt% sodium acetate were added to the dimethyl terephthalate.

The methanol is distilled out while gradually raising the temperature to 240 ° C., and after the transesterification reaction, 0.03% by weight of trimethyl phosphate is added to the dimethyl terephthalate as a heat stabilizer, and after 5 minutes, dimethyl terephthalate is added to the antimony trioxide. 0.045% by weight relative to the amount, and after 5 minutes, 0.03% by weight relative to the dimethyl terephthalate was added to the silica particles having an average particle diameter of 2 μm, and the stirring was continued for 5 minutes.

After transferring the mixture in the oligomer state to another reactor equipped with a vacuum equipment, an isophthalic acid copolyester (isophthalic acid concentration: 10 mol%) was prepared while raising the temperature from 250 ° C to 280 ° C. The intrinsic viscosity of the copolyester is 0.65 dl / g.

< Production Example  3> Neopentyl glycol  Copolyester ( PETN40 Manufacturing

1000 kg of dimethyl terephthalate, 447 kg of ethylene glycol and 322 kg of neopentyl glycol were added to the reaction tube, and 0.08% by weight of manganese acetate was added to the reaction tube relative to the dimethyl terephthalate. The methanol is distilled out while gradually raising the temperature to 240 ° C, 0.03% by weight of the thermal stabilizer trimethyl phosphate is added to the dimethyl terephthalate after the transesterification reaction, and after 5 minutes, 0.03% by weight of the antimony tree is compared with the dimethyl terephthalate. Oxide was added and stirred for 5 minutes. Again 0.8% by weight of silica particles (average particle size 6.5㎛) was added to the dimethyl terephthalate and stirred for 5 minutes to prepare a mixture in the oligomeric state. The mixture in the oligomer state was transferred to another reactor equipped with a vacuum equipment, and then reacted while raising the temperature from 250 ° C to 280 ° C to synthesize neopentyl glycol copolymer polyester having an intrinsic viscosity of about 0.7 dl / g. At this time, the content of neopentyl glycol contained in the copolyester was 40 mol%.

< Production Example  4> 2- Methylpropanol  Copolyester ( PETM Manufacturing

1000 kg of dimethyl terephthalate, 575 kg of ethylene glycol and 95 kg of 2-methylpropanediol were added to the reaction tube, 0.09% by weight of manganese acetate was added to the dimethyl terephthalate, and methanol was discharged while gradually warming up to 240 ° C. After removal of the transesterification reaction, 0.09% by weight of heat stabilizer trimethylphosphate was added to dimethyl terephthalate, and after 5 minutes, 0.05% by weight of antimonytrioxide was added to dimethylterephthalate, followed by stirring for 5 minutes. A mixture was prepared. The mixture in the oligomer state was transferred to another reactor equipped with a vacuum equipment, and then reacted while raising the temperature from 250 ° C to 280 ° C to synthesize a copolymerized polyester resin having an intrinsic viscosity of 0.65 dl / g (2-methyl in the copolymerized polyester resin). Propanediol is present in 20 mole percent).

< Production Example  5> Polybutylene terephthalate ( PBT Manufacturing

After 2000 kg of dimethyl terephthalate and 1856 kg of 1,4-butanediol were added to the reaction tube, 750 g of tetrabutyl titanate and 150 g of hydrate monobutyl tin oxide, 2500 g of sodium 2,2'-methylene bis- (4, After 1250 g of Iganox 1010 (manufactured by Ciba-Geigy Co., Ltd.) was added as 6-di- t -butylphenyl) phosphate and a heat resistant agent, methanol was generated while the reaction tube was gradually heated to 240 ° C. After completion of the transesterification reaction, 225 g of lithium acetate and 750 g of tetrabutyl titanate were added and then transferred to another reactor equipped with a vacuum equipment, followed by reaction while raising the temperature to 250 ° C to 280 ° C, Polybutylene terephthalate (PBT) having an intrinsic viscosity of 0.83 dl / g was obtained.

< Production Example  6> Polyethylene terephthalate ( PET Manufacturing

2000 kg of dimethyl terephthalate and 1270 kg of ethylene glycol were added to the reaction tube.

And, 0.09% by weight of manganese acetate compared to the dimethyl terephthalate was added to the reaction tube. The methanol is distilled out while gradually raising the temperature to 240 ° C, 0.09% by weight of the heat stabilizer trimethyl phosphate is added to the dimethyl terephthalate after the completion of the transesterification reaction, and after 5 minutes, 0.05% by weight of the antimony trioxide is added to the dimethyl terephthalate. And again stirred for 5 minutes to prepare a mixture of oligomeric state.

The oligomeric mixture was transferred to another reactor equipped with a vacuum equipment, and then reacted while raising the temperature from 250 ° C. to 280 ° C. to synthesize polyethylene terephthalate having an intrinsic viscosity of about 0.65 dl / g.

< Production Example  7> Neopentyl glycol  Copolyester ( PETN20 Manufacturing

1000 kg of dimethyl terephthalate, 510 kg of ethylene glycol and 220 kg of neopentyl glycol were added to the reaction tube, and 0.08% by weight of manganese acetate relative to the dimethyl terephthalate was added to the reaction tube. The methanol is distilled out while gradually raising the temperature to 240 ° C., and 0.03 wt% of the heat stabilizer trimethyl phosphate is added to the dimethyl terephthalate after the transesterification reaction, and after 5 minutes, 0.03 wt% of the antimony tree is compared to the dimethyl terephthalate. Oxide was added and stirred for 5 minutes. Again 0.8% by weight of silica particles (average particle size 6.5㎛) was added to the dimethyl terephthalate and stirred for 5 minutes to prepare a mixture in the oligomeric state.

The mixture in the oligomer state was transferred to another reactor equipped with a vacuum equipment, and then reacted while raising the temperature from 250 ° C to 280 ° C to synthesize neopentyl glycol copolymer polyester (E) having an intrinsic viscosity of about 0.7 dl / g. At this time, the content of neopentyl glycol contained in the copolyester was 20 mol%.

< Production Example  8> Polypropylene Terephthalate ( PPT Manufacturing

After 2000 kg of dimethyl terephthalate and 1600 kg of propylene glycol were added to the reaction tube, tetrabutyl titanate was added to 0.05wt% of dimethyl terephthalate. The methanol is distilled out while gradually increasing the temperature to 230 ° C., and after completion of the transesterification reaction, trimethyl phosphate is added 0.045 wt% to dimethyl terephthalate as a heat stabilizer, and after 5 minutes, antimony trioxide is 0.03 wt% to dimethyl terephthalate. After the addition, stirring was continued for 5 minutes. The oligomeric mixture was transferred to another reactor equipped with a vacuum equipment, and then reacted while raising the temperature from 230 ° C to 250 ° C to synthesize polypropylene terephthalate resin (PPT) having an intrinsic viscosity of 0.8.

< Example  1>

75 wt% of cyclohexanedimethanol copolymerized polyester (PETG) prepared in Preparation Example 1 and 25 wt% of titanium oxide (TiO ₂ ) particles having an average particle diameter of 0.5 μm as a pigment were uniformly mixed and melt-extruded at 160 to 260 ° C. Masterbatch chips were prepared by pelleting (chipting).

60 wt% of the prepared master batch chip and 40 wt% of cyclohexanedimethanol copolymerized polyester (PETG) chip of Preparation Example 1 were mixed to prepare a raw material of the copolyester layer (A), and prepared in Preparation Example 1 again. Cyclohexanedimethanol copolyester (PETG) was prepared as a raw material for the copolyester layer (B).

The copolyester polyester layer (A) raw material and the raw material of the layer (B) were put into separate twin screw extruders, mixed and melted and joined with a feed block, and then melt-extruded from a T-shaped die at 260 ° C., By tightly cooling and solidifying to the cooling casting drum by the electrostatic application method, the layer thickness ratio was 1/1/1, and the unstretched laminated copolymer polyester film of the A / B / A structure of 50 micrometers in total thickness was manufactured (melting). Filter during extrusion is 250 mesh).

< Example  2>

75% by weight of cyclohexanedimethanol copolymerized polyester (PETG) prepared in Preparation Example 1 and 25% by weight of carbon black having an average particle diameter of 23 nm as a pigment were uniformly mixed and melt-extruded at 160 to 260 ° C to pelletize (chip). Masterbatch chips were prepared.

The prepared masterbatch chip was prepared as a raw material of the copolyester polyester layer (A), and isophthalic acid copolyester (PETI) prepared in Preparation Example 2 was prepared as a raw material of the copolyester polyester layer (B).

The copolyester polyester layer (A) raw material and the raw material of the layer (B) were put into separate twin screw extruders, mixed and melted and joined with a feed block, and then melt-extruded from a T-shaped die at 260 ° C., By tightly cooling and solidifying the cooling casting drum by an electrostatic application method, the layer thickness ratio was 1/3/1, whereby an unstretched laminated copolymer polyester film having an A / B / A structure having a total thickness of 80 µm was prepared (melt). 150 mesh filters during the extrusion process).

< Example  3>

70 wt% of neopentyl glycol copolymerized polyester (PETN40) prepared in Preparation Example 3 and 30 wt% of green pigment as a pigment were uniformly mixed and melt-extruded at 160 to 260 ° C. to pelletize (chip) to prepare a masterbatch chip. It was.

The prepared master batch chip as a raw material of the copolyester polyester layer (A), again 50 wt% of neopentyl glycol copolyester (PETN40) prepared in Preparation Example 3 and polyethylene terephthalate prepared in Preparation Example 6 ( PET) 50% by weight was mixed to prepare a raw material of the copolyester layer (B).

The copolyester polyester layer (A) raw material was introduced into a twin screw extruder, melt mixed at 260 ° C., and the layer (B) raw material was also fed into a separate twin screw extruder and melt mixed at 280 ° C. The raw materials were joined by a feed block, and then a molten sheet was formed from the T-shaped die, followed by solidifying and solidifying tightly to the cooling casting drum by an electrostatic application method, with a total thickness of 100 μm with a layer thickness ratio of 1/8/1. An unstretched laminated co-polyester film having an A / B / A structure was prepared (200 mesh applied to the filter during the melt extrusion process).

< Example  4 to 11

As shown in Tables 1 to 5 below, except that the thickness, layer composition ratio, pigment, master batch chip concentration, (A) layer chip mixing ratio, and (B) layer chip mixing ratio were differently performed. It prepared as in Example 1.

However, when the polyethylene terephthalate (PET) prepared in Preparation Example 6 is mixed, the melting point of polyethylene terephthalate is higher than other co-polyester resins, the temperature of the twin screw extruder from 260 ℃ to 280 ℃ Adjust the melt extrusion temperature to an extent.

< Comparative example  1 to 6>

As shown in Tables 1 to 5 below, except that the thickness, layer composition ratio, pigment, master batch chip concentration, (A) layer chip mixing ratio, and (B) layer chip mixing ratio were differently performed. It prepared as in Example 1.

< Example  12>

70 wt% of cyclohexanedimethanol copolymerized polyester of Preparation Example 1 and 30 wt% of titanium oxide (TiO ₂ ) particles having an average particle diameter of 0.6 μm as a pigment were uniformly mixed and melt-extruded at 160 to 260 ° C. to pelletize (chip). To prepare a master batch chip.

80 wt% of the prepared master batch chip and 20 wt% of the crystalline polystyrene resin (manufactured by G797N Nippon Polystyrene Co., Ltd.) were mixed to prepare a raw material of the copolymerized polyester layer (A), and the cyclohexanedi prepared in Preparation Example 1 again. Methanol copolyester (PETG) was prepared as a raw material for the copolyester layer (B).

The copolyester polyester layer (A) raw material and the raw material of the layer (B) were put into separate twin screw extruders, mixed and melted and joined with a feed block, and then melt-extruded from a T-shaped die at 260 ° C., By tightly cooling and solidifying the cooling casting drum by the calendaring method, an unstretched laminated copolymer polyester film having an A / B / A structure having a total thickness of 250 µm was prepared at a layer thickness ratio of 1/8/1 (melt extrusion process). Filters in the 200 mesh).

< Example  13>

75% by weight of cyclohexanedimethanol copolymerized polyester of Preparation Example 1 and 25% by weight of titanium oxide (TiO ₂ ) particles having an average particle diameter of 0.6 μm as a pigment were uniformly mixed and melt-extruded at 160 to 260 ° C. to pelletize (chip). To prepare a masterbatch chip was prepared as a raw material of the copolyester layer (A).

The recycled raw material prepared below was prepared as a raw material of the copolyester layer (B).

The copolyester polyester layer (A) raw material and the raw material of the layer (B) were put into separate twin screw extruders, mixed and melted and joined with a feed block, and then melt-extruded from a T-shaped die at 260 ° C., By tightly cooling and solidifying the cooling casting drum by the calendaring method, an unstretched laminated copolymer polyester film having an A / B / A structure having a total thickness of 250 µm was prepared with a layer thickness ratio of 1/8/1 (melt extrusion process). Filters in the 200 mesh).

Recyclable Raw Material Manufacturing:

In the production process of the film (film containing 5% by weight of titanium oxide), the outermost edge portion was cut out and ground again in a grinder. At this time, the pulverized material may be utilized as a recycled raw material. Here, the milled product was further melt-extruded, and then further processed into a long strand (strand), and then cut into a chip to prepare a chip, which was used as a recycled raw material.

< Comparative example  7>

As a composition for molding a printed sheet, 0.8 parts by weight of Montan lubricant (trade name of US Clariant, WE-40), phosphite-based antioxidant (Shiba Shiva Corporation) based on 100 parts by weight of PET-G resin (Eastman, GS) 0.5 parts by weight of a trade name, Irganox B-561), 0.3 parts by weight of an ultraviolet (UV) stabilizer (trade name of Shiva, Switzerland, Tinuvin-1577), and 6.0 parts by weight of titanium (trade name of Kermekki, CR-834, Australia) PET-G resin composition was obtained. Thereafter, the composition was sufficiently gelled in a half-barrier and placed in a calender roll to prepare a PET-G sheet having a thickness of 0.1 mm (Korean Patent No. 642817).

< Experimental Example  1>

The laminated copolymer polyester films prepared in Examples 1 to 13 and Comparative Examples 1 to 7 were subjected to property evaluation as follows.

(1) appearance

The appearance of the laminated co-polyester films prepared in Examples 1 to 13 and Comparative Examples 1 to 7 was visually inspected for foreign matters or flow marks. Inspection judgment criteria are as follows.

○: no foreign matter or flow marks (good)

△: 1 to 5 levels (usually) of foreign matter or flow marks per 1 m ²

×: debris flows, or its more than 6 per 1m ² levels (bad)

 (2) ink adhesion

3 g of rhodamine-B, 10 ml of 1-butanol, 250 ml of ethylene glycol monomethyl ether, and 10 ml of methyl ethyl ketone were mixed and stirred. 25 g of cellulose acetate butyrate was slowly added thereto and dissolved therein to prepare an ink solution. The prepared ink solution was applied to the laminated co-polyester films prepared in Examples 1 to 13 and Comparative Examples 1 to 7 using a wire bar (# 3), and dried in a 40 ° C. hot air dryer for 10 minutes.

Thereafter, 100 scratches were made on the coating layer in the form of a checkerboard. The cellophane tape (3M 610) was stuck to the scratches on the surface where the checkerboard scratches were formed, and this tape was strongly rubbed five times with a thumb through a soft gauze or the like and completely compressed. Then, a part of the tape was peeled off a little, and then quickly peeled off by hand, and peeling of the coating layer was observed and evaluated.

Evaluation criteria are as follows.

○: peeled off is less than 5 out of 100 checkerboard scratches (good)

(Triangle | delta): The peeled part is 5-20 pieces in 100 checkerboard scratches (usually).

×: When the peeled off portion exceeds 20 out of 100 check marks (bad)

 (3) Back R value (unit: μm)

The film was cut out in the width direction from one roll, and the thickness was measured in the width direction of the roll using a back gauge. In this collected data, the difference between the maximum value and the minimum value was defined as an R value.

(4) tensile elongation

Tensile strength of the laminated co-polyester films prepared in Examples 1 to 13 and Comparative Examples 1 to 7 were measured by ASTM-D882 method.

When the tensile elongation exceeds 170%, the moldability is excellent, the moldability is normal between 100 and 170%, and when the tensile elongation is less than 10 to 100%, the moldability is lowered. In particular, breakage occurs when the elongation is less than 10%.

(5) total light transmittance

About the laminated co-polyester film produced in the said Examples 1-13 and Comparative Examples 1-7, the total light transmittance was measured according to JIS-K-7136 method using the Nippon Densoku machine (NDH 300A).

(6) windability

When winding the film with a width of 1300mm and a length of 2000m, the rolled roll has a uniform cross section, and if the roll has no irregularities, it is determined that the wound appearance is "good", otherwise the appearance is "bad" ) ”.

Evaluation results of physical properties and appearance characteristics of the laminated co-polyester films obtained in Examples 1 to 13 and Comparative Examples 1 to 7 are shown in Tables 1 to 5 below.

As shown in Table 1 to Table 5, the laminated copolyester film prepared in Examples 1 to 13 of the present invention exhibited a tensile elongation of 170% or more, up to 553%, thereby ensuring excellent moldability.

In addition, in the case of the laminated co-polyester film produced in Examples 1 to 13 of the present invention, excellent shielding property was confirmed when the total light transmittance was 30% or less. In addition, it was confirmed that ink adhesiveness and winding property were excellent and film thickness was uniform.

Therefore, the laminated co-polyester film of the present invention has excellent physical properties excellent in adhesiveness, moldability, shielding properties and coloring properties, it can be utilized for the decor sheet.

In addition, the laminated co-polyester film of the present invention contains the pigment in the outermost layer (layer (A)) of the final film, and can be produced using recycled raw materials as the polyester raw material, reducing the cost burden of the final film Can be.

As described above, the present invention provides a polyester film for decorating sheet having a structure in which a copolyester layer (A) having a shielding property, colorability, and adhesiveness is laminated on at least one side of the copolyester layer (B). .

Thus, firstly, as a raw material of the laminated co-polyester film, the second component 5 to 95 in a single or mixed form selected from dicarboxylic acid or diol, in the polyester first component consisting of repeating units of dicarboxylic acid and diol By containing mol%, the polyester film for decor sheets excellent in the printing adhesive force and the moldability was provided.

Second, by further containing a pigment in the raw material of the laminated copolyester film, in particular, by containing the pigment in the copolyester polyester layer (A), to provide a polyester film for decor sheet excellent in the shielding and coloring properties and cost reduction effect It was.

Third, the optimum method for producing the laminated co-polyester film of the present invention provided a polyester film for decorating sheet, in which the uniformity of the film thickness and foreign matter generation were minimized.

Fourth, as a raw material of the laminated co-polyester film, a laminated co-polyester film with reduced cost burden was provided by using a recycled raw material.

Fifth, the polyester film for decorating sheet of the present invention can be applied to overlay, lapping, member lane, high-gloss, interior sheet applications.

Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and modifications belong to the appended claims.

Claims (19)

At least a copolyester layer (B) containing from 5 to 95 mol% of a second component in a single or mixed form selected from dicarboxylic acids or diols in a polyester first component consisting of a repeating unit of dicarboxylic acid and diol On one side, Pigment is further contained in the copolyester raw material containing 5 to 95 mol% of the second component in a single or mixed form selected from dicarboxylic acid or diol, in the polyester first component comprising a repeating unit of dicarboxylic acid and diol. A polyester film for decorating sheet, wherein the copolyester layer (A) is laminated. The polyester film for decorating sheet according to claim 1, wherein the pigment is contained in an amount of 0.1 to 40% by weight based on the weight of the copolyester raw material. The polyester film for decorating sheet according to claim 1, wherein the pigment is at least one selected from the group consisting of a white pigment, a black pigment, a red pigment, a yellow pigment, a green pigment, a blue pigment, and a purple pigment. . The polyester film for decorating sheet according to claim 1, wherein the total thickness of the polyester film for decorating sheet is 40 to 1200 µm. The thickness of the said copolyester layer (A) is 1-500 micrometers, The said polyester film for decorative sheets of Claim 1 characterized by the above-mentioned. The structure according to claim 1, wherein the polyester film for decor sheet has a copolymer polyester layer (A) laminated on both sides of the copolymer polyester layer (B) (layer (A) / layer (B) / layer (A)). ), The thickness ratio is 1: 1: 1 to 1: 50: 1 polyester film for decorating sheet, characterized in that. The thickness of claim 1, wherein the polyester film for decor sheet has a structure (layer (A) / layer (B)) in which a copolymerized polyester layer (A) is laminated on one surface of the copolymer polyester layer (B). The ratio is 1: 1 to 1:50 polyester film for decorating sheet, characterized in that. The said polyester film for decor sheets of Claim 1 whose said co-polyester layer (A) or co-polyester layer (B) is a regeneration raw material. The polyester film for decorating sheet according to claim 1, wherein the tensile elongation of the polyester film for decorating sheet is 170% or more. The polyester film for decorating sheet according to claim 1, wherein the total light transmittance of the polyester film for decorating sheet is 50% or less. The dicarboxylic acid second component is isophthalic acid, 2,6-naphthalenedicarboxylic acid, sebacic acid, adipic acid, diphenyldicarboxylic acid, 5-tert-butyl butyl isophthalic acid, 2,2,6,6-tetramethyldiphenyl-4,4-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindan-4,5-dicarboxylic acid, 5-sodium sulfoisophthalic acid, Trimellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimeric acid, azelaic acid, pyromellitic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and dimethyl- The polyester film for decor sheet, characterized in that any one or more selected from the group consisting of 1,4-cyclohexanedicarboxylic acid. The diol second component is diethylene glycol, triethylene glycol, hexanediol, pentanediol, diol of 2,2- (4-oxyphenol) propane derivative, xylene glycol, 1,4-butanediol , 1,3-butanediol, 1,2-butanediol, 1,3-propanediol, 1,2-propanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, polytetramethylene glycol, polyethylene glycol, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol Polyester film for the decor sheet, characterized in that at least one selected from the group consisting of. Copolymerized polyester layer (B) and copolymerization containing 5 to 95 mol% of second components in a single or mixed form selected from dicarboxylic acids or diols in a polyester first component comprising a repeating unit of dicarboxylic acid and diol The raw material of the polyester layer (A) is put into a separate extruder, melt-extruded, a melt sheet is produced in a multilayered laminated structure, and the melt sheet is produced by bringing the melt sheet into close contact with a cold rotating roll. Method for producing a polyester film for decor sheet. The copolymerized polyolefin of claim 13, wherein at least one pigment selected from the group consisting of a white pigment, a black pigment, a red pigment, a yellow pigment, a green pigment, a blue pigment, and a purple pigment is added to the copolyester layer (A). The production method, characterized in that containing 0.1 to 40% by weight based on the weight of the ester. The method of claim 13, wherein the melt extrusion process is performed at 160 to 280 ℃. The said laminated structure is a structure (layer (A) / layer (B) / layer (A)) by which the co-polyester layer (A) was laminated | stacked on both surfaces of the co-polyester layer (B), The manufacturing method, characterized in that the thickness ratio of each layer is 1: 1: 1 to 1: 50: 1. The layer structure according to claim 13, wherein the laminated structure is a structure in which a copolyester layer (A) is laminated on one surface of the copolyester layer (B) (layer (A) / layer (B)), and the thickness ratio of each layer is 1. The production method, characterized in that: 1 to 1:50. The said manufacturing method of Claim 13 whose total thickness of the said polyester film for decoration sheets is 40-1200 micrometers. The said manufacturing method of Claim 13 whose thickness of the said copolyester layer (A) is 1-500 micrometers.