KR102318574B1 - Decoration film, preparation method thereof and membrane formed article comprising the same - Google Patents

Abstract

The present invention relates to a decor film, a method for manufacturing the same, and a membrane molded article comprising the same, and more particularly, the decor film includes a calendering polyester resin layer, and the calendering polyester resin layer is neopentyl as a diol repeating unit. Since it contains any one residue selected from the group consisting of 2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, and combinations thereof together with the glycol residue, calender processability It is excellent in this, and it is excellent in printability and thermal paper lamination property.

Description

DECORATION FILM, PREPARATION METHOD THEREOF AND MEMBRANE FORMED ARTICLE COMPRISING THE SAME

The present invention relates to a decorative film having excellent calendering property, excellent printability and thermal lamination, a method for manufacturing the same, and a membrane molded article including the same.

The calendering process is a process of forming a film, sheet, etc. using a calender, that is, a rolling machine in which several heating rolls are arranged. The calendering process has been mainly used to make films, sheets, etc. because it has a faster production rate and relatively easy processing to a thin thickness compared to an extrusion process.

PVC (Polyvinyl Chloride), PP (polypropylene), etc. are used as the material of the film manufactured by the calendering process. However, PVC is difficult to recycle and has non-environmental characteristics such as a high possibility of generating harmful gases when discarded, so there is a high demand for a material that can replace PVC. Although PP (Polypropylene) has excellent calendering properties, it is not eco-friendly, and it has the inconvenience of requiring a separate primer treatment for printing or lamination. In addition, there is also a problem of defects due to delamination even after making a thermoplastic molded product.

In addition, PET (Polyethylene Terephthalate) film manufactured by the conventional extrusion method has a certain limit on the lower limit of the production thickness, and can be produced with a thinner thickness by the stretching process, but the productivity tends to decrease compared to the calendering process. have.

Korean Patent Publication No. 10-2004-0051808 (published on June 19, 2004) Korean Patent Registration No. 10-1108471 (Announcement on Jan. 31, 2012)

An object of the present invention is to provide an eco-friendly decorative film that is excellent in calendering property and excellent in printability and can be manufactured to a thin thickness capable of thermal lamination, a manufacturing method thereof, and a membrane molded article including the same.

In order to achieve the above object, one aspect of the present invention is a base layer; And a decorative film comprising a coating layer positioned on the base layer; wherein at least one of the base layer and the coating layer is a calendering polyester resin layer comprising a dicarboxylic acid repeating unit and a diol repeating unit, The diol repeating unit includes a neopentyl glycol residue, and the diol repeating unit contains i) 2-methyl-1,3-propanediol residue in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or ii) a residue of 2-methyl-1,3-propanediol and a residue of 2-ethyl-2-methyl-1,3-propanediol, wherein the residue of 2-methyl-1,3-propanediol is the diol repeating unit. It is contained in an amount of 1 to 15 mol% based on the total, and the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of more than 0 and 30 mol% or less based on the total amount of the diol repeating unit, and the decor The film has a gray scale of 1.0 or less after 1000 hours of exposure based on weather resistance according to KS M ISO 4892-2 2012, and the decorative film provides a decorative film with 4 or more grades in chemical resistance according to KS G ISO 4211:2009.

The 2-ethyl-2-methyl-1,3-propanediol residue may be contained in an amount of 1 to 16 mol% based on the total amount of the diol repeating unit.

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A printed layer positioned on the base layer may be further included.

The printing layer may have a bonding strength of 5B or more applied to the ASTM D 2259 standard.

The decorative film is thermally laminated, and when the base layer and the coating layer are tested with 180 ° peel adhesion, it may have lamination properties of 10N/20mm or more.
The thermally laminated decorative film may have an area peeled off after thermal lamination of 10% or less.

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Another aspect of the present invention includes a coating layer, wherein the coating layer is a base layer; and a coating layer positioned on the base layer, wherein at least one of the base layer and the coating layer is a calendering polyester resin layer comprising a dicarboxylic acid repeating unit and a diol repeating unit, and the diol repeating unit contains a neopentyl glycol residue and a diol residue, and the diol repeating unit contains i) 2-methyl-1,3-propanediol residue in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or ii ) 2-methyl-1,3-propanediol residue and 2-ethyl-2-methyl-1,3-propanediol residue, wherein the 2-methyl-1,3-propanediol residue is the whole of the diol repeating unit. 1 to 15 mol% based on the , the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of more than 0 and 30 mol% or less based on the entire diol repeating unit, and the coating layer is According to KS M ISO 4892-2 2012, the gray scale after 1000 hours of exposure is 1.0 or less, and the coating layer provides a membrane molded article having 4 or more grades in chemical resistance according to KS G ISO 4211:2009.

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The decorative film is thermally laminated, and when the coating layer is tested with 180 ° peel adhesion, it may have lamination properties of 10N/20mm or more.

The base layer and the coating layer may be thermally laminated with or without a printed layer disposed therebetween.

The coating layer may have no cloudiness in the bent or bent portion.

The polyester resin layer may have a thickness of 40 um or more.

A printed layer positioned on the base layer may be further included.

The printing layer may have a bonding strength of 5B or more applied to the ASTM D 2259 standard.

Another aspect of the present invention, a resin manufacturing step of preparing a polyester resin composition comprising a dicarboxylic acid compound and a diol compound; calendering step of preparing the polyester resin composition as a polyester resin layer by a calendering method; And a film manufacturing step of laminating two or more layers of the polyester resin in a plurality of layers and thermally laminating to prepare a decor film; to prepare a decor film, including, wherein the decor film is a dicarboxylic acid repeating unit and a diol repeating unit wherein the diol repeating unit contains i) 2-methyl-1,3-propanediol residue in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or ii) 2-methyl-1,3- It contains a propanediol residue and a 2-ethyl-2-methyl-1,3-propanediol residue, and the 2-methyl-1,3-propanediol residue is present in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit. and the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount greater than 0 and 30 mol% or less based on the entire diol repeating unit, and the decorative film is in accordance with KS M ISO 4892-2 2012. The gray scale is 1.0 or less after 1000 hours of exposure on the basis of the weather resistance by

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In the film manufacturing step, thermal lamination may be performed at a temperature of 120 to 180 ° C and a pressure of 0.3 to 0.5 Mpa.

According to the decorative film and the like of the present invention, it is excellent in calendering property, excellent in printability, and provides a decorative film, etc. in which the interlayer thermal lamination is possible without the application of a separate primer or adhesive layer. In addition, the decorative film has the advantage of being easy to apply to a membrane molded article, etc. excellent in membrane formability and weather resistance. The decor film can be applied as a decor film to molded articles such as MDF substrates, and can be applied to doors such as closets, table tops, partitions, decorative panels, and the like.

1 is a view for explaining a cross-section of a decorative film according to an embodiment of the present invention.
2 is a view for explaining a cross-section of a membrane molded article according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein. Throughout the specification, like reference numerals are assigned to similar parts.

Throughout this specification, the term "combination of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, and the components It is meant to include one or more selected from the group consisting of.

In the present specification, "~ system" may mean including a compound corresponding to "~" or a derivative of "~" in the compound. “Derivative” refers to a compound in which the structure and properties of the parent are not changed, such as introduction of functional groups, oxidation, reduction, substitution of atoms, etc., using a specific compound as a parent.

In this specification, the meaning that B is positioned on A means that B is positioned so that it directly abuts on A or that B is positioned on A while another layer is positioned between them, and B is positioned so that it abuts on the surface of A It is not construed as being limited to

In the present specification, unless otherwise specified, the expression "a" or "a" is interpreted as meaning including the singular or the plural as interpreted in context.

While the inventors of the present invention continued research on decorative films with excellent moldability applied to decorative panels, etc., 2-methyl-1,3-propanediol compound (MPDO), 2-ethyl-2-methyl as diol-based compounds When -1,3-propanediol compound (EMPO), etc. is applied together with neopentyl glycol compound (NPG), membrane molding is possible even with a film having a thinner thickness, and a film with excellent moldability, weather resistance, and thermal lamination properties is produced. It was confirmed that it can be manufactured, and the present invention was completed.

1 is a view for explaining a cross-section of a decorative film 100 according to an embodiment of the present invention, Figure 1 (a) is a base layer 10; And a cross-section of the decor film including the coating layer 20 positioned on the base layer, FIG. 1 (b) is a decor further comprising a printed layer 30 between the base layer 10 and the coating layer 20 A cross section of the film is shown. 2 is a view for explaining a cross-section of the membrane molded article 200 according to an embodiment of the present invention. Hereinafter, the present invention will be described in more detail.

In order to achieve the above object, the decorative film 100 according to an embodiment of the present invention includes a base layer 10; and a coating layer 20 positioned on the base layer. The decorative film 100 may further include a printed layer 30 between the base layer and the coating layer.

The base layer 10 and the coating layer 20 may be colored layers containing dyes or pigments.

At least one of the base layer 10 and the coating layer 20 may be a calendering polyester resin layer containing a dicarboxylic acid repeating unit and a diol repeating unit.

The base layer 10 and the coating layer 20 may be calendering polyester resin layers each containing a dicarboxylic acid repeating unit and a diol repeating unit.

The polyester resin layer includes a dicarboxylic acid repeating unit and a diol repeating unit. That is, the polyester resin layer is formed by polymerization by applying a dicarboxylic acid-based compound and a diol-based compound as a monomer, and has repeating units derived from the dicarboxylic acid-based compound and the diol-based compound as a residue. .

A dicarboxylic acid-based compound and a diol-based compound are included in the composition for synthesizing the resin to form the polyester resin layer.

The composition for synthesizing the resin may include the diol-based compound in an amount of 1.05 to 3 moles based on 1 mole of the dicarboxylic acid-based compound. Specifically, the polyester resin layer may be prepared by mixing the dicarboxylic acid component and the diol component in a molar ratio of 1:1.05 to 1:2.0 to perform an esterification reaction. More specifically, the polyester resin layer may be prepared by mixing the dicarboxylic acid component and the diol component in a molar ratio of 1:1.05 to 1:1.5 to perform an esterification reaction.

When the molar ratio of the dicarboxylic acid component and the diol component is within the above range, the esterification reaction proceeds stably, sufficient ester oligomer can be formed, and advantageous properties derived from the neopentyl glycol component, etc., which will be described later, are expressed. may be easier to

The dicarboxylic acid repeating unit is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, succinic acid, glutaric acid, orthothalic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid Compounds comprising an acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid and derivatives thereof, or combinations thereof including those derived from

Specifically, the dicarboxylic acid repeating unit may be derived from any one compound selected from the group consisting of terephthalic acid, naphthalene dicarboxylic acid, and combinations thereof.

The diol-based repeating unit is any one selected from the group consisting of a 2-methyl-1,3-propanediol compound, a 2-ethyl-2-methyl-1,3-propanediol compound, and a combination thereof together with a neopentyl glycol compound. Contains residues derived from one compound.

The polyester resin layer is any one selected from the group consisting of a neopentyl glycol residue, a 2-methyl-1,3-propanediol residue, a 2-ethyl-2-methyl-1,3-propanediol residue, and combinations thereof. It may contain one moiety.

The decorative film 100 of the present invention is a polyester resin layer included therein with a neopenkyl glycol repeating unit, a 2-methyl-1,3-propanediol repeating unit, 2-ethyl-2-methyl-1,3- It is characterized in that it comprises any one repeating unit selected from the group consisting of propanediol and combinations thereof.

The neopentyl glycol has two methyl groups branched in the middle of the chain in addition to the hydroxyl group at the terminal participating in the polymerization reaction, and is included in the main chain of the polyester resin layer together with the carboxylic acid-derived repeating unit between the main chains adjacent to each other. An appropriate space is formed, which is thought to affect calendering property, printability, thermal lamination property, and membrane formability of the calendering polyester resin.

The polyester resin layer may contain 20 to 70 mol% of neopentyl glycol residues as diol residues.

The polyester resin layer may include a 2-methyl-1,3-propanediol residue and/or a 2-ethyl-2-methyl-1,3-propanediol residue in a main chain as a diol residue.

The 2-methyl-1,3-propanediol residue may be contained in an amount greater than 0 and 30 mol% or less based on the total diol residue. Specifically, the 2-methyl-1,3-propanediol residue is 1 to 30 mol%, 1 to 25 mol%, 1 to 15 mol%, 1 to 10 mol%, 1 to 5 based on the total diol residue. It may contain mol%.

The 2-ethyl-2-methyl-1,3-propanediol residue may be contained in an amount greater than 0 and 30 mol% or less based on the total diol residue. Specifically, the 2-ethyl-2-methyl-1,3-propanediol residue is 1 to 30 mol%, 1 to 25 mol%, 1 to 16 mol%, 1 to 10 mol%, based on the total diol residue; It may be 1 to 5 mol%.

When neopentyl glycol, 2-methyl-1,3-propanediol, and 2-ethyl-2-methyl-1,3-propanediol are included in the diol-based compound within this range, calendering processability can be further improved. In addition, it is possible to improve the color, mechanical properties, etc. of the manufactured film.

The polyester resin layer has carbon atoms in the remaining amount other than i) the neopentyl glycol residue and ii) the 2-methyl-1,3-propanediol residue and/or the 2-ethyl-2-methyl-1,3-propanediol residue. 2 to 10 linear or branched aliphatic diols.

The linear or branched aliphatic diol compound having 2 to 10 carbon atoms is specifically, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3- butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,1-dimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-3 -Methyl-1,5-hexanediol, 2-ethyl-3-ethyl-1,5-hexanediol, 1,7-heptanediol, 2-ethyl-3-methyl-1,5-heptanediol, 2-ethyl derivatives such as -3-ethyl-1,6-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, or a combination thereof. More specifically, it may include an ethylene glycol residue.

The polyester resin layer applied in the present invention includes 2-methyl-1,3-propanediol and/or 2-ethyl-2-methyl-1,3-propanediol, each of which has a molecular size similar to that of neopentyl glycol. Compared with the polyester resin layer to which the neopentyl glycol residue is applied by having a methyl or ethyl group as a side chain while having This allows the polymer chains included in the polyester resin layer to form a relatively constant space between the chains without being bulky. It is thought to be one of the causes. And the limited irregularity induced in the polyester resin layer described above is considered to be one of the causes of bringing about better thermal lamination and printability.

The polyester resin layer may substantially not include an alicyclic diol as the diol-based compound. The alicyclic diol includes, for example, cyclohexanedimethanol, isosorbide, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and the like. When the alicyclic diol is applied to the ester resin layer, it may not be possible to obtain sufficient physical properties of the decorative film of the present invention due to bulky characteristics.

The polyester resin layer may have a non-crystalline characteristic. When the polyester resin layer having such amorphous characteristics is manufactured by a calendering method, workability of the process may be further improved.

The composition for synthesizing the resin may further include components such as a polycondensation catalyst, a stabilizer, and a colorant. The polycondensation catalyst, stabilizer, and colorant may be added to the product of the esterification reaction or transesterification reaction before the start of the polymerization reaction, and before the esterification reaction, a mixed slurry comprising a dicarboxylic acid and a diolide It may be added to the phase, or may be added in the middle of the esterification step.

The polycondensation catalyst may include, as a metal catalyst, an antimony-based compound, a titanium-based compound, a germanic compound, an aluminum-based compound, or a mixture thereof. The antimony-based compound may include, for example, antimony trioxide, antimony acetate, antimony glycolate, and the like. The titanium-based compound may include, for example, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, titanium dioxide, titanium dioxide/silicon dioxide copolymer, and the like. The germanic compound may include, for example, germanium dioxide, germanium acetate, germanium glycolate, and the like. The polycondensation catalyst may be used in an amount of specifically 50 to 500 ppm, more specifically 50 to 400 ppm, based on the weight of the polyester resin.

As the stabilizer, for example, a phosphorus-based compound selected from the group consisting of phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, hindered phenol, and combinations thereof may be additionally used. It is not particularly limited as long as it can be commonly used in The stabilizer may be added in an amount of 3000 ppm or less, more specifically 1000 ppm or less, based on the weight of the polyester resin.

The colorant may be further included to improve color, for example, cobalt acetate, cobalt propionate, etc. may be used. In addition to the colorant, a component selected from the group consisting of an organic compound colorant, an inorganic compound colorant, a dye, and a combination thereof may be used. The colorant may be used in an amount of 5 to 100 ppm based on the weight of the polyester resin.

The decor film 100 may include a base layer 10 including a polyester resin layer and a coating layer 20 thermally laminated on one surface of the base layer.

The decor film 100 is located on the base layer 10 and the printed layer 30 printed with a chromatic or achromatic pattern formed on the base layer, the printed layer, and the base layer 10 and the It may include a thermally laminated coating layer 20 with the printing layer 30 interposed therebetween.

The printing layer 30 may be formed by applying a printing method applied to a conventional polyester film, and the printing layer may be formed by, for example, gravure printing, but is not limited thereto.

The printing layer may have a bonding strength of 5B or more applied to the ASTM D 2259 standard. This means that the printed layer 30 formed on the base layer 10 has excellent printing stability.

The thermal lamination is performed between the substrate layer 10 and the coating layer 20, which are located up and down with a printed layer therebetween, or between the substrate layer 10 and the coating layer 20 on which a printing layer is not formed. can

The thermal lamination may be specifically performed for 10 seconds to 1 minute at a lamination temperature of 120 to 180 ℃ with a lamination pressure of 0.3 to 0.5 Mpa, and a lamination pressure of 0.35 to 0.45 Mpa at a lamination temperature of 140 to 160 ℃ 20 seconds It may proceed for from 40 seconds. When the thermal lamination is performed at this lamination temperature and lamination pressure, lamination can be efficiently carried out between the base layer 10 and the coating layer 20, and a decor film having a lamination property of a certain level or higher required for a decor film. can be prepared without a separate primer treatment or adhesive layer treatment.

The thermally laminated decorative film may have an area of 10% or less that is peeled with respect to the total area laminated in a peel force test based on an area of 30 X 50 mm. This shows that thermal lamination is possible with excellent bonding strength without applying a separate primer layer or adhesive layer.

The decorative film is thermally laminated, and as a result of testing the base layer and the coating layer with 180 ° peel adhesion, it may have a laminability of 10N/20mm or more, and may have a laminability of 12N/20mm or more, and 15N/20mm or more. It may have synthetic properties. This means that the interlayer bonding strength after thermal lamination is quite excellent, and when the decorative film is applied as a coating film, it means that it has excellent interlayer durability.

The decorative film may satisfy the weather resistance standard measured by KS M ISO 4892-2: 2012 (*) method (confirmed by gray scale value at 1000 hr) by 4 or more grades, and more specifically, by 5 or more grades.

Specifically, the decorative film may have a gray scale of 1.0 or less and 0.8 or less after exposure for 1000 hours based on weather resistance according to KS M ISO 4892-2 2012. The decor film having these characteristics can provide a decor film with minimal quality change even after long-term use by having excellent weather resistance.

The decorative film may have a chemical resistance of 4 or higher according to KS G ISO 4211:2009. This means that the decorative film has excellent chemical resistance, and when applied to a membrane molded article, a coating layer having excellent chemical resistance can be formed.

The polyester resin layer may have a thickness of 40 um or more, or 50 um or more. The decorative film 100 including the polyester resin layer as the base layer 10 and/or the coating layer 20, respectively, may have a thickness of 90 um or more and 100 um or less.

The polyester resin layer may have a thickness of 500 um or less, or 400 um or less. The decorative film 100 including the polyester resin layer as the base layer 10 and/or the coating layer 20, respectively, may have a thickness of 900 um or less, and may be 850 um or less.

The polyester resin layer can be calendered to a relatively thin thickness, and when the prepared layer is applied to the decoration film, a decoration film having excellent membrane moldability can be manufactured. In addition, the polyester resin layer has excellent laminating power and printability between layers by thermal lamination, so it can have excellent laminating properties without applying a separate primer or adhesive layer, and can be used as a coating layer for membrane molded products with superior physical properties do.

The membrane molded article 200 according to another embodiment of the present invention includes a coating layer 210 on which the decorative film 100 is coated by a membrane molding method on the uncoated molded article 220 . Since the detailed description of the decorative film 100 overlaps with the above description, the description thereof will be omitted.

The uncoated molded article 220 may be, for example, an MDF wood panel, but is not limited thereto, and is applicable as long as it is manufactured by coating a decorative film in a membrane molding method.

The coating layer 210 included in the membrane molded article 200 does not cause cloudiness in the bent or bent portion.

The coating layer 210 is thermally laminated, and as a result of testing with 180 ° peel adhesion, it may have an adhesive force of 10N/20mm or more, may have an adhesive force of 12N/20mm or more, and may have an adhesive force of 15 N/20mm or more. In the case of having such peel adhesion, superior interlayer durability may be obtained.

The coating layer may have a gray scale of 1.0 or less and 0.8 or less after exposure for 1000 hours based on weather resistance according to KS M ISO 4892-2 2012. The coating layer having these characteristics has excellent weather resistance, so that quality change is insignificant even after long-term use.

The coating layer may specifically satisfy the chemical resistance standard measured by the KS G ISO 4211:2009 method by 4 or more grades, and more specifically, by 5 or more grades.

The coating layer can specifically satisfy the weather resistance standard measured by KS M ISO 4892-2: 2012 (*) method (confirmed by gray scale value at 1000hr) by 4 or more grades, and more specifically, by 5 or more grades. .

Specifically, the coating layer may have a gray scale of 1.0 or less and 0.8 or less after exposure for 1000 hours based on weather resistance according to KS M ISO 4892-2 2012. The coating layer having these characteristics has excellent weather resistance, and thus it is possible to provide a coating layer with minimal quality change even after long-term use.

The coating layer may be one in which the base layer and the protective layer are thermally laminated, and the thermal lamination is specifically performed at a laminating temperature of 120 to 180 ℃ and a laminating pressure of 0.3 to 0.5 Mpa for 10 seconds to 1 minute. At a lamination temperature of 140 to 160 °C, a lamination pressure of 0.35 to 0.45 Mpa may be performed for 20 to 40 seconds. When the thermal lamination is performed at this lamination temperature and lamination pressure, lamination can be efficiently carried out between the base layer 10 and the coating layer 20, and a decor film having a lamination property of a certain level or higher required for a decor film. can be prepared without a separate primer treatment or adhesive layer treatment.

A method of manufacturing a decor film according to another embodiment of the present invention includes: i) a dicarboxylic acid compound; and ii) a diol comprising any one selected from the group consisting of 2-methyl-1,3-propanediol residue, 2-ethyl-2-methyl-1,3-propanediol, and combinations thereof together with neopentyl glycol A resin manufacturing step of preparing a polyester resin composition comprising a compound; a calendering step of administering the polyester resin composition to a calendering roll to prepare a polyester resin layer in a calendering method; And a film manufacturing step of laminating two or more layers of the polyester resin in a plurality of layers and thermal lamination to produce a decorative film.

In the resin manufacturing step, the dicarboxylic acid compound and the diol compound may be esterified to prepare a product, and the product may be polycondensed to prepare a polyester resin composition.

The resin prepared from the polyester resin composition may specifically have an intrinsic viscosity (IV) of 0.6 to 1 dl/g, 0.6 to 1 dl/g, and 0.65 to 0.85 dl/g. When the intrinsic viscosity of the polyester resin is within the above range, the calendering property is excellent, the kinematic viscosity retention during the calendering process is excellent, and the thickness uniformity of the sheet and the film is excellent.

The calendering step may form a polyester resin layer by molding the polyester resin composition into a film or sheet form.

The calendering polyester resin layer may include a neopentyl glycol-derived diol repeating unit, and specifically, the neopentyl glycol may be included in an amount of 20 to 70 mol% based on the total diol repeating unit of the polyester resin layer. have. That is, the calendering polyester resin layer may be made of a composition for synthesizing the resin, and the detailed description of the composition for synthesizing the resin overlaps with the above description, and thus the description thereof will be omitted.

The calendering step may include rolling at a temperature of 120 to 250 °C using a plurality of calender rolls.

Specifically, the calendering step sequentially includes a kneading process, a rolling process, and a cooling process performed by applying a plurality of rolls.

The plurality of layers includes a first polyester resin layer and a second polyester resin layer, and corresponds to the base layer 10 and the coating layer 20 described above, respectively.

The first composition applied to the first polyester resin layer and the second composition applied to the second polyester resin layer may be the same as or different from each other in the polyester resin composition described above.

The first composition and the second composition may be administered to the first calendaring roll and the second calendaring roll, respectively, to be prepared into a first polyester resin layer and a second polyester resin layer, and these are laminated and thermally laminated. It can form a decorative film.

When the polyester film is manufactured by applying the calendering process in this way, the production rate is improved compared to the extrusion process, and a film having excellent physical properties can be manufactured.

The method of manufacturing the decorative film may further include a printing layer forming step between the pallindering step and the film manufacturing step.

In the step of forming the printed layer, a printed layer of a predetermined pattern is formed on one side of the base layer or at least one side of the coating layer.

The method of forming the print layer may be exemplarily applied to a method such as gravure printing, but is not limited thereto, and any method that does not interfere with the thermal lamination process to be described later is applicable.

The thermal lamination may be specifically performed for 10 seconds to 1 minute at a lamination temperature of 120 to 180 ℃ with a lamination pressure of 0.3 to 0.5 Mpa, and a lamination pressure of 0.35 to 0.45 Mpa at a lamination temperature of 140 to 160 ℃ 20 seconds It may proceed for from 40 seconds. In the case of thermal lamination under the above conditions, two or more polyester resin layers comprising a plurality of layers may be reliably laminated without deformation between each other.

The decorative film according to the present invention and the membrane molded article to which the decorative film is applied as a coating layer satisfy all moldability, weather resistance, chemical resistance, thermal lamination properties, printability, etc., and are more excellent in that they are environmentally friendly.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely examples to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

Examples 1 to 8: Preparation of polyester decorative film

A polyester resin was prepared by sequentially applying an ester reaction and a polycondensation reaction to a composition for synthesizing a resin including a dicarboxylic acid compound and a diol compound.

Specifically, terephthalic acid was applied as the dicarboxylic acid compound, and 2-methyl-1,3-propanediol and/or 2-ethyl-2-methyl-1 together with ethylene glycol and neopentyl glycol as the diol compound; 3-propanediol was applied as shown in Table 1 below. In the composition for synthesizing the resin, the molar ratio of dicarboxylic acid: diol is 1:1.05 to 3.0, but 20 to 70 mol% of neopentyl glycol based on the total diol compound, 2-methyl-1,3- Propanediol greater than 0 and 30 mol% or less, 2-ethyl-2-methyl-1,3-propanediol greater than 0 and 30 mol% or less, the esterification reaction was carried out at 230 to 270° C. and 0.1 to 3.0 kg/cm 2 conditions. Proceeded to form an ester oligomer. A polycondensation catalyst and a stabilizer were further mixed with the thus formed ester oligomer to carry out a polycondensation reaction to prepare a polyester resin.

The polyester resin was put into calendering equipment to prepare a polyester resin layer having a thickness of 50 μm or more.

The polyester resin layer was laminated in two or more layers, and was applied at 150° C. and 0.4 Mpa and thermal lamination for 30 seconds to prepare a decorative film.

Comparative Examples 1 to 5: Preparation of polyester decorative film

It was carried out in the same manner as in Examples 1 to 8, except that the components and contents indicated in Table 2 were used.

Measurement of physical properties

The films prepared in Examples and Comparative Examples were evaluated for physical properties in the following manner, and the results are summarized in Tables 1 and 2.

1. Intrinsic Viscosity (IV)

After dissolving the resins prepared in Examples 1 to 8 and Comparative Examples 1 to 5 in 100 ° C. Ortho-Chlorophenol, the drop time of the sample with an Ostwald viscometer in a constant temperature bath at 35 ° C. was obtained and the intrinsic viscosity (IV) was measured.

2. Calenderability

The calendering properties of the films prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were evaluated through the surface state of the film (non-gelled material, the presence or absence of flow marks).

◎: Excellent surface condition when ungelled cargo, flow marks, etc. occur within 10%

○: When ungelled cargo, flow marks, etc. occur in more than 10% and less than 20%,

△: When ungelled cargo, flow marks, etc. occur in more than 20% and less than 30%

X: When ungelled cargo, flow marks, etc. occur more than 30%, the surface condition is poor

3. Printability

After gravure printing was performed on the films of Examples 1 to 8 and Comparative Examples 1 to 5 under the conditions of a temperature of 150° C. or less, a speed of 100 m/s, and a pressure of 20 to 40 kgf/cm ^{2 , the ink composition was respectively applied to the ink layer.} was formed.

Adhesion was evaluated by applying the printed layer to ASTM D 2259 standard, and the average of the results of repeating this three times is shown in Table 2.

The ASTM D 2259 standard is to determine the degree of the ink layer separated from the film when the adhesive tape is attached to the substrate (film) and the adhesive tape is slowly removed after pressing with the same force, as shown below 1B to 5B divided by .

5B: Separated ink layer O % (best)

4B: 5% or less of the separated ink layer

3B: separated ink layer 5~15%

2B: Separated ink layer 15 ~ 35%

1B: separated ink layer 35 ~ 65%

0B: Separated ink layer 65% or more (worst)

4. Thermoplasticity

After laminating the films of Examples 1 to 8 and Comparative Examples 1 to 5, respectively, and constant pressurization at the same temperature and pressure (150 ° C., 0.4 Mpa, 30 seconds) with a thermal lamination apparatus, lamination property according to the following criteria It was evaluated (the combined total area is 30 X 50 mm).

◎: When the total area laminated does not fall at all

○: In case of peeling in less than 10% of the total area of lamination

△: When peeled in the range of 10 to 30% with respect to the total area of the laminated

×: In case of peeling in excess of 30% of the total area laminated

5. Formability

After preparing MDF wood, placing the films of Examples 1 to 8 and Comparative Examples 1 to 5 on the MDF wood, membrane molding at 80 ° C., observing the molding state, and evaluating the results according to the following criteria did.

◎: Very good, ○: Good, △: Good but rounded corners, ×: Not molded

6. Whitening resistance

The films of Examples 1 to 8 and Comparative Examples 1 to 5 were molded with a vacuum molding machine, and moldability was evaluated by relatively comparing how much cloudiness occurs in the corners.

◎: does not occur at all

○: Occurs within 20%, but commercialization is possible

△: Occurs within 20 ~ 40_%, but cannot be commercialized

×: It is impossible to commercialize due to the occurrence of more than 40%

7. Weather resistance

The films of Examples 1 to 8 and Comparative Examples 1 to 5 were measured by the KS M ISO 4892-2 2012 (*) test method, and the gray scale value was checked at 1000 hr and evaluated according to the following grades.

The gray scale values were evaluated as follows.

Grade 5 within 0 ± 0.2,

If it is within 0.8 ± 0.2, grades 4 to 5,

Grade 4 if within 1.7 ± 0.3;

3 to 4 grades within 2.5 ± 0.35;

Grade 3 if within 3.4 ± 0.4;

2 to 3 grades for 4.8 ± 0.5;

Grade 2 for 6.8 ± 0.6;

1~2 grade for 9.6 ± 0.7, 1 grade for 13.6 ± 1.0

8. Chemical resistance

The films of Examples 1 to 8 and Comparative Examples 1 to 5 were measured by the KS G ISO 4211:2009 method, and after chemical treatment on the film, the surface condition was checked after 24 hours to evaluate the chemical resistance as follows.

A rating of 5 (best) if the measurement results show no visible damage;

Grade 4 if there is a slight change in gloss,

Grade 3 if there is a slight mark on the surface by the drug,

Grade 2, if clear contamination marks are visible but the structure of the sheet surface does not change.

Grade 1 if there are obvious stain marks and sheet structure changes or the surface material is completely or partially peeled off.

division Furtherance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 diecide
(Unit: mole %) TPA 90 90 90 90 90 90 90 90 IPA 10 10 10 10 10 10 10 10 Dior
(Unit: mole %) NPG 28 32 36 42 27 68 20 33 MPDO One 3 One 5 20 7 10 - EMPO - 2 - - 9 - 15 10 CHDM - - - - - - - - EG 71 63 63 53 44 25 55 57 intrinsic viscosity 0.78 0.76 0.68 0.83 0.77 0.77 0.85 0.72 Calender Machinability ○ ◎ ◎ ◎ ◎ ◎ ○ ◎ printability 5B 5B 5B 5B 5B 5B 5B 5B thermal paper ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ formability ◎ ◎ ◎ ○ ○ ○ ◎ ○ whitening resistance ◎ ◎ ◎ ○ ○ ○ ◎ ○ weather resistance 4-5 grades 4-5 grades 4-5 grades 4-5 grades 4-5 grades 4-5 grades 4-5 grades 4-5 grades chemical resistance 5th grade 5th grade 5th grade 4th grade 4th grade 4th grade 4th grade 4th grade

division Furtherance Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 diecide
(Unit: mole %) TPA 90 90 90 90 90 IPA 10 10 10 10 10 Dior
(Unit: mole %) NPG 15 - 85 66 10 MPDO - - - - 30 EMPO - - - - 25 CHDM - 33 - - - EG 85 67 15 34 35 intrinsic viscosity 0.61 0.75 0.68 0.78 0.70 Calender Machinability X ○ △ ◎ △ printability 3B 5B 4B 5B 4B thermal paper X ○ X ◎ △ formability X ○ X ○ △ whitening resistance X ◎ ◎ ○ ○ weather resistance 4-5 grades 2-3 grades 2-3 grades 4-5 grades 2-3 grades chemical resistance 4th grade 3rd grade 3rd grade 4th grade 3rd grade

Referring to the results of Tables 1 and 2, the film of Example 1 to 8 is a 2-methyl-1,3-propanediol residue and/or 2-ethyl-2-methyl-1,3 together with neopentyl glycol. - By applying propanediol, it can be confirmed that it has excellent calendering property, printability, thermal paper, moldability, whitening resistance, weather resistance, chemical resistance, and the like. In particular, in the case of Example 2 in which all three types of neopentyl glycol, 2-methyl-1,3-propanediol, and 2-ethyl-2-methyl-1,3-propanediol were used as diol compounds, 50 μm Although it was possible to form a film with a thickness, it was excellent in calendering property, printability, thermal lamination, moldability, whitening resistance, weather resistance, and chemical resistance. In addition, in the case of Example 3 in which neopentyl glycol and 2-methyl-1,3-propanediol were used as diol compounds, excellent physical properties were also shown.

Comparative Examples 1, 3, and 4 showed that calender processability, printability, thermal paper, moldability, whitening resistance, weather resistance, chemical resistance, etc. were somewhat insufficient when only neopentyl glycol was applied as a diol compound, and dimethylcyclohexanedimethylol Comparative Example 2 to which (CHDM) was applied had excellent printability and whitening resistance, but lacked weather resistance and chemical resistance.

The polyester resin according to the present invention is calendered by using a predetermined amount of 2-methyl-1,3-propanediol and/or 2-ethyl-2-methyl-1,3-propanediol other than neopentyl glycol as a diol compound. Due to its excellent processability, it was possible to obtain excellent physical properties such as printability, thermal lamination properties, moldability and weather resistance even with a film having a fairly thin thickness of about 50 μm or more.

Although the preferred embodiment of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

100: decorative film 10: base layer
20: coating layer 30: printing layer
200: membrane molded article 210: coating layer
220: uncoated molded article

Claims (14)

base layer; And as a decorative film comprising a coating layer located on the base layer,
At least one of the base layer and the coating layer is a calendering polyester resin layer comprising a dicarboxylic acid repeating unit and a diol repeating unit,
The diol repeating unit includes a neopentyl glycol residue and a diol residue,
The diol repeating unit is
i) 2-methyl-1,3-propanediol residue is contained in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or
ii) a residue of 2-methyl-1,3-propanediol and a residue of 2-ethyl-2-methyl-1,3-propanediol, wherein the residue of 2-methyl-1,3-propanediol is the diol repeating unit. It is contained in an amount of 1 to 15 mol% based on the total, and the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of more than 0 and 30 mol% or less based on the total amount of the diol repeating unit,
The decorative film has a gray scale of 1.0 or less after 1000 hours of exposure based on weather resistance according to KS M ISO 4892-2 2012,
The decorative film has a chemical resistance of grade 4 or higher according to KS G ISO 4211:2009,
deco film.
delete According to claim 1,
The 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of 1 to 16 mol% based on the total amount of the diol repeating unit, the decorative film.
According to claim 1,
Further comprising a printed layer positioned on the base layer,
The printing layer has a bonding strength of 5B or more applied to ASTM D 2259 standard, a decorative film.
According to claim 1,
The base layer and the coating layer are thermally laminated,
When the base layer and the coating layer were tested with 180 ° peel adhesion, having a laminating property of 10N/20mm or more,
deco film.
6. The method of claim 5,
The thermally laminated deco film is 10% or less of the area to be peeled off after thermal lamination, deco film.
delete delete a coating layer,
The coating layer is
base layer; and a coating layer positioned on the base layer,
At least one of the base layer and the coating layer is a calendering polyester resin layer comprising a dicarboxylic acid repeating unit and a diol repeating unit,
The diol repeating unit includes a neopentyl glycol residue and a diol residue,
The diol repeating unit is
i) 2-methyl-1,3-propanediol residue is contained in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or
ii) a residue of 2-methyl-1,3-propanediol and a residue of 2-ethyl-2-methyl-1,3-propanediol, wherein the residue of 2-methyl-1,3-propanediol is the diol repeating unit. It is contained in an amount of 1 to 15 mol% based on the total, and the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of more than 0 and 30 mol% or less based on the total amount of the diol repeating unit,
The coating layer has a gray scale of 1.0 or less after 1000 hours of exposure based on weather resistance according to KS M ISO 4892-2 2012,
The coating layer has a chemical resistance of grade 4 or higher according to KS G ISO 4211:2009,
Membrane molded parts.
10. The method of claim 9,
The base layer and the coating layer are thermally laminated,
When the coating layer was tested with 180 ° peel adhesion, having a laminability of 10N/20mm or more,
Membrane molded parts.
10. The method of claim 9,
Wherein the coating layer does not cause cloudiness in the bent or bent portion, the membrane molded article.
10. The method of claim 9,
The polyester resin layer will have a thickness of 40 um or more, a membrane molded article.
A resin manufacturing step of preparing a polyester resin composition comprising a dicarboxylic acid compound and a diol compound;
calendering step of preparing the polyester resin composition as a polyester resin layer by a calendering method; and
A film manufacturing step of laminating two or more layers of the polyester resin in a plurality of layers and thermal lamination to produce a decorative film;
The decor film includes a dicarboxylic acid repeating unit and a diol repeating unit,
The diol repeating unit is
i) 2-methyl-1,3-propanediol residue is contained in an amount of 1 to 15 mol% based on the total amount of the diol repeating unit, or
ii) a residue of 2-methyl-1,3-propanediol and a residue of 2-ethyl-2-methyl-1,3-propanediol, wherein the residue of 2-methyl-1,3-propanediol is the diol repeating unit. It is contained in an amount of 1 to 15 mol% based on the total, and the 2-ethyl-2-methyl-1,3-propanediol residue is contained in an amount of more than 0 and 30 mol% or less based on the total amount of the diol repeating unit,
The decorative film has a gray scale of 1.0 or less after 1000 hours of exposure based on weather resistance according to KS M ISO 4892-2 2012,
The decorative film has a chemical resistance of grade 4 or higher according to KS G ISO 4211:2009,
A method of manufacturing a decor film.
14. The method of claim 13,
The thermal lamination is a method of manufacturing a decor film performed at a temperature of 120 to 180 ℃ 0.3 to 0.5 Mpa pressure conditions.

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