KR20200015955A - A composition of polyester resin and polyester film comprising of the same - Google Patents

Abstract

A polyester resin composition comprises a polyester resin in which a dicarboxylic acid-based repeating unit and a diol-based repeating unit are polymerized and 0.3 to 14 parts by weight of an impact modifier with respect to 100 parts by weight of the polyester resin. The impact modifier may be a butadiene-based copolymer having a core-shell structure. According to the present invention, a polyester film having improved impact resistance and excellent optical properties can be provided.

Description

Polyester resin composition and polyester film containing same {A COMPOSITION OF POLYESTER RESIN AND POLYESTER FILM COMPRISING OF THE SAME}

The present invention relates to a polyester resin composition, a polyester film, etc., which have excellent impact resistance and are environmentally friendly, and thus have excellent utility as a decor sheet.

A calendering process is a process of shape | molding a film, a sheet | seat, etc. using the calender, ie, the rolling machine which arranged several heating rolls. The calendering process has been mainly used to make films, sheets, and the like because the production speed is faster and easier to process than the extrusion process.

PVC (Polyvinyl Chloride), PP (polypropylene) is used as the material of the film produced by the calendering process. However, PVC has a great need for a material that replaces PVC because it is difficult to recycle and has an unfriendly environment such as a high possibility of generating harmful gas upon disposal. PP resin also has excellent calenderability, but it is not environmentally friendly, and it is necessary to process a primer for printing or lamination. Polyethylene Terephthalate Glycol (PETG) using cyclohexanedimethanol (CHDM) can be used in the calendaring process, but its use is limited due to its high cost.

Patent Document 1: Korean Patent Publication No. 10-2007-0022974 Patent Document 2: Korea Patent Registration No. 10-0758937

An object of the present invention is to provide a polyester film and the like with excellent impact resistance, excellent optical properties and excellent utilization as an eco-friendly decor sheet.

Polyester resin composition according to an embodiment of the present invention is a polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit; And 0.3 to 14 parts by weight of an impact resistant agent, based on 100 parts by weight of the polyester resin, wherein the impact resistant agent includes a diene polymer.

The impact resistant agent has a core-shell structure, and the diene polymer included in the impact resistant agent may be a diene rubber positioned in the core.

The diene polymer may include butadiene repeat units.

The refractive index difference between the polyester resin and the impact resistant agent may be 0.3 or less.

The impact resistant agent may have a refractive index of 1.3 to 1.8.

The polyester resin may be amorphous.

The impact resistant agent may be spherical particles having a diameter of 0.3 μm or less.

The diol repeating unit may include neopentyl glycol, and the neopentylglycol may include 20 to 90 mol% based on the entire diol repeating unit.

The calendering polyester film according to another embodiment of the present invention is a calendering polyester film comprising a polymerized polyester resin including a dicarboxylic acid repeating unit and a diol repeating unit and an impact resistant agent, wherein the polyester The film has a haze value of 20% or less, and a breakage ratio of 30% or less evaluated by a Film Impact Tester.

The impact resistant agent has a refractive index of 1.3 to 1.8, and the polyester film may include 0.3 to 14 parts by weight of the impact resistant agent based on 100 parts by weight of the polyester resin.

The polyester film may be at least 85% elongation of 85 ℃.

Polyester film according to another embodiment of the present invention, the resin manufacturing step of producing a polyester resin from the composition for resin synthesis comprising a dicarboxylic acid compound and a diol compound; A mixing step of preparing a polyester resin composition comprising 100 parts by weight of the polyester resin and 0.1 to 14 parts by weight of an impact resistant agent; And a calendering step of manufacturing the polyester film by calendering the polyester resin composition; including, a haze value of 20% or less, and a breakage ratio of 30% or less evaluated by a film impact tester. Prepare ester film.

The resin manufacturing step may include a first polymerization step of forming an ester oligomer by performing an esterification reaction from a composition for resin synthesis containing a dicarboxylic acid compound and a diol compound; And a second polymerization step of performing a polycondensation of the polycondensation composition containing the ester oligomer to produce a polyester resin.

The calendering step includes the step of rolling at a temperature of 120 to 250 ℃ using a plurality of calender rolls.

According to the polyester resin composition of this invention, the polyester film etc. which are excellent in an optical characteristic at the same time as the impact resistance of a film itself improves can be provided. The polyester film can be manufactured by applying a calendering method, and is environmentally friendly, has excellent printability, sharpness, and the like, and also impact resistance, and is limited to parts requiring strong impact resistance such as furniture corners and window frame corners. It can be applied as a deco film without

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

In the present specification, "~ system" may mean to include a compound corresponding to "~" or a derivative of "~" in the compound. By "derivative" is meant a compound that has been modified as long as the structure and properties of the parent are unchanged, such as introduction of a specific compound, oxidation, reduction, substitution of atoms, etc. as a parent.

As used herein, B on A means that B is on direct contact with A, or B on A, with another layer in between, and B on a surface. It is limited to what does and is not interpreted.

In the present specification, the singular forms “a,” “an” and “the” are intended to be interpreted in the context of the singular or plural, unless the context describes otherwise.

Hereinafter, a polyester resin composition according to an embodiment of the present invention will be described.

The polyester resin composition according to an embodiment of the present invention includes i) a polyester resin polymerized with a dicarboxylic acid compound and a diol compound, and ii) an impact resistant agent.

Polyester resin composition according to an embodiment of the present invention may be a polyester resin composition for a calendaring process. The polyester resin may be amorphous.

The polyester resin includes a dicarboxylic acid repeating unit and a diol repeating unit. The polyester resin is formed by applying a dicarboxylic acid compound and a diol compound as a monomer to polymerize.

The polyester resin has a repeating unit derived from a dicarboxylic acid compound and a diol compound. In addition, the polyester resin may be a polymerized three or more monomers.

The composition for resin synthesis including the dicarboxylic acid compound and the diol compound may include the diol compound in a ratio of 1.05 to 3 moles based on 1 mole of the dicarboxylic acid compound. When applied at this ratio, the esterification reaction for ester oligomer synthesis can proceed stably to form a sufficient ester oligomer.

The dicarboxylic acid-based compound is terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, succinic acid, glutaric acid, orthotalic acid, adipic acid, azelaic acid, sebacic acid, decandicarboxylic acid , 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-bibenzoic acid and derivatives thereof, or combinations thereof. .

The dicarboxylic acid compound includes any one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid, and combinations thereof.

The diol-based compound may include linear or branched aliphatic diols, aromatic diols, and the like.

The linear or branched aliphatic diol is specifically, ethylene glycol, diethylene glycol, neopentyl 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 combinations thereof.

When the film or sheet is prepared by calendering using the composition for resin synthesis including the linear or branched aliphatic diol, the packing may be made relatively well to further improve the chemical resistance and surface strength of the film or sheet. .

Specifically, the diol-based compound may include any one glycol component selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, and combinations thereof.

More specifically, the diol-based compound may include neopentyl glycol as the glycol component.

The diol compound may include neopentyl glycol in 20 to 90 mol%, may include 30 to 80 mol% neopentyl glycol, and 30 to 60 mol% based on the entire diol compound. It may include neopentyl glycol. When neopentyl glycol is included in the diol-based compound in this range, the intrinsic viscosity of the resin is set in an appropriate range to further improve the calendaring processability, and also improve the color, mechanical properties, etc. of the manufactured film. have.

The diol compound does not substantially contain the alicyclic diol.

The alicyclic diols include, for example, cyclohexanedimethanol, isosorbide, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and the like.

In the case where neopentyl glycol is included as described above without substantially containing the alicyclic diol, it may be structurally strongly bound to the impact agent described below, and thus the impact strength of the film may be further improved.

The polyester resin may be amorphous. It is preferable that the polyester resin is amorphous in order to be applied to film production by a calendering process. If the crystalline resin or the semi-crystalline resin is applied to the calendering process, the viscosity may be drastically changed during the temperature rising process, and thus the workability of the calendering process may be degraded, and the calendering method is not suitable for application.

The polyester resin composition includes an impact resistant agent including a diene polymer.

The impact resistant agent may be included in the polyester resin composition or the film according to an embodiment of the present invention to improve the impact resistance of the film or sheet.

The content of the impact resistant agent is 0.3 to 14 parts by weight based on 100 parts by weight of the polyester resin. When the content of the impact agent is less than 0.3 part by weight based on 100 parts by weight of the polyester resin, the impact resistance improvement effect may be insignificant, and when the content of the impact agent exceeds 14 parts by weight, the optical properties of the film may be lowered.

The content of the impact agent may be 0.5 to 12 parts by weight, based on 100 parts by weight of the polyester resin, may be 1 to 10 parts by weight. When applying the impact resistant agent in the range of this content, it is possible to obtain a film excellent in impact resistance and sharpness when printing a pattern on the film at the same time by suppressing the increase in haze at the same time as the impact strength improvement effect of the film.

The impact resistant agent includes a diene polymer, and specifically, may be a copolymer having a core-shell structure. More specifically, the impact resistant agent may include a diene rubber in the core, and the diene rubber may specifically include a butadiene repeating unit.

The impact resistant agent may be a core shell copolymer having a spherical form. Thus, the impact agent of the spherical core shell structure having a diene-based rubber core can be produced a polyester film having excellent impact resistance since the impact agent is not substantially damaged during the kneading and rolling process.

The core component of the impact resistant agent may include an elastomer including butadiene repeat units, styrene repeat units, or copolymers thereof.

The butadiene repeating unit may be included in the core component in an amount of 10 to 90 wt%. In addition, the styrene repeating unit in the core component may be included in 10 to 90% by weight.

The shell component of the impact resistant agent may include a vinyl-based repeating unit.

The impact resistant agent may be an elastomer including butadiene repeat units, styrene repeat units, or copolymers thereof as a core, and the shell may be graft copolymer particles including vinyl-based repeat units.

The vinyl repeating unit may include an alkyl (meth) acrylate repeating unit, an aromatic vinyl repeating unit, or both.

The shell may further include a crosslinkable repeating unit as necessary. Specifically, the crosslinkable repeating unit may include a di or tri (meth) acrylate-based repeating unit and an allyl (meth) acrylate-based repeating unit of the Dhaka alcohol.

The impact resistant agent may include 60 to 80 parts by weight of the core component and 40 to 20 parts by weight of the shell component.

The impact resistant agent may be a methyl (meth) acrylate-butadiene-styrene graft copolymer. The butadiene and the styrene constitute butadiene rubber and styrene rubber, respectively, and are included in the core to impart elasticity to the impact resistant agent. In addition, the methyl (meth) acrylate may further improve the miscibility with the polyester resin is the graft copolymerization of the shell portion.

The impact resistant agent may be formed by a method of polymerizing monomers of the shell component in the presence of the core component, and may be formed by a method of grafting polymerization in one step or in multiple steps.

The impact resistant agent may be 0.3 um or less in diameter, and may have a spherical shape of 0.3 um or less. At this time, the spherical shape generally means spherical shape and does not mean to limit the complete spherical shape.

The impact resistant agent may be spherical particles having a diameter of 0.1 to 0.3 um. When applying spherical particles of this size, impact resistance can be efficiently improved while minimizing the influence on other physical properties such as optical properties of the film.

The refractive index of the impact resistant agent may be 1.3 to 1.8, 1.4. To 1.7, and may be 1.5 to 1.6. The refractive index range of the impact resistant agent has a small refractive index difference from a polyester resin serving as a matrix in which the impact resistant agent is dispersed, and thus has excellent optical properties as a whole. Can be improved.

Specifically, the difference between the refractive index of the impact resistant agent and the refractive index of the polyester resin (meaning a polymerized polyester resin not containing an impact agent) may be 0.3 or less, 0.2 or less. The impact resistant agent having such a refractive index difference value includes a case where the refractive index of the impact resistant agent is smaller than the refractive index of the polyester resin as well as a large case.

In the case where the impact agent having a smaller refractive index difference is applied to the film production, the impact resistance of the film can be improved and the optical properties can be improved to the same level or higher. As a result, it is possible to further improve the clarity and visibility of printing.

The polyester resin composition may further include components such as a polycondensation catalyst, a stabilizer and a colorant. The polycondensation catalyst, stabilizer, 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 mixed dicarboxylic acid and diol compound phase It may be added to, and may be added in the middle of the esterification step.

The polycondensation catalyst may include, for example, an antimony compound, a titanium compound, a German compound, an aluminum compound, or a mixture thereof. Antimony-based compounds may include, for example, antimony trioxide, antimony acetate, antimony glycolate, and the like. The titanium 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 stabilizer may include, for example, a phosphorus compound. The phosphorus compound may include, for example, phosphoric acid, trimethyl phosphate, triethyl phosphate, and the like. The addition amount may be 10 to 100 ppm relative to the weight of the final polymer based on the mass of phosphorus. If the amount of the stabilizer is less than 10 ppm, the stabilization effect is negligible, and yellowing of the final polymer may occur. If the amount of the stabilizer is more than 100 ppm, the activity of the polycondensation catalyst may be inhibited to obtain a polymer having a high degree of polymerization. have.

The colorant may improve the color of the polymer. The colorant may include, for example, a cobalt acetate, a cobalt propionate metal salt colorant, or a colorant that is a dye component. The amount of the colorant added may be greater than 0 and 100 ppm or less based on the weight of the final polymer.

The polyester resin composition is applied to manufacture a polyester film, the polyester film may be included in the decor sheet.

The decor sheet may include the polyester film, a printing layer positioned on one surface of the polyester film, and a transparent film covering the polyester film and the printing layer. An adhesive layer may be further positioned on the other surface of the polyester film.

The printing layer may include one layer of the polyester film, and may include a plurality of layers of two or more layers.

The polyester film made of the polyester resin composition may have a haze value of 20% or less, 0.2-20%, and 5-15%. In the case of having such a haze range, visibility at the time of forming the printed layer, light transmittance of the polyester film, and the like can be maintained at the same level as before the impact resistant agent is applied.

The polyester film prepared from the polyester resin composition may have a breakage rate of 30% or less, 20% or less, or 0 to 10%, as measured by a film impact tester. This breaking rate is based on the results of repeated experiments based on 10 sheets of 500 um thick film.

The polyester resin composition includes a polyester resin including a dicarboxylic acid repeating unit and a diol repeating unit as a polyester resin, and an impact agent, and a polyester film applicable to an environmentally friendly decor film having improved impact resistance. Can provide.

The calendering polyester film according to another embodiment of the present invention is a calendering polyester film comprising a polymerized polyester resin including a dicarboxylic acid repeating unit and a diol repeating unit and an impact resistant agent, and has a haze value. It is 20% or less, and the fracture rate evaluated by the Film Impact Tester is 30% or less.

The polyester film may have a haze value of 0.2 to 20% and 5 to 15%. In the case of having such a haze range, visibility at the time of forming the printed layer, light transmittance of the polyester film, and the like can be maintained at the same level as before the impact resistant agent is applied.

The polyester film may have a cracking rate of 20% or less, and may be 0 to 10%, as evaluated by a film impact tester. This cracking ratio is based on the results of repeated experiments of 500 um thick films based on 10 sheets, and the polyester film is included in the decor sheet so that the cracking does not occur even when applied to the corners of the product. It can have sufficient impact strength at.

The monomers applied in the preparation of the polyester film, specific features, contents, etc. of the impact resistant agent are overlapped with the description above, and thus description thereof is omitted. In addition, since the description of the preparation method thereof is also redundant with the description of the composition and the description of the manufacturing method described later, the description thereof is omitted.

In particular, the polyester film may include neopentyl glycol-derived diol repeating units, and specifically, the neopentyl glycol may be included in 20 to 90 mol% based on the total diol repeating units of the polyester film. Same as described above.

The neopentyl glycol is hydroxy at both ends and has two methyl groups branched in the middle of the chain. Even when polymerized to form a polyester film, the two methyl groups are branched to repeat the polyester polymer chain. It is included in a unit. The neopentyl glycol-derived repeating unit occupies a relatively small volume compared to the carboxylic acid-derived repeating unit and may form a space between the chain and the chain.

The impact agent to be applied in the present invention provides sufficient impact resistance to the film even in the case of small size particles and at the same time excellent in compatibility with the copolyester polyester resin is stable in the fine space between the chain and the chain formed by the neopentyl glycol It is thought that the physical properties of the polymer chains are dispersed and dispersed, so that the impact resistance is improved by the addition of the impact agent, while the influence on the arrangement of the polymer chain is relatively small compared to the application of the other impact agent.

The polyester film may have a tensile strength of 3500 to 5500 N / cm ² measured according to KS M 3001: 2011.

The polyester film may have a tear strength of 800 to 2000 N / cm measured according to KS M 3001: 2011.

The polyester film may be at least 85% elongation of 85 ℃.

This, the polyester resin composition of the present invention can form a polyester film with improved impact resistance by the calendering process, the optical properties, tensile properties and the like of the formed film can be maintained within a relatively excellent range.

Method for producing a polyester film according to another embodiment of the present invention is a resin manufacturing step of producing a polyester resin from a composition for resin synthesis comprising a dicarboxylic acid compound and a diol compound; A mixing step of preparing a polyester resin composition comprising 100 parts by weight of the polyester resin and 0.1 to 14 parts by weight of an impact resistant agent; And a calendering step of preparing a polyester film by calendering the polyester resin composition.

The polyester film produced by this manufacturing method is a polyester film having a haze value of 20% or less and a breakage ratio of 30% or less, which is evaluated by a film impact tester, and is excellent in its utilization as a deco film.

The resin manufacturing step may include a first polymerization step of forming an ester oligomer by performing an esterification reaction from a composition for resin synthesis containing a dicarboxylic acid compound and a diol compound; And a second polymerization step of performing a polycondensation of the polycondensation composition containing the ester oligomer to produce a polyester resin.

In the resin manufacturing step, the dicarboxylic acid may include any one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid, and combinations thereof.

In the resin manufacturing step, the diol may include any one selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, and combinations thereof.

Detailed description of each of the monomers and their content applied in the resin manufacturing step is omitted as described above.

The secondary polymerization step may be carried out at the conditions of 230 to 270 ℃ and 0.1 to 3.0 kg / ㎠, in this case it can be produced a polyester film excellent mechanical properties.

The second polymerization step may be performed under a polycondensation catalyst. The polycondensation catalyst may include, for example, an antimony compound, a titanium compound, a German compound, an aluminum compound, or a mixture thereof. Antimony-based compounds may include, for example, antimony trioxide, antimony acetate, antimony glycolate, and the like. The titanium 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 calendaring step may include a process of rolling at a temperature of 120 to 250 ℃ 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.

When the polyester film is manufactured by applying the calendering process as described above, the production speed is improved compared to the extrusion process, and a film having excellent physical properties may be manufactured.

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

Examples 1-5

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

Specifically, terephthalic acid was applied as the dicarboxylic acid compound, and three kinds of ethylene glycol, neopentyl glycol, and cyclohexanedimethanol were applied as the diol compound. The resin composition is a molar ratio of dicarboxylic acid: diol is applied at 1: 1.05 to 3.0, the neopentyl glycol is applied at 20 to 90 mol% based on the entire diol compound 230 to 270 ℃ and 0.1 The esterification reaction was carried out under the condition of -3.0 kg / cm 2 to form an ester oligomer. The polycondensation catalyst, stabilizer, etc. were further mixed with the thus formed ester oligomer to advance the polycondensation reaction to prepare a polyester resin (a refractive index of about 1.6 of the polyester resin).

The polyester resin is based on 100 parts by weight of the polyester resin, the impactor A is added to the content shown in Table 1 to prepare a polyester resin composition, and put into a calendering equipment to prepare a 200 ㎛ thick film. Impactor A has a core-shell structure, and the core contains butadiene. Mitsubishi's Metablen C150S (refractive index 1.58, particle size 0.15 um) was applied.

Example 1 Example 2 Example 3 Example 4 Example 5 Shock Resistant A 1.0 phr 2.5 phr 5.0 phr 7.5 phr 10 phr

* phr is an abbreviation for part per hundred resin and indicates the amount of application based on 100 parts by weight of polyester resin.

Comparative Example 1

The same procedure as in Example 1 was conducted except that the impact resistant agent A was not added.

Comparative Examples 2 to 3

Except the impactor A was carried out in the same manner as in Example 1, except that the content shown in Table 2.

Comparative Examples 4 to 5

As the impact resistant agent B, ABS (Acrylonitrile Butadiene Styrene, refractive index 1.54) was used, and was carried out in the same manner as in Example 1 except for including the content shown in Table 2 below.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Shock Resistant A - 0.1 15 - - Shock Resistant B - - - One 10

Property measurement

1. Impact resistance

Each of the 10 films produced was subjected to impact resistance evaluation using Toyoseiki Film Impact Tester No. 195, and the broken ratio (0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100%) was measured. The impact resistance evaluation results of Examples 1 to 5 and the impact resistance evaluation results of Comparative Examples 1 to 5 are shown in Table 3 below.

2. Haze

The haze value was measured for the produced film using the haze meter. The haze value measurement results of Examples 1 to 5 and the haze value measurement results of Comparative Examples 1 to 5 are shown in Table 3 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Breaking rate 10% 0% 0% 0% 0% Haze 3.1 5.5 8.1 11.2 18.2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Breaking rate 100% 90% 0% 80% 0% Haze (%) 0.2 0.7 29.6 15 67

Referring to the results of Table 3, Example 1 showed a significantly low cracking rate, and no cracking phenomenon was observed in Examples 2 to 4. On the other hand, Comparative Examples 1, 2 and 4 had a high cracking ratio of 80% or more, and Comparative Examples 3 and 5 showed that they were not broken. However, as described later, the haze value was high, and it was evaluated that there was a possibility of adversely affecting the sharpness of the printed layer and the like when applied to the decor sheet. In addition, Examples 1 to 5 had significantly lower haze values, while Comparative Examples 3 and 5 had significantly higher haze values of 25% or more.

Taken together, the samples capable of satisfying both the haze and impact resistance properties were evaluated as the samples of Examples 1 to 5 above, and in particular, the samples of Examples 2 to 5 were the average values of 10 samples tested. The break rate was less than 10%, and the haze value was 15% or less based on the 500 um thick film, which showed a fairly good result.

In addition, as a result of evaluating the thickness uniformity of the sheet of all the samples of Examples 1 to 5, the thickness uniformity of the film as a whole was 10% or less, it was evaluated that both of the calender processability is excellent.

As such, those skilled in the art will appreciate that the present invention can be implemented in other specific forms without changing the technical idea or essential features thereof. Therefore, it is to be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (13)

Polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit; And 0.3 to 14 parts by weight of an impact resistant agent based on 100 parts by weight of the polyester resin.
The impact resistant agent comprises a diene polymer, polyester resin composition.
The method of claim 1,
The impact resistant agent has a core-shell structure, and the diene polymer included in the impact resistant agent is a diene rubber positioned in the core, the polyester resin composition.
The method of claim 1,
The polyester resin composition whose refractive index difference of the said polyester resin and the said impact resistant agent is 0.3 or less.
The method of claim 1,
The impact resistant agent is a polyester resin composition, the refractive index is 1.3 to 1.8.
The method of claim 1,
The polyester resin is amorphous, the polyester resin composition.
The method of claim 1,
The impact resistant agent is a polyester resin composition, which is spherical particles having a diameter of 0.3 um or less.
The method of claim 1,
The diol repeating unit includes neopentyl glycol,
The neopentyl glycol is contained in 20 to 90 mol% based on the entire diol repeating unit, polyester resin composition.
A calendered polyester film comprising a polymerized polyester resin comprising a dicarboxylic acid repeating unit and a diol repeating unit and an impact resistant agent,
The said polyester film has a haze value of 20% or less, and the cracking ratio evaluated by the Film Impact Tester is 30% or less, The calendering polyester film.
The method of claim 8,
The impact resistant agent has a refractive index of 1.3 to 1.8,
The polyester film comprises 0.3 to 14 parts by weight of the impact resistant agent based on 100 parts by weight of the polyester resin, calendaring polyester film.
The method of claim 8,
The polyester film is a calendering polyester film, 85 ℃ elongation is 700% or more.
Resin manufacturing step of preparing a polyester resin from a composition for resin synthesis comprising a dicarboxylic acid compound and a diol compound;
A mixing step of preparing a polyester resin composition comprising 100 parts by weight of the polyester resin and 0.1 to 14 parts by weight of an impact resistant agent; And
Including; calendering step of producing a polyester film by calendering the polyester resin composition; including,
The manufacturing method of the polyester film which manufactures the polyester film whose haze value is 20% or less, and the crack ratio evaluated by the Film Impact Tester is 30% or less.
The method of claim 11,
The resin production step may include a first polymerization step of forming an ester oligomer by performing an esterification reaction from a composition for resin synthesis including a dicarboxylic acid compound and a diol compound; And a second polymerization step of carrying out the polycondensation of the polycondensation composition comprising the ester oligomer to produce a polyester resin.
The method of claim 11,
The calendering step comprises the step of rolling at a temperature of 120 to 250 ℃ using a plurality of calender rolls, a method for producing a polyester film.