KR20180079193A - Manufacturing method of polyester resin - Google Patents

Abstract

The present invention relates to a method of manufacturing polyester resin for a master batch, and more specifically, relates to a method of manufacturing polyester resin for a master batch, capable of suppressing the re-condensation of inorganic particles, having excellent dispersion stability, and including high-concentration inorganic particles. In particular, since the dispersion stability and condensation of particles are improved, a secondary particle condensation size has reduced condensation by no less than 10μm, and when a film having a thickness of 20-40μm is manufactured, its smoothness is excellent, there is no defect on the film, and the number of effective protrusions having a size of 0.1-0.2μm do not exceed 100 units/mm^2.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a polyester resin,

The present invention relates to a process for producing a polyester resin for a masterbatch, and relates to a process for producing a polyester resin for a masterbatch which suppresses re-aggregation of inorganic particles and is excellent in dispersion stability and contains inorganic particles at a high concentration . More specifically, by improving dispersion stability and agglomeration of particles, secondary particle aggregation size is less cohesion of 10 mu m or more, and when a film having a thickness of 20 to 40 mu m is produced, smoothness is excellent, there are no defects on the film, And having a number of effective protrusions of 0.1 to 0.2 μm in size of 100 / mm 2 or more.

The polyester film is excellent in stability of physical properties over a wide temperature range from low temperature to high temperature and has excellent chemical resistance compared with other polymer resins and is excellent in mechanical strength, surface characteristics and thickness uniformity, Since it has applicability, it is being applied to capacitors, photographic films, labels, pressure sensitive tapes, decorative laminates, transfer tapes, polarizing plates and ceramic green sheets for separating ceramics. In recent years, Trend.

Electronic parts such as capacitors and inductors have been downsized in recent years in accordance with the trend toward miniaturization of electronic devices, and ceramic green sheets themselves are also becoming thinner. Therefore, in order to realize high quality and miniaturization while exhibiting the same capacity even if the size is reduced, the most urgent task is to reduce the thickness and thickness uniformity of the ceramic green sheet. Therefore, there is a demand for a releasing film having a high degree of smoothness capable of minimizing the thickness deviation of the green sheet. However, the provision of the release film satisfying this purpose is insufficient.

The polyester film is used as a base film for coating a green sheet in a process of manufacturing a multilayer ceramic capacitor (MLCC) by coating a ceramic green sheet, and a silicone release agent is coated before the green sheet coating to easily release the green sheet As a base film. In order to improve the processability, the polyester film that performs such a role generally disperses organic particles or inorganic particles, which are anti-blocking agents, to form irregularities on the surface, thereby preventing surface scratches, And the like.

Also, in order to make the thickness of the green sheet significantly affecting the performance of the ceramic capacitor, the thickness of the film should be controlled to be small, and there should be no defects on the film which causes defects on the green sheet, It should have roughness.

In order to solve this problem, Japanese Unexamined Patent Publication (Kokai) No. 1999-320764 (Patent Document 1) discloses a method for producing a green sheet by flattening the surface of a polyester film contacting with a release layer to form a thin film. However, There is a problem that the green sheet is transferred to the roll or corrugated, thereby deteriorating the flatness of the green sheet, and forming a pin hole or the like.

Japanese Patent Application Laid-Open No. 2003-291291 (Patent Document 2) discloses a method for producing a polyester film containing aluminum oxide particles in order to prevent occurrence of blocking, generation of pinholes, transfer of a release layer, and the like , There is a problem that the haze of the film is too high to be suitable for the green sheet.

In order to prevent the flatness and defects of the film, the conventional techniques described above used flattening of the surface of the polyester film and control of the particles, but they have a limitation in manufacturing defective films and having sufficient transparency.

Japanese Laid-Open Patent Application No. 1999-320764 Japanese Patent Application Laid-Open No. 2003-291291

An object of the present invention is to provide a method for producing a polyester resin for a release film of a multilayer ceramic capacitor (MLCC).

The present invention aims at solving the problem of the conventional polymerization method in which aggregation of inorganic particles occurs and excessively large projections are formed. More specifically, the present invention relates to a polyester for masterbatches, which suppresses the occurrence of re-aggregation of inorganic particles to reduce secondary aggregation particles having a secondary particle aggregation size of 10 占 퐉 or more, exhibits excellent dispersion stability of inorganic particles, It is an object of the present invention to provide a method for producing a resin.

The present invention also relates to a polyester resin which is excellent in smoothness in film production, free from defects on the film, and capable of satisfying physical properties with effective protrusions of 0.1 to 0.2 탆 in a size of 0.1 to 0.2 탆 in a film having a thickness of 20 to 40 탆, And to provide a method for manufacturing the same.

In order to accomplish the above object, the present invention provides a method for producing a polyester resin by using two or more kinds of inorganic particles having different average particle diameters, combining a specific catalyst or a divided catalyst of a specific catalyst, And the number of the second agglomerated particles having a particle diameter of 10 탆 or more is small and the effective protrusions having a size of 0.1 to 0.2 탆 can be satisfied at a density of 100 per mm 2 or more in the production of a film.

The effective protrusions are protrusions protruding from the surface of the film. If the thickness of the protrusions protruding from the surface of the film is too large as the thickness of the thin film is increased, scratches or poor slipperiness may occur on the surface of the film. In order to use the film as a film for a release film of a multilayer ceramic capacitor (MLCC) of the present invention, the protrusions having a height of 0.1 to 0.2 탆 protruding from the surface of the film are formed so as to have better releasability and running properties. In order to form a secondary aggregation particle having a particle diameter of 10 탆 or more.

More specifically, when a large amount of two or more kinds of inorganic particles having different average particle diameters are added in polymerization of polyester resin, secondary particles agglomerated by a catalyst and a heat stabilizer are added in order to control the polymerization rate and the physical properties of the polyester resin As a result of research to solve this problem, secondary particles having an average particle diameter of 10 탆 or more can be prevented from being produced by separately injecting a specific combination catalyst and a specific catalyst. It is confirmed that the number of effective protrusions is increased. That is, the present invention is characterized by the combination of the catalyst, the heat stabilizer and the inorganic particles and the order of introduction.

The present invention relates to a method for producing a polyester resin,

a) an ester exchange reaction step of reacting a dicarboxylic acid component with a glycol component and a magnesium-based single catalyst to produce a polyester oligomer; And

b) a polycondensation reaction step in which after the transesterification reaction, an antimony catalyst, phosphorus thermal stabilizer and two or more inorganic particles having different average particle diameters are added to produce a polycondensation polyester;

Wherein the number of protrusions having a height of 0.1 to 0.2 탆 and protruding from the surface during the production of a film is 100 / mm 2 or more.

The present invention also provides a process for producing a polyester oligomer comprising the steps of: a) an ester exchange reaction step of reacting a dicarboxylic acid component, a glycol component, and a magnesium catalyst and a mixed catalyst of an antimony catalyst to produce a polyester oligomer; And

b) a polycondensation reaction step of adding a phosphorus thermal stabilizer and two or more kinds of inorganic particles having different average particle diameters after the transesterification reaction to produce a polycondensation polyester;

Wherein the number of protrusions having a height of 0.1 to 0.2 탆 and protruding from the surface during the production of a film is 100 / mm 2 or more.

The polyester resin produced by the production method of the present invention can produce a polyester resin for master batch in which aggregation of the secondary particles is small and the inorganic particles are evenly dispersed.

When a film is produced by using such a polyester resin, the film is excellent in smoothness, has a large number of effective projections, is excellent in releasability and running property, and has a property suitable for use as a release film of a multilayer ceramic capacitor (MLCC).

The present invention will be described in more detail by way of the following specific examples or examples. It should be understood, however, that the invention is not limited thereto and that various changes and modifications may be made without departing from the spirit and scope of the invention.

Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention is merely intended to effectively describe a specific embodiment and is not intended to limit the invention.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In a first aspect of the present invention,

a) an ester exchange reaction step of reacting a dicarboxylic acid component with a glycol component and a magnesium-based single catalyst to produce a polyester oligomer; And

b) a polycondensation reaction step in which after the transesterification reaction, an antimony catalyst, phosphorus thermal stabilizer and two or more inorganic particles having different average particle diameters are added to produce a polycondensation polyester;

Wherein the number of protrusions having a height of 0.1 to 0.2 占 퐉 protruding from the surface during the production of a film is 100 / mm2 or more.

A second aspect of the present invention is

a) an ester exchange reaction step of reacting a dicarboxylic acid component, a glycol component, and a mixed catalyst of a magnesium catalyst and an antimony catalyst to produce a polyester oligomer; And

b) a polycondensation reaction step of adding a phosphorus thermal stabilizer and two or more kinds of inorganic particles having different average particle diameters after the transesterification reaction to produce a polycondensation polyester;

Wherein the number of protrusions having a height of 0.1 to 0.2 占 퐉 protruding from the surface during the production of a film is 100 / mm2 or more.

It is obvious that the first and second aspects are merely illustrative and not restrictive, and that known configurations known to those skilled in the art can be added.

The present inventors have found that when the film is made into a film having a thickness of 20 to 40 탆, effective protrusions having a size of 0.1 to 0.2 탆 are formed at 100 As a result of studies on a polyester resin capable of producing a film having excellent running property and releasability in a number of pieces / mm 2 / mm 2, it was found that the kind of the catalyst, the order of introduction, An ester film can be produced. Thus, the present invention has been completed.

The step of producing the polyester resin of the present invention comprises: esterifying the dicarboxylic acid component and the glycol component; And polycondensation of the reaction product of the esterification reaction. If necessary, the polycondensation reaction may be followed by solid phase polymerization.

More specifically, it is preferable that the ester exchange reaction step a) is carried out at 130 to 150 ° C for 30 to 90 minutes, and then the reaction is continued for 1 to 10 hours while the reaction temperature is increased to 200 to 240 ° C. The preliminary reaction is carried out at 130 to 150 ° C for 30 to 90 minutes to sufficiently dissolve the starting material, and then the methanol spill and transesterification reaction can proceed smoothly.

The dicarboxylic acid component may be selected from the group consisting of terephthalic acid, oxalic acid, malonic acid, azelaic acid, fumaric acid, pimelic acid, Suberic acid, isophthalic acid, dodecane dicarboxylic acid, naphthalene dicarboxylic acid, biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, succinic acid, glutaric acid, Adipic acid, sebacic acid, 2,6-naphthalene dicarboxylic acid, 1,2-Norbornane dicarboxylic acid, ), 1,3-cyclobutane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid (1,4-cyclohexane dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-Lithium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, and the like, or a mixture of two or more thereof. Specific examples thereof include esters of the dicarboxylic acid compounds, that is, dimethyl terephthalate, diethyl terephthalate, terephthalic acid-2-hydroxyethyl methyl ester, 2 , Dimethyl 6-naphthalene dicarboxylate, dimethyl isophthalate, dimethyl adipate, dimethyl maleate, dimethyl dimer, and the like, but not limited thereto.

The glycol component may be selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, Butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,3-propylene glycol, Diethylene glycol, triethylene glycol, 1,2-cyclohexane diol, 1,3-cyclohexane diol, 1,4-cyclohexane diol, diol, propanediol, hexanediol, tetramethylcyclobutanediol, 1,4-cyclohexane diethanol, 1,10-decamethylene glycol, ), 1,12-dodecanediol, polyoxyethylene glycol, polyoxyethylene Ethylene glycol (Polyoxymethylene glycol), polyoxyethylene glycol is tetraethylene to (Polyoxytetramethylene glycol) and glycerol (Glycerol) either one or may use a mixture of two or more selected from ethylene glycol can be used preferably.

The polyester resin of the present invention may be polyethylene terephthalate prepared by using terephthalic acid as a dicarboxylic acid and ethylene glycol as a glycol according to the production method of the polyester resin, But is not limited thereto.

In the present invention, it has been confirmed that, in the transesterification reaction, the magnesium-based catalyst is used alone, or the magnesium-based catalyst and the antimony-based catalyst are used in combination to reduce the objective secondary aggregated particles, .

At this time, the magnesium-based catalyst is used for controlling the electrostatic characteristics at the time of activation of the transesterification reaction and film casting, and specifically, for example, one or two selected from magnesium oxide, magnesium acetate, Or more. The content of the dicarboxylic acid component and the content of the magnesium component may be 200 to 1000 ppm, more preferably 400 to 800 ppm, based on the total amount of the glycol component and the glycol component. Within the above range, a resin having a high conversion ratio of transesterification reaction and a low foreign matter can be produced, which is preferable.

The antimony-based catalyst is used for increasing the polycondensation rate between dicarboxylic acid and glycol, and may be added during transesterification reaction or polycondensation reaction. Specific examples thereof include antimony trioxide (Sb ₂ O ₃ ), antimony And may be any one or a mixture of two or more selected from antimony oxalate, antimony glucoxide and antimony butoxide. The content thereof may be such that the content of antimony atom is in the range of 150 to 600 ppm, more preferably 200 to 400 ppm, based on the total amount of the dicarboxylic acid component and the glycol component. The antimony-based catalyst may increase the rate of polycondensation between the dicarboxylic acid and the glycol to promote the production of the polyester prepolymer. However, when an excessive amount of the antimony-based catalyst is used, the deterioration It is preferable to use it in the above-mentioned content range. In addition, it is preferable that the reaction rate is controlled within the above range, and pyrolysis does not occur.

Next, the step b) is a step of polycondensation of a reaction product of the esterification reaction of a dicarboxylic acid and a glycol. The polycondensation of the reaction product of the esterification reaction may be carried out at a temperature of 230 to 300 ° C, preferably 260 to 290 ° C and a reduced pressure of 0.1 to 1 torr. More specifically, the reaction may be carried out for 1 to 6 hours while sequentially raising the temperature to 230 to 300 ° C. It is possible to produce a polyester resin having an intrinsic viscosity of 0.6 to 0.7 dl / g and a carboxyl end group content of 15 to 20 eq / 10 ⁶ g in the range satisfying the above temperature range and reaction time. Within the above range, hydrolysis in the meltson is minimized during film production, and excellent physical properties can be exhibited without deterioration of the physical properties of the film, and the compatibility with the base resin mixed in the production of the film is excellent.

At this time, in the polycondensation step, a phosphorus thermal stabilizer and at least two or more inorganic particles having different average particle sizes are added. In the transesterification reaction, an antimony catalyst is added, or an antimony catalyst is used in the transesterification reaction If not, the antimony catalyst may be added in the polycondensation step.

The phosphorus thermal stabilizer may serve to prevent deterioration and discoloration in the production of the polyester resin. Specifically, the phosphorus compound can prevent deterioration due to heat applied to the transesterification reaction and the polycondensation reaction, reaction heat generated as the reaction progresses, and the like, and the colorbody generated by the reverse reaction or decomposition reactions, Or inhibiting the unintended addition reaction by controlling the activity of the catalyst so as to suppress the yellowing of the finally formed polyester, thereby making the color of the polyester resin transparent and close to colorless. Specific examples thereof include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phenylphosphine, and 2-carboxyethylphenyl phosphinic acid. Or a mixture of two or more thereof. The phosphorus compound can form a BHT-P complex or a BHT-Metal-P complex by reacting with bis-2-hydroxyethyl terephthalate (BHT) produced in the esterification process, It can also form a complex with the antimony metal used. Such a composite may remain as a defect in the polyester resin to be finally produced, and the complex may be a cause of lowering the crystallization rate because a polymer is produced in a branched structure. Therefore, when the phosphorus compound is added in too much amount, it may remain as a defect of the polyester resin or may bind to the catalyst and degrade the activity of the catalyst. Therefore, the content of phosphorus atoms relative to the total amount of the dicarboxylic acid and glycol It may be added in a content of 50 to 500 ppm. And more preferably 100 to 400 ppm, and 200 to 300 ppm.

The inorganic particles are used to form protrusions protruding from the surface during the production of the film. They are generally used for polyester films such as titanium dioxide, barium sulfate, calcium carbonate, magnesium carbonate, calcium phosphate, silica, alumina, talc and kaolin But can be used without limitation. The inorganic particles may be a mixture of at least two or more inorganic particles having different average particle diameters, wherein the types of the particles may be the same or different. From the viewpoint of producing a film having a height of 0.1 to 0.2 탆 protruding from the surface in the production of a film having a thickness of 20 to 40 탆 at a number of 100 / mm 2 or more, the average particle size of the inorganic particles is 0.1 to 7.0 탆, May be 0.1 to 5.0 탆, and particles having different average particle diameters may be mixed in the above range. Further, the difference in average particle diameter of each inorganic particle may be 0.1 to 2 占 퐉. That is, when two kinds of inorganic particles are used, the difference in average particle diameter between the first inorganic particle and the second inorganic particle may be 0.1 to 2 占 퐉. When three kinds of inorganic particles are used, The difference in average particle diameter between the first inorganic particle and the third inorganic particle is 0.1 to 2 mu m, the difference in average particle diameter between the first inorganic particle and the third inorganic particle is 0.1 to 2 mu m, To 2 [mu] m.

In the present invention, the protrusion means a protrusion protruding from the surface of the film observed through an optical microscope after biaxially stretching the film to produce a film. The protrusion has a protruding height of 0.1 to 0.2 탆 and a ratio of 100 / The film is excellent in winding property, running property and releasability, so that a film suitable for use as a release film of a multilayer ceramic capacitor (MLCC) can be produced.

The total content of the inorganic particles used herein is not limited, but may be 0.1 to 5 wt%, more preferably 1 to 3 wt%, in the polyester resin for masterbatch. The present invention specifies the type of catalyst and the order of introduction, and it is possible to manufacture a resin having a smaller amount of secondary aggregated particles having an aggregation size of 10 탆 or more even when the content of inorganic particles is heavily used have.

In one embodiment of the present invention, the inorganic particles may be calcium carbonate, more specifically, a mixture of calcium carbonate having an average particle diameter of d1 and calcium carbonate having an average particle diameter of d2, 3 < / RTI >

0.1 占 퐉? D1? 1.0 占 퐉 [Formula 1]

0.5 占 퐉? D2? 3.0 占 퐉 2?

0.1 占 퐉? | D1-d2 | &Amp;le; 2 mu m [Formula 3]

The first calcium carbonate may have an average particle diameter of 0.1 to 1.0 탆, more preferably 0.1 to 0.6 탆, an average particle diameter of the second calcium carbonate of 0.5 to 3.0 탆, more preferably 0.7 to 1.5 탆, It is not.

Next, in the method for producing a polyester resin in one embodiment, the polyester polycondensation product prepared by the above-mentioned method can be solid-phase polymerized. The solid phase polymerization may be any solid phase polymerization method known to be used in the production of polyester resins such as a batch polymerization method and a continuous solid phase polymerization method.

The step of solid-phase polymerizing the polyester polycondensate may further include a step of pre-crystallizing at a temperature of 100 ° C to 250 ° C. More specifically, the step of pre-crystallizing the polyester polycondensate can be carried out by drying and crystallizing at 100 to 250 ° C, specifically 150 to 220 ° C under inert gas or vacuum for about 1 to 10 hours.

The solid phase polymerization may solid phase polymerize the pre-crystallized polyester resin at a temperature of 150 to 300 DEG C and an inert gas. More specifically, the solid phase polymerization may be carried out at a temperature of from 150 to 250 ° C, preferably from 170 to 250 ° C, and may be solid-phase polymerized at a temperature in the above-mentioned range for a certain period of time. In addition, the inert gas may be nitrogen gas, and may be solid-phase polymerized for 1 to 40 hours, but is not limited thereto.

Further, the polyester resin for master batch produced by the above-mentioned production method is melt-extruded by the conventionally known T-die method to obtain an unstretched sheet, and the obtained non-stretched sheet is stretched 2 to 7 times in the machine direction, Preferably 3 to 5 times, and then stretched 2 to 7 times, preferably 3 to 5 times, in the transverse direction with respect to the machine direction to produce a polyester film.

If necessary, the polyester resin for masterbatches may be mixed with a polyester resin containing no inorganic particles to prepare a film. In this case, the content of the inorganic particles in the film may be from 0.05 to 1% by weight, more preferably from 0.1 to 1.0% by weight, and the smoothness and running property of the film may be excellent in the above range to prevent slippage during the production process . Further, a film having an average surface roughness of less than 20 nm and a projection height of 0.1 to 0.2 占 퐉 on the surface of not less than 100 number / mm2 can be produced.

The film may be a single layer or a laminate of two or more layers. In the case of a polyester film laminated in several layers, at least one layer may be composed of the polyester film according to the present invention. More preferably, the polyester resin for masterbatch according to the present invention may be used for the surface layer. The total thickness of the produced film is not limited, but may be 1 to 100 탆, specifically 10 to 50 탆, more specifically 20 to 40 탆.

The polyester resin and film of the present invention produced by the above production method is suitable for use as a release film for a high performance multilayer ceramic capacitor, and is excellent in smoothness and has a large protrusion and a fish eye, Can be used.

In the polyester film for a release film according to the present invention, the average surface roughness Ra of the film may be less than 20 nm, more specifically, 1 to 20 nm. When the Ra is 1 nm or less, the adhesion is excessively high, which may cause appearance problems such as scratches and pressing. Ra of 20 nm or more may act as a defect in the coating process.

The polyester film for a release film according to the present invention preferably has one or more giant protrusions or fish eyes. If the number of fish eyes is more than one, it causes deviation in the surface height of the film, So that defects in the multilayer ceramic capacitor can be caused.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The following properties were evaluated as follows.

1) Intrinsic viscosity

In 25 ml of 2-chlorophenol, 2 g of a polyester resin prepared by melt polymerization in the following examples and comparative examples was added and dissolved in a thermostatic bath at 100 ° C for 60 minutes, transferred to an Ostwald viscometer, Minute, and the falling seconds of the solution can be obtained by using a viscometer and an aspirator. The number of drops of the solvent was also determined by the same method, and then the intrinsic viscosity (I.V.) was calculated by the following equations (1) and (2). In the following equation, C represents the concentration of the sample.

[Equation 1]

R.V. = Samples falling in water / solvent drops in seconds

[Equation 2]

2) Carboxyl (-COOH) end group content

0.5 g of a PET pellet sample having a size of 4 mm was placed in a 100 mL dissolution tube, and 25 mL of an ortho-chlorophenol solvent was added and dissolved at 100 DEG C for 1 hour to prepare a sample. The sample was titrated with 0.02 M KOH methanol solution and measured. The unit is eq / 10 ⁶ g.

3) Surface roughness

The surface of the polyester film was cut into three portions on the left, middle and right sides according to JIS B0601, and then cut into pieces each having a size of 3 cm x 3 cm. Using a surface roughness meter (model: SE-3300) manufactured by KOSAKA And the average surface roughness Ra value was evaluated by measuring at least five surface roughness of at least five points on the surface of the film under the following measurement conditions. The unit is nm.

(L: measurement length)

Speed: 0.05 mm / s

Cut off: 0.08㎜

Measurement length (L): 1.50 mm

The maximum surface roughness (Rmax) is measured using the same surface roughness meter, and represents the sum of the highest mountain height (Rp) in the average line and the depth (Rv) from the lowest bone.

That is, Rmax = Rp + | Rv |

4) Color

The color of the resin was measured using a Spectro color meter (ColorMate 430, manufactured by Shinco). The amount of resin to be measured was 15 g, and was measured using a cylindrical container (jig).

5) Number of effective projections

The polyester film was cut into three portions at left, middle, and right according to JIS B0601-1994, and further cut into pieces each having a size of 3 cm x 3 cm. The surface of the polyester film was measured with a surface roughness meter (model name: Surfcom 590A, manufactured by Tokyoseimitsu Co., ) Is used to measure at least five images of the film surface under the following measurement conditions, and the number of effective projections is measured by measuring the size distribution of the particles measured by the built-in software (Model: Surfcom 3DF-12) Respectively.

Specifically, the projection profile of the film surface was measured with a three-dimensional roughness measuring apparatus Surfcom 590A (manufactured by Tokyo Seimitsu Co., Ltd.) under conditions of cutoff 0.08 mm, measuring length 1.0 mm, scanning pitch 2 占 퐉, The projection profile was recorded at a magnification of 100 times in the scanning direction. The number of protrusions (number of protrusions / mm 2) was measured at intervals of 0.05 탆 from the obtained protrusion profile (transverse axis: protrusion height, vertical axis: protrusion profile number of protrusions). For the analysis, a three-dimensional roughness analyzer Surfcom 3DF-12 (manufactured by Tokyo Seimitsu Co., Ltd.) was used.

6) Film running ability

The running property of the film was expressed by a dynamic friction coefficient, and the measurement thereof was carried out in accordance with ASTM D-1894. The measurement was carried out in an atmosphere of a temperature of 23 ± 1 ° C and a humidity of 50 ± 5% RH. The size of the sample used was 100 mm in width, 200 mm in length and tensile speed of 200 mm / min.

 And the average value of the remaining values excluding the maximum value and the minimum value was obtained.

7) Number of fish eyes

Fisheye numbers of 10 μm or more were measured by evaluating film samples of 1 cm in width and 1 cm in width, taken at five points with respect to the film width direction at an optical microscope transmission of 200 times.

[Example 1]

1) Production of polyester resin

50 parts by weight of ethylene glycol and 450 ppm based on magnesium atom of magnesium acetate were added to 100 parts by weight of terephthalic acid in the esterification reactor and reacted at 140 DEG C for 1 hour and then sequentially heated from 140 DEG C to 205 DEG C The transesterification reaction was carried out for 3 hours to prepare a prepolymer BHET (bis-β-hydroxyethyl terephthalate). Methanol generated during the reaction was separated through a distillation column, and ethylene glycol, which was generated after completion of the esterification reaction, was also separated through a distillation column. The temperature was raised from 205 ° C to 230 ° C, and further reaction was carried out for 30 minutes, after which the transesterification reaction was terminated.

Thereafter, the reactor was charged with 150 ppm of antimony trioxide antimony trioxide, 250 ppm of phosphorus atom of trimethyl phosphate, and calcium carbonate having an average particle diameter of 0.6 占 퐉 and calcium carbonate having an average particle diameter of 1.0 占 퐉 at a ratio of 1: And the reaction was carried out at 230 DEG C for 30 minutes. Then, the polyethylene terephthalate resin master batch chip was prepared by performing a polycondensation reaction for 2 hours while sequentially heating from 230 DEG C to 283 DEG C .

2) Production of film

The polyethylene terephthalate resin master batch chip prepared as described above and the polyethylene terephthalate resin master batch chip prepared above were mixed and fed to an extruder. The polyethylene terephthalate resin master batch chip was added so as to have a particle content of 0.1 wt% in the final film Respectively. Extruded through an extruder, and then quenched and solidified by a casting drum having a surface temperature of 20 ° C to prepare an unoriented sheet. The prepared polyester sheet was stretched 3.8 times in the machine direction (MD) and 4.0 times in the transverse direction (TD), and then heat set at 230 DEG C to obtain a 35 mu m thick biaxially oriented film having a particle content of 1 wt% . The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 2]

1) Production of polyester resin

50 parts by weight of ethylene glycol, 450 ppm based on magnesium atom of magnesium acetate, and 150 ppm based on antimony atom of antimony trioxide were added to 100 parts by weight of terephthalic acid and reacted at 140 占 폚 for 1 hour and then reacted at 140 占 폚 To 205 ° C for 3 hours to prepare a prepolymer BHET (bis-β-hydroxyethyl terephthalate). Methanol generated during the reaction was separated through a distillation column, and ethylene glycol, which was generated after completion of the esterification reaction, was also separated through a distillation column. The temperature was raised from 205 ° C to 230 ° C, and further reaction was carried out for 30 minutes, after which the transesterification reaction was terminated.

Thereafter, calcium carbonate having an average particle diameter of 0.6 mu m and calcium carbonate having an average particle diameter of 1.0 mu m were mixed in a ratio of 1: 1 by weight based on phosphorus atom of trimethyl phosphate of trimethyl phosphate and added to the resin so that the total content in the resin became 2 wt% The reaction was carried out at 230 ° C for 30 minutes, and the resulting mixture was subjected to a polycondensation reaction for 2 hours while sequentially heating from 230 ° C to 283 ° C to prepare a polyethylene terephthalate master batch chip.

 2) Production of film

The polyethylene terephthalate resin master batch chip prepared as described above and the polyethylene terephthalate resin master batch chip prepared above were mixed and injected into an extruder. The polyethylene terephthalate resin master batch chip had a particle content of 0.1 wt% in the final film. . Extruded through an extruder, and then quenched and solidified by a casting drum having a surface temperature of 20 ° C to prepare an unoriented sheet. The prepared polyester sheet was stretched 3.8 times in the machine direction (MD) and 4.0 times in the transverse direction (TD), and then heat set at 230 DEG C to obtain a 35 mu m thick biaxially oriented film having a particle content of 1 wt% . The physical properties of the prepared film were measured and are shown in Table 1 below.

[Example 3]

In the preparation of the polyester resin in Example 1, the average particle diameter was 0.6 And a silica having an average particle diameter of 1.0 탆 were mixed in a weight ratio of 1: 1, and the total content of the calcium carbonate and the silica was adjusted to 2% by weight, a polyethylene terephthalate resin master batch chip .

Further, a film was prepared in the same manner as in Example 1, and physical properties of the produced film were measured and shown in Table 1 below.

[Example 4]

In the same manner as in Example 1 except that calcium carbonate having an average particle diameter of 0.6 占 퐉 and calcium carbonate having an average particle diameter of 3.0 占 퐉 were mixed in a weight ratio of 1: 1 and the total content in the resin was 2 wt% After the transesterification reaction, the polycondensation reaction was carried out to prepare a polyethylene terephthalate resin.

A film was prepared in the same manner as in Example 1, and physical properties were measured and shown in Table 1 below.

[Comparative Example 1]

A polyethylene terephthalate resin was prepared in the same manner as in Example 2, except that 350 ppm of calcium acetate based on calcium acetate was further added during the transesterification reaction in Example 2 above.

A film was prepared in the same manner as in Example 2, and physical properties were measured and shown in Table 1 below.

[Comparative Example 2]

50 parts by weight of ethylene glycol, 450 ppm based on magnesium atom of magnesium acetate, 150 ppm based on the antimony atom of antimony trioxide, and 250 ppm based on phosphorus atom of trimethyl phosphate were added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, The reaction was carried out under the same conditions as in Example 1,

During the polycondensation reaction, calcium carbonate having an average particle diameter of 0.6 mu m and calcium carbonate having an average particle diameter of 1.0 mu m were mixed at a weight ratio of 1: 1 by weight based on the calcium atom of calcium acetate at 350 ppm, and the total content of the calcium carbonate was adjusted to 2 wt% , A transesterification reaction was carried out under the same conditions as in Example 1, and a polycondensation reaction was carried out to prepare a polyethylene terephthalate resin.

A film was prepared in the same manner as in Example 1, and physical properties were measured and shown in Table 1 below.

[Comparative Example 3]

Except that terephthalic acid, ethylene glycol, magnesium acetate, antimony trioxide, trimethyl phosphate, calcium carbonate having an average particle diameter of 0.6 mu m, and calcium carbonate having an average particle diameter of 1.0 mu m were charged at the same time as in Example 1 After the transesterification reaction, a polycondensation reaction was carried out to prepare a polyethylene terephthalate resin.

A film was prepared in the same manner as in Example 1, and physical properties were measured and shown in Table 1 below.

[Comparative Example 4]

A polycondensation reaction was carried out after transesterification under the same conditions as in Example 1, except that calcium carbonate having an average particle diameter of 0.6 占 퐉 was used so that the total content in the resin was 2% by weight in Example 1, Terephthalate resin was prepared.

A film was prepared in the same manner as in Example 1, and physical properties were measured and shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Inorganic particle | d2-d1 | 0.4 0.4 0.4 2.4 0.4 0.4 0.4 - Surface roughness
(nm) Ra 18 15 15 25 14 10 11 14 Rp 383 379 360 451 324 310 307 277 Rv -231 -207 -205 -365 -130 -115 -111 -187 Rmax 614 586 565 816 454 425 418 464 Number of effective projections Total number
(ea / mm 2) 151 101 103 394 99 99 99 82 0.1 to 0.2 μm 151 101 103 240 91 88 86 80 Greater than 0.2 μm 0 0 0 154 8 11 13 2 Coefficient of film friction 0.31 0.35 0.37 0.88 0.45 0.47 0.47 0.30 Number of fish eyes 0 0 0 22 4 5 9 7

As shown in Table 1, Examples 1 to 3 did not contain secondary aggregated particles having a particle size of 10 占 퐉, and thus it was confirmed that the number of projections having a height of 0.2 占 퐉 or more protruded to the surface was zero. In addition, it was found that the number of effective projections having a height of 0.1 to 0.2 탆 protruding from the surface was 100 / mm < 2 > or more so that the running property and releasability could be satisfied and fish eyes did not occur. It was also found that the surface of the film was smooth and the surface roughness Ra was less than 20 nm and that the surface of the film was smooth. In the case of Example 4, when the average particle diameter of calcium carbonate was 0.6 mu m and 3.0 mu m, a large amount of effective protrusions were present, but the amount of secondary aggregation particles having a particle diameter of 10 mu m was large and the height protruded to the surface exceeded 0.2 mu m And the number of protrusions was increased. Also, it was confirmed that the surface roughness Ra was increased.

Comparative Examples 1 to 3, in which the order of introduction of the catalyst was changed, included secondary aggregated particles having a particle diameter of 10 占 퐉, so that the number of effective projections having a height of 0.1 to 0.2 占 퐉 protruding from the surface was small, And it was found that the fishy eye occurred and the driving force was not good due to the high coefficient of friction.

Also in the case of Comparative Example 4 using single particles, it was confirmed that the number of effective protrusions having a protruded height of 0.1 to 0.2 탆 was small, protrusions exceeding 0.2 탆 were somewhat generated, and fish eyes were generated.

Claims (10)

a) an ester exchange reaction step of reacting a dicarboxylic acid component with a glycol component and a magnesium-based single catalyst to produce a polyester oligomer; And
b) a polycondensation reaction step in which after the transesterification reaction, an antimony catalyst, phosphorus thermal stabilizer and two or more inorganic particles having different average particle diameters are added to produce a polycondensation polyester;
Wherein the number of protrusions having a height of 0.1 to 0.2 占 퐉 protruding from the surface during the production of the film is 100 / mm2 or more. a) an ester exchange reaction step of reacting a dicarboxylic acid component, a glycol component, and a mixed catalyst of a magnesium catalyst and an antimony catalyst to produce a polyester oligomer; And
b) a polycondensation reaction step of adding a phosphorus thermal stabilizer and two or more kinds of inorganic particles having different average particle diameters after the transesterification reaction to produce a polycondensation polyester;
Wherein the number of protrusions having a height of 0.1 to 0.2 占 퐉 protruding from the surface during the production of the film is 100 / mm2 or more. 3. The method according to claim 1 or 2,
Wherein the inorganic particles are at least one selected from titanium dioxide, barium sulfate, calcium carbonate, magnesium carbonate, calcium phosphate, silica, alumina, talc and kaolin and the average particle size of the inorganic particles is 0.1 to 7.0 탆. A method for producing a polyester resin for batch. The method of claim 3,
Wherein the two or more inorganic particles having different average particle diameters have a difference in average particle diameter of the respective inorganic particles of 0.1 to 2 占 퐉. 5. The method of claim 4,
Wherein the inorganic particles are contained in an amount of 0.1 to 5% by weight. 6. The method of claim 5,
Wherein the inorganic particles are a mixture of calcium carbonate having an average particle diameter of d1 and calcium carbonate having an average particle diameter of d2 and satisfying the following formulas 1 to 3:
0.1 占 퐉? D1? 1.0 占 퐉 [Formula 1]
0.5 占 퐉? D2? 3.0 占 퐉 2?
0.1 占 퐉? | D1-d2 | &Amp;le; 2 mu m [Formula 3] 3. The method according to claim 1 or 2,
Wherein the step a) is carried out at 130 to 150 ° C for 30 to 90 minutes, and then the reaction is carried out at a temperature of 200 to 240 ° C for 1 to 10 hours while gradually increasing the reaction temperature. 3. The method according to claim 1 or 2,
Wherein the step b) is carried out for 1 to 6 hours while sequentially raising the temperature from 230 ° C to 300 ° C. A polyester composition for a film obtained by mixing the polyester resin for master batch produced by the production method of claim 1 or 2 with a polyester resin containing no inorganic particles, wherein the content of the particles in the total composition is 0.05 to 1 weight % ≪ / RTI > A polyester film using the polyester composition of claim 9,
Wherein the content of the particles in the whole film is 0.05 to 1 wt%, the average surface roughness is less than 20 nm, and the number of protrusions having a height of 0.1 to 0.2 mu m projected on the surface is 100 / mm <