JP7113074B2 - Polyester polymerization composition, polyester resin masterbatch chip and polyester film using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyester polymerization composition, a polyester resin masterbatch chip, and a polyester film using the same, in which the dispersibility of silica particles, more particularly silica fine particles, is further improved and the content of aggregated particles is reduced.

In general, polyester, especially polyethylene terephthalate (hereinafter referred to as PET), has excellent heat resistance, mechanical strength, transparency, and chemical resistance. , machinery and electronic parts, and its price is lower than that of other high-performance resins, so its applications and usage tend to continue to expand. In particular, polyester films that are currently industrially produced are widely used as base films for magnetic recording media, various packaging materials, and other industrial uses. Along with this, the market for optical films is expanding.

Recently, with the development of display electronic products, optical films used for them, such as prism sheets, light diffusion sheets, touch panel substrate films, etc., are required to have higher brightness and sharpness. There is a demand for techniques for minimizing internal defects and surface defects that impair transparency and smoothness.

The term "internal defect" as used herein is defined only in the present invention, and means a factor that exists inside the PET and has a different refractive index, causing reflection and scattering of light to reduce the transparency of the PET. do. The cause is caused by inorganic metals, external foreign matter, particle aggregation, carbides, and the like. Further, the surface defects are present on the surface of the PET film and mean not only reflection and scattering of light but also scratches, surface unevenness, etc., which pose problems in subsequent processes.

When polyester is used for a film or the like, particles are added for the purpose of imparting excellent windability to the resulting film. However, with the recent trend toward thinner films, a higher degree of surface flatness than in the past or features with fewer defects are required. In particular, when silica fine particles having a small average particle size are used to produce a thin film, aggregation of locally generated silica particles, specifically silica particles, or silica particles and silica particles are added as a catalyst. Agglomeration with metal components may occur, resulting in large protrusions on the surface, or defects such as fish eyes during film formation.

The present invention can achieve excellent dispersibility of silica particles, improves the dispersibility of silica particles having a smaller average particle size, specifically 5 μm or less, and reduces particle agglomeration during film production. It is an object of the present invention to provide a polyester polymer composition with a reduced number of defects. That is, it is an object of the present invention to provide a polyester composition in which silica particles are suppressed from locally forming large aggregates so that the aggregates are too small or do not occur, and silica particles are uniformly dispersed. .

Another object of the present invention is to provide a polyester film having few or almost no internal defects using the polyester resin composition.

One aspect of the present invention comprises a monomer composition comprising a diol component and a dicarboxylic acid component or a prepolymerized composition of the monomer composition and a silica slurry composition,
The silica slurry composition comprises a copolymer containing polymerized units derived from a polyoxyalkylene compound (a) represented by the following chemical formula 1 and polymerized units derived from an acid or an acid derivative (b), a diol component and A polyester polymeric composition comprising silica particles.

[Chemical Formula 1]
_{R1O (} R2O) _nR3

In the above chemical formula 1, R ₁ is a C1-C18 hydrocarbon group,
The R ₂ O is one or a combination of two or more selected from C1-C10 oxyalkylene groups, and must contain an oxyethylene group, and the oxyethylene group and the C1 and C3-C10 oxyalkylene groups when combined, the content of oxyethylene groups is greater than the content of C1 and C3-C10 oxyalkylene groups;
said R ₃ is selected from the group consisting of a C2-C5 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 1-50.

Another aspect of the present invention is a polyester resin masterbatch chip produced by polymerizing the polyester polymer composition.

Yet another aspect of the present invention is a polyester film produced by melt extruding and stretching the resin composition containing the polyester resin masterbatch chips.

Yet another aspect of the present invention is a copolymer comprising polymerized units derived from the polyoxyalkylene compound (a) represented by Chemical Formula 1 and polymerized units derived from an acid or acid derivative (b) , a diol component, and a silica slurry composition comprising silica particles, and polymerizing the resulting polyester resin masterbatch chip.

The present invention can improve the dispersibility and dispersion stability of silica fine particles in a slurry, and also has the effect of suppressing reaggregation of silica fine particles that can occur when silica fine particles are introduced into a high-temperature polycondensation process. very good at

In addition, the film according to the present invention can eliminate the drawback associated with the aggregation of silica fine particles, thereby providing a film that can be applied to optical films and the like.

Hereinafter, the present invention will be described in more detail through specific examples or examples of the present invention. However, the specific examples or examples below are merely an example for explaining the present invention in detail, and the present invention is not limited thereto and can be embodied in various forms.

Also, unless defined otherwise, 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 herein is merely for the purpose of effectively describing particular embodiments and is not intended to be limiting of the invention.

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

One aspect of the present invention comprises a monomer composition comprising a diol component and a dicarboxylic acid component or a prepolymerized composition of the monomer composition and a silica slurry composition,
The silica slurry composition comprises a copolymer containing polymerized units derived from a polyoxyalkylene compound (a) represented by the following chemical formula 1 and polymerized units derived from an acid or an acid derivative (b), a diol component and A polyester polymeric composition comprising silica particles.

[Chemical Formula 1]
_{R1O (} R2O) _nR3

In the above chemical formula 1, R ₁ is a C1-C18 hydrocarbon group,
The R ₂ O is one or a combination of two or more selected from C1-C10 oxyalkylene groups, and must contain an oxyethylene group, and the oxyethylene group and the C1 and C3-C10 oxyalkylene groups when combined, the content of oxyethylene groups is greater than the content of C1 and C3-C10 oxyalkylene groups;
said R ₃ is selected from the group consisting of a C2-C5 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 1-50.

In one embodiment of the present invention, in Formula 1, R ₁ is a C1-C4 hydrocarbon group,
The R ₂ O may be an oxyethylene group alone or a combination of an oxyethylene group and an oxypropylene group. In the case of the combination, the content of the oxyethylene group is greater than the content of the oxypropylene group,
said R ₃ is selected from the group consisting of a C3-C4 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is preferably an integer of 10-40.

In one aspect of the present invention, the acid or acid derivative (b) includes acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, maleic anhydride, allylsulfonic acid, Any one or a combination of two or more selected from the group consisting of maleic acid alkyl ester, vinyl acetate, allylsulfonic acid, methallylsulfonic acid and salts thereof may be used.

In one aspect of the present invention, the copolymer includes methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, p-styrenesulfonic acid, indene, isobutylene, isoprene, and N-phenylmaleimide. , N-cyclohexylmaleimide, polymerized units derived from any one or two or more comonomers (c).

In one embodiment of the present invention, the copolymer may have a viscosity of 1,000-20,000 cP and a saponification value of 10-200 mgKOH/g.

In one aspect of the present invention, the silica particles may have an average particle size of 0.01 to 5 μm.

In one aspect of the present invention, the silica particles may be included in the polyester polymerization composition in an amount of 0.001-3% by weight.

In one aspect of the present invention, the copolymer may be contained in an amount of 0.01 to 5% by weight based on the content of particles contained in the polyester polymerization composition.

In one aspect of the present invention, in the silica slurry composition, the number of aggregated particles having an average particle size of 10 μm or more may satisfy the following formula 1.

[Formula 1]
_P2 < _P1

In the above formula 1, P ₁ is the number of aggregated particles (number/15 ml) having an average particle size of 10 μm or more in the silica slurry composition that does not contain the copolymer, and P ₂ is the copolymer is the number of aggregated particles having an average particle size of 10 μm or more (number/15 ml) in the silica slurry composition containing

In one aspect of the present invention, the silica slurry composition may have a number of aggregated particles having an average particle size of 10 μm or more of 1/15 ml or less.

In one aspect of the present invention, the polyester polymerization composition may further include any one or a combination of two or more selected from the group consisting of a catalyst, an electrostatic pinning agent and a heat stabilizer.

Another aspect of the present invention is a polyester resin masterbatch chip produced by polymerizing the polyester polymer composition.

In one aspect of the present invention, the polyester resin masterbatch chip may have 6 or less aggregated particles having an average particle size of 10 μm or more in an area of 448 μm×336 μm.

Another aspect of the present invention is a polyester film produced by melt extruding and stretching the resin composition containing the polyester resin masterbatch chips.

In one aspect of the present invention, the polyester film may have a thickness of 10-300 μm.

A silica slurry composition containing a copolymer containing polymerized units derived from a polyoxyalkylene compound (a) represented by the following chemical formula 1 and polymerized units derived from an acid or an acid derivative (b), a diol component, and silica particles A method for producing a polyester resin masterbatch chip, comprising the step of adding and polymerizing a substance in an esterification reaction step or a polycondensation reaction step.

[Chemical Formula 1]
_{R1O (} R2O) _nR3

In the above chemical formula 1, R ₁ is a C1-C18 hydrocarbon group,
The R ₂ O is one or a combination of two or more selected from C1-C10 oxyalkylene groups, and must contain an oxyethylene group, and the oxyethylene group and the C1 and C3-C10 oxyalkylene groups when combined, the content of oxyethylene groups is greater than the content of C1 and C3-C10 oxyalkylene groups;
said R ₃ is selected from the group consisting of a C2-C5 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 1-50.

In one aspect of the invention, the copolymer comprises methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, p-styrenesulfonic acid, indene, isobutylene, isoprene, N-phenylmaleimide, It may further contain polymerized units derived from any one or two or more comonomers (c) selected from N-cyclohexylmaleimide.

In one embodiment of the present invention, the copolymer may have a viscosity of 1,000-20,000 cP and a saponification value of 10-200 mgKOH/g.

In one aspect of the invention, the silica slurry composition may be introduced prior to the polycondensation reaction.

Hereinafter, each configuration of the present invention will be described more specifically.

(Polyester polymerization composition)
In one aspect of the present invention, the polyester polymerization composition refers to a composition that is charged into a reactor to produce a polyester resin.

In one aspect of the present invention, the polyester polymer composition comprises polymerized units derived from the polyoxyalkylene compound (a) represented by Chemical Formula 1 and polymerized units derived from the acid or acid derivative (b). A silica slurry composition comprising a copolymer, a diol component and silica particles is included.

More specifically, the polyester polymerization composition is produced by an esterification or transesterification reaction of a dicarboxylic acid component and a diol component, such as a melt polycondensation method, to produce a normal homopolymer or copolymer polyester. It may be a composition for

Generally, when polymerizing a polyester resin, inorganic particles can be added in the form of a slurry of inorganic particles dispersed in a diol component, more specifically, ethylene glycol. When a silica slurry composition is prepared using silica as the inorganic particles and then introduced into the polymerization reaction of the polyester resin, aggregation of the particles occurs, which increases internal defects during film production. In particular, during the high-temperature polycondensation reaction, when the slurry was added, the particles agglomerated more severely.

The inventors of the present invention prepared a copolymer containing a polymerized unit derived from the polyoxyalkylene compound (a) represented by the above chemical formula 1 and a polymerized unit derived from an acid or an acid derivative (b). By containing, it is possible to further improve the dispersibility of the silica particles in the slurry, and even if the slurry is added during the high-temperature polycondensation reaction, it is possible to prevent the particles from aggregating, thereby masterbatch chips and It has been found that internal defects due to reaggregation of silica can be eliminated during film production.

In one aspect of the present invention, the first aspect of the polyester polymerization composition can include a monomer composition comprising a diol component and a dicarboxylic acid component; and a silica slurry composition; , a copolymer containing a polymer unit derived from the polyoxyalkylene compound (a) represented by the above chemical formula 1 and a polymer unit derived from an acid or an acid derivative (b), a diol component, and silica particles can include

A second aspect of the polyester polymerization composition may include a prepolymerization composition of a monomer composition containing a diol component and a dicarboxylic acid component and a silica slurry composition, wherein the silica slurry composition is represented by Formula 1 A polymerized unit derived from a polyoxyalkylene compound (a) represented by and a copolymer containing a polymerized unit derived from an acid or an acid derivative (b), a diol component, and silica particles. can.

A third aspect of the polyester polymerization composition may further include a catalyst, an electrostatic pinning agent, and a heat stabilizer in the first aspect or the third aspect.

A fourth aspect of the polyester polymer composition is, in the first to third aspects, an antistatic agent, an auxiliary flame retardant, a pigment, a dye, a glass fiber, a filler, a heat-resistant agent, an impact aid, and a fluorescent brightener. and a hue improving agent, or a combination of two or more thereof.

The first to fourth aspects are merely examples for more specifically explaining the present invention, and are not intended to limit the present invention.

In one aspect of the present invention, the additives such as the electrostatic pinning agent and the heat stabilizer may be added during the polymerization of the polyester resin or may be added during melt molding. It is preferably added at the time of polymerization from the viewpoint of dispersing and adjusting the content of terminal carboxyl groups and the content of diethylene glycol. When added at the time of polymerization, the time of addition is arbitrary before the ester exchange reaction stage during polyester polymerization or after the end of the ester exchange reaction and at the beginning of the polycondensation reaction, specifically, for example, until the intrinsic viscosity is less than 0.3. may be added at the time of More preferably, each diol component, more specifically, ethylene glycol is dissolved or completely mixed in order to prevent reaggregation or polymerization of itself, and it is produced in a solution or slurry state. It is desirable to input At this time, it is preferable that the slurry has a solid content of 3% by weight or less in order to effectively prevent re-agglomeration, but it is not limited thereto.

In one aspect of the present invention, the dicarboxylic acid component is not limited, but examples include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, and eicosane. Aliphatic dicarboxylic acids such as dioic acid, pimelic acid, azelaic acid, methylmalonic acid and ethylmalonic acid, alicyclic dicarboxylic acids such as adamantanedicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid and decalindicarboxylic acid, terephthalic acid , isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4, Dicarboxylic acids such as 4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendane dicarboxylic acid, anthracenedicarboxylic acid, phenanthenedicarboxylic acid, aromatic dicarboxylic acids such as 9,9'-bis(4-carboxyphenyl)fluoric acid Acid components include, but are not limited to. Moreover, these can be used individually or in combination of 2 or more. More specifically, the dicarboxylic acid component may be terephthalic acid.

In one aspect of the present invention, the diol component is not limited, but examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2- Aliphatic diols such as butanediol and 1,3-butanediol, alicyclic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, bisphenol S, 1,3-benzenedimethanol, 1,4- Examples include, but are not limited to, diols such as benzenedimethanol, 9,9'-bis(4-hydroxyphenyl)fluorene, aromatic diols, and a plurality of the above diols linked together. Moreover, these can be used individually or in combination of two or more as needed. More specifically, the diol component may be ethylene glycol.

In one aspect of the present invention, the polyester polymer composition comprises polymerized units derived from a polyoxyalkylene compound (a) represented by Chemical Formula 1 below and polymerized units derived from an acid or an acid derivative (b). By containing the copolymer, the dispersibility of the silica particles can be improved, reaggregation can be prevented, and the slurry can be added at the high-temperature polycondensation stage.

[Chemical Formula 1]
_{R1O (} R2O) _nR3

In the above chemical formula 1, R ₁ is a C1-C18 hydrocarbon group,
The R ₂ O is one or a combination of two or more selected from C1-C10 oxyalkylene groups, and must contain an oxyethylene group, and the oxyethylene group and the C1 and C3-C10 oxyalkylene groups when combined, the content of oxyethylene groups is greater than the content of C1 and C3-C10 oxyalkylene groups;
said R ₃ is selected from the group consisting of a C2-C5 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 1-50.

In one embodiment of the present invention, in Formula 1 above, R ₁ is selected from C1-C18 hydrocarbon groups, specifically C1-C18 alkyl, C3-C18 cycloalkyl and C6-C18 aryl. may be More specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group , octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclohexyl, phenyl and benzyl groups. More specifically, it may be a C1-C4 hydrocarbon group, but is not limited thereto.

In one aspect of the present invention, the R ₂ O may be one or a combination of two or more selected from C1-C10 oxyalkylene groups, and when an oxyethylene group is always included, the diol component, More specifically, it has excellent affinity for ethylene glycol, further improves the dispersibility of silica particles, prevents aggregation, and can prevent re-aggregation even when added during the polycondensation reaction. In the case of two or more types, the form of addition may be random or block-like.

At this time, when one or more other types of oxyalkylene groups are further included in addition to the oxyethylene group, the content of the oxyethylene group is higher than the content of the other oxyalkylene groups. It is more desirable because it has excellent dispersibility and miscibility with respect to the diol component, more specifically, ethylene glycol, which is added during production, and can further improve the dispersibility of the particles. More specifically, the content of oxyethylene groups is 51 mol% or more, more specifically 51 to 99 mol%, and the content of oxyalkylene groups excluding the oxyethylene groups is 1 to 49 mol%. can be included.

More specifically, R ₂ O may be one or a combination of two or more selected from C2-C4 oxyalkylene groups. Examples of the C2-C4 oxyalkylene groups include: oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group and the like.

More specifically, R ₂ O may be an oxyethylene group alone, or a combination of an oxyethylene group and one or more selected from C3-C4 oxyalkylene groups.

Even more specifically, said R ₂ O is an oxyethylene group alone or a combination of an oxyethylene group and an oxypropylene group, and when said combination, the content of oxyethylene groups is oxypropylene group may be higher than the content of

In one aspect of the present invention, said R ₃ is selected from the group consisting of hydrogen, a C2-C5 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group, more particularly a C2-C5 unsaturated hydrocarbon group may be selected from the group consisting of groups, acryloyl groups and methacryloyl groups.

Examples of the C2-C5 unsaturated hydrocarbon group include vinyl group, allyl group, isopropenyl, 1-propenyl group, methallyl group, and 3-butenyl group. More specifically, it may be a C3-C4 unsaturated hydrocarbon group, and more specifically, it may be a C3-C4 allyl group and methallyl group.

In one embodiment of the present invention, n represents the average number of added moles of oxyalkylene groups, and is 1-50, specifically 5-45, more specifically 10-40. Provided is a copolymer capable of exhibiting a viscosity suitable for dispersing silica fine particles in such a range, preferably satisfying a viscosity range of 1,000 to 20,000 cP, more preferably 2,000 to 10,000 cP. Although it is desirable because it can be done, it is not limited to this. It is preferable that the viscosity is within such a range, since the handling property is good and the dispersibility of the silica particles can be further improved. The said viscosity is measured by the measuring method mentioned later.

In one aspect of the present invention, in the acid or acid derivative (b), the acid may be a carboxylic acid or a salt thereof, and the acid derivative is an acid anhydride, a polyacid obtained from an acid anhydride, and may be a salt of

More specifically, the acid or acid derivative (b) includes, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, maleic anhydride, allylsulfonic acid, Any one or a combination of two or more selected from the group consisting of maleic acid alkyl ester, vinyl acetate, allylsulfonic acid, methallylsulfonic acid and salts thereof may be used. More specifically, said acid or acid derivative (b) may be selected from maleic acid, maleic anhydride and salts thereof.

In one aspect of the present invention, the copolymer can be prepared by copolymerizing 5 to 95 mol% of the polyoxyalkylene compound (a) and 5 to 95 mol% of the acid or acid derivative (b), but is limited thereto. not to be Also, the copolymer has a weight average molecular weight of 500 to 100,000, more specifically 1,000 to 20,000, but is not limited thereto.

In one aspect of the present invention, the copolymer includes methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, p-styrenesulfonic acid, indene, isobutylene, isoprene, N-phenylmaleimide, It can further contain polymerized units derived from any one or more comonomers (c) selected from N-cyclohexylmaleimide. More specifically, the comonomer may be styrene. The content of the comonomer (c) is not limited, but may be 1 to 50 mol %. More specifically, the copolymer contains 1 to 95 mol% of a polyoxyalkylene compound (a), 1 to 95 mol% of an acid or acid derivative (b) and 1 to 50 mol% of a comonomer (c). can be produced by copolymerizing, but is not limited to this.

In one aspect of the present invention, the viscosity of the copolymer may range from 1,000 to 20,000 cP, preferably from 1,500 to 10,000 cP, and in such a range the dispersibility of the silica particles is Further, it is desirable to improve the miscibility with other components during the production of the polyester polymer composition, but it is not limited thereto.

In one aspect of the present invention, the copolymer may have a saponification value of 10-200 mgKOH/g, specifically 60-200 mgKOH/g, more specifically 100-150 mgKOH/g. The greater the saponification value, the better the affinity with the particles. However, when the saponification value increases above a certain amount, the oxyalkylene structure that prevents aggregation between particles becomes relatively small, so aggregation cannot be effectively prevented. Therefore, it is desirable to prevent dispersibility between particles and re-aggregation within such a range, but it is not limited to this range.

In one aspect of the present invention, the copolymer is contained in an amount of 0.01 to 5% by weight, more specifically 0.1 to 3% by weight, based on the content of particles contained in the polyester polymerization composition. may If the copolymer is added in excess, it may act as an impurity and degrade the color and reaction rate of the masterbatch chip. It is possible because it is not. Therefore, the content within the above range is desirable because it is sufficient to improve the dispersibility of the silica particles, but the content is not limited thereto.

In one aspect of the present invention, the polyester polymer composition may contain inorganic particles, more specifically silica particles, in order to impart antiblocking properties required during film production. Although the average particle size of the silica particles is not limited, the average particle size may be 0.01 to 5 μm, more specifically 0.1 to 3 μm. Generally, when fine particles in such a range are used, re-aggregation of particles occurs and many internal defects occur. Since the dispersibility of the particles can be greatly improved, reaggregation can be prevented even when fine particles having the above average particle size are used. In addition, the slurry can be introduced even in the high-temperature polycondensation reaction stage where aggregation of inorganic particles occurs more frequently.

The content of the silica particles may be 0.001 to 3% by weight, more specifically 0.1 to 2% by weight, of the polyester polymerization composition, and such a range is required for the optical film. Although it is desirable because it can achieve haze and slip properties, it is not limited to this.

In one aspect of the present invention, the silica slurry composition contains the copolymer and silica particles, so that the number of aggregated particles having an average particle size of 10 μm or more can satisfy Formula 1 below.

[Formula 1]
_P2 < _P1

In the above formula 1, P ₁ is the number of aggregated particles (number/15 ml) having an average particle size of 10 μm or more in the silica slurry composition that does not contain the copolymer, and P ₂ is the copolymer The number of aggregated particles having an average particle size of 10 μm or more (number/15 ml) in the silica slurry composition containing.

More specifically, in the silica slurry composition, the number of aggregated particles having an average particle size of 10 μm or more is 1/15 ml or less, preferably 0.5/15 ml or less.

In one aspect of the present invention, the order of adding the copolymer is not limited during the preparation of the silica slurry composition. Specifically, for example, the silica particles may be added to the diol component, more specifically, to be dispersed in ethylene glycol immediately after being added, or the copolymer may be added after the silica particles are sufficiently dispersed in ethylene glycol. good.

In one aspect of the present invention, the polyester polymer composition comprises a catalyst, an electrostatic pinning agent, a heat stabilizer, an auxiliary flame retardant, a pigment, a dye, a glass fiber, a filler, a heat-resistant agent, an impact aid, and an optical brightener. and color improvers, but not limited thereto.

In one aspect of the present invention, the catalyst is not limited as long as it is used for polyester polycondensation, and more preferably, metal catalysts such as tin and antimony can be used. Specifically, for example, antimony compounds, tin compounds, titanium compounds, germanium compounds, and the like can be used, and they can be used alone or in combination of two or more. The content of the catalyst is preferably 80 to 400 ppm, preferably 100 to 300 ppm, in the polyester polymerization composition, and it is preferable because the reactivity is excellent in such a range, but it is limited to this. is not.

In one aspect of the present invention, the electrostatic pinning agent is not limited as long as it is commonly used, but preferably a metal-based pinning agent can be used. More specifically, it is desirable to use, for example, alkali metal compounds, alkaline earth metal compounds, manganese compounds, cobalt compounds, zinc compounds, etc., because of their high electrostatic activity. Specific examples thereof include magnesium acetate, sodium acetate, calcium acetate, lithium acetate, calcium phosphate, magnesium oxide, magnesium hydroxide, magnesium alkoxide, manganese acetate, zinc acetate and the like. Any combination of the above can be used. The content of the electrostatic pinning agent can be 10 to 100 ppm, preferably 10 to 50 ppm, in the polyester polymerization composition. It is desirable because it can produce a film with low haze, but it is not limited to this.

In one aspect of the present invention, the heat stabilizer is not limited as long as it is commonly used in the field, and a specific example thereof is a phosphorus compound. As specific examples, trimethyl phosphate, triethyl phosphate, phosphoric acid, and the like can be used. The phosphorus compound can impart an effect of improving pinning property as well as a heat stabilizing effect. The content of the heat stabilizer is 10 to 150 ppm, preferably 10 to 100 ppm, in the polyester polymerization composition, and this range is sufficient to achieve the effect of improving heat stability and pinning properties. Therefore, it is desirable, but it is not limited to this.

(Polyester resin masterbatch chip and its manufacturing method)
In one aspect of the present invention, polyester resin masterbatch chips refer to polyester resin chips containing inorganic particles, specifically silica particles. In general, as a method of adding inorganic particles during film production, it is possible to add during polymerization of the polyester resin or during melt extrusion of the resin, and by adding during polymerization of the polyester resin, the inorganic particles Dispersibility can be further improved. The present invention can further improve the dispersibility of silica particles by adding a silica slurry composition containing the copolymer during polymerization.

In one aspect of the present invention, the polyester resin masterbatch chip may be produced by polymerizing the polyester polymer composition described above. More specifically, it can be produced by including a transesterification reaction step and a polycondensation reaction step. Also, it may be manufactured by further including a solid phase polymerization step after the polycondensation reaction step.

In one aspect of the present invention, the order of adding the silica slurry composition is not limited, and it can be added before the transesterification reaction step or before the polycondensation reaction step. In the present invention, by including the copolymer, the dispersibility of the particles in the silica slurry composition is very excellent, it is possible to prevent the occurrence of reaggregation, and it is introduced even in a high-temperature reaction stage such as a polycondensation reaction. is possible, and reaggregation of particles hardly occurs even if it is added in the polycondensation reaction stage.

The first mode for producing the polyester resin masterbatch chip of the present invention is
a step of mixing a dicarboxylic acid or an ester derivative thereof with a diol component and allowing an ester reaction to proceed to produce a prepolymer;
and adding a catalyst, an electrostatic pinning agent, a heat stabilizer, and a silica slurry composition to the prepolymer to perform a polycondensation reaction.

The second mode for producing the polyester resin masterbatch chip of the present invention is
a step of mixing a dicarboxylic acid or an ester derivative thereof with a diol component and allowing an ester reaction to proceed to produce a prepolymer;
adding a catalyst, an electrostatic pinning agent, a heat stabilizer and a silica slurry composition to the prepolymer to carry out a polycondensation reaction;
and performing solid state polymerization.

In one aspect of the present invention, the prepolymer may be a low molecular weight substance (low molecular weight oligomer), more specifically BHET (bis-β-hydroxyethyl terephthalate).

The step of preparing the prepolymer is not limited, but is preferably carried out at 170 to 270° C., and preferably under a pressure of 760 to 1500 torr while allowing water to flow out of the reactor. Although the reaction time is not limited, it is preferably 1 to 10 hours.

In one aspect of the present invention, the polycondensation reaction is preferably performed at 250 to 290° C., although not limited, and preferably under a reduced pressure of 1 torr or less. Although the reaction time is not limited, it is preferably 1 to 10 hours.

In one aspect of the present invention, the produced polyester resin masterbatch chip preferably has an intrinsic viscosity of 0.6 to 0.9 dL / g, and in such a range, excellent film formation stability during film production is obtained. However, it is not limited to this.

In one aspect of the present invention, the number of agglomerated particles having an average particle size of 10 μm or more contained in the polyester resin masterbatch chip is smaller than when the copolymer is not included. can be. More specifically, the number of aggregated particles having an average particle size of 10 μm or more in an area of 448 μm×336 μm may be 6 or less, but the present invention is not limited to this.

(Polyester film and its manufacturing method)
In one aspect of the present invention, the polyester resin masterbatch chip containing the silica particles is used alone, or a polyester resin masterbatch chip containing the silica particles and a polyester resin chip to which no inorganic particles are added are combined. A film can be produced by mixing.

More specifically, the content of the polyester resin masterbatch chips can be added so that the content of silica particles in the final film is 0.001 to 3% by weight. , which is preferable because it can provide a film excellent in permeability, slip property and running property, but is not limited thereto.

In one aspect of the present invention, the polyester film can be produced by a conventional method. More specifically, the polyester resin masterbatch chips containing the silica particles and the polyester resin chips to which inorganic particles are not added are mixed and melt-extruded by an extruder to produce an unstretched sheet, and the unstretched sheet is produced. A sheet can be stretched to produce a film. Also, after the stretching, the step of heat setting and relaxing may be further included.

In one aspect of the present invention, the polyester film has a skin layer of the polyester resin masterbatch chip containing the silica particles, or the polyester resin masterbatch chip containing the silica particles and inorganic particles are not added. Polyester resin chips are used as a skin layer, and polyester resin chips to which inorganic particles are not added are used as a core layer, and at least one or more skin layers located on one or both sides of the core layer. can be co-extruded such that they are laminated together to produce a multilayer film. More specifically, an unstretched sheet can be produced by co-extrusion, and a film can be produced by stretching the unstretched sheet. Also, after the stretching, the step of heat setting and relaxing may be further included.

In one aspect of the present invention, the stretching can be uniaxial or biaxial, and the biaxial stretching is multi-stage stretching in which the machine direction is stretched and then the width direction is stretched, or the machine direction and the width direction are stretched. It can be carried out as simultaneous stretching. The stretching ratio is not limited, but the machine direction is 1.1 to 10 times, more specifically 2 to 5 times, and the width direction is 1.1 to 10 times, more specifically 4 to 6 times. is preferred. At the above draw ratio, the thermal dimensional stability of the polymer structure can be further increased and heat shrinkage can be reduced, which is desirable, but not limited thereto.

In one aspect of the present invention, the polyester film may be biaxially stretched and then heat-treated at 200-250° C. to relax 1-10%. Specifically, relaxation can be imparted at the same time as the heat treatment, and specifically, it is preferable to relax 1 to 10%, more specifically 2 to 4% in the width direction. Within this range, the film maintains a tensioned state in the width direction, the density of the polymer structure increases, and deformation due to heat can be reduced, which is desirable, but not limited to this. .

In one aspect of the present invention, the polyester film preferably has a thickness of 10 to 300 μm, more specifically 15 to 200 μm, but is not limited thereto.

In one aspect of the present invention, the polyester film may have a smaller number of agglomerated particles having an average particle size of 10 μm or more than the polyester film that does not contain the copolymer. Specifically, the number of aggregated particles having an average particle size of 10 μm or more in an area of 448 μm×336 μm is preferably 45/10 m ² or less, more specifically 40/10 m ² or less.

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

The following physical properties were measured by the following measuring methods.

1) Number of Aggregated Particles in Slurry The number of coarse particles of 10 μm or more in the silica slurry composition was measured using a Coulter Counter (Multisizer 4e manufactured by Beckman). The measurement was repeated three times and the average value was calculated.

Measurement conditions are as follows.

Electrolyte solution: ISOTON (0.9% NaCl aqueous solution)
Aperture Tube Size: 100 μm
Measurement range (Range): 2 to 60 μm
Sample injection volume in electrolyte: 15 μL
Amount of measurement/1 time: Amount of measurement/1 time

2) Number of Aggregated Particles in Masterbatch Chip A polyester resin masterbatch chip (chip) manufactured in the form of pellets was melted on a slide glass to prepare a sample with a thickness of 40 μm, and a DIC was prepared. Using a (Different Interference Contrast) microscope, defects due to aggregated particles were observed at a magnification of 200 to measure the number of aggregated particles having a size of 10 μm or more in an area of 448 μm×336 μm. It was calculated by averaging the number of defects in a total of 5 micrographs. Also, the defect size was measured with a microscope scale bar and measured with the long axis of the defect as a reference.

3) Number of Aggregated Particles in Film For the area of 10 m ² of the produced film, a polarizer (Shinto Kagaku Co., Ltd. (Heidon), distortion tester Type 25W) was used to make the polarizers orthogonal, The sample was placed and observed, and all glittering defects larger than 10 µm were marked as internal defects. The morphology of the internal defect was observed with a microscope (Leica DM2700M) at a magnification of 500 times to classify foreign matter having the form of agglomerated particles, and then the number of the foreign matter was measured.

4) Intrinsic viscosity measurement method 0.4 g of PET pellets (sample) was added to 100 ml of ortho-chlorophenol reagent and dissolved for 100 minutes. Then, using a viscometer and an aspirator, the number of seconds the solution fell was determined. After determining the number of seconds for the solvent to drop in the same manner, the RV and IV values were calculated by the following formulas.

RV = sample fall seconds/solvent fall seconds

5) Affinity with Ethylene Glycol 1 g of the copolymer shown in Table 1 below was added to 100 ml of ethylene glycol, stirred for 10 minutes, and the state of the solution was visually observed.

Good: the solution was clear and thoroughly mixed after 10 minutes of stirring.
Fair: cloudy after 10 minutes of stirring, clear after 1 hour of stirring.
Poor: no mixing occurred after stirring for 10 minutes and layer separation occurred.

6) Saponification value Measured according to ASTM D5558-95.

7) Viscosity After preparing the sample at 25° C., the viscosity was measured at 50 rpm after mounting a No. 64 spindle on a Brookfield viscometer (DV1MRVTJO).

8) Color (b ^* )
The hue of the film was confirmed using a color meter. As for the measurement method, Konica Minolta (CM-512m3) equipment was used, and the hues of the films were compared with b ^* , which indicates the hue of the films.

The physical properties of the copolymers used in the preparation examples are as follows.

In Table 1 above, EO is oxyethylene and PO is oxypropylene. EO/PO is a random addition form of oxyethylene and oxypropylene. 2 mol % of the styrene was used.

[Example 1]
1) Preparation of silica slurry composition To 99.23% by weight of ethylene glycol was added 7% by weight of silica particles having an average particle size of 1.9 μm, and 0.07% by weight of copolymer (1) in Table 1 above ( 1% by weight with respect to the content of the particles), and stirred at 3500 rpm for 6 hours using a homomixer to prepare a silica slurry composition 1. The number of aggregated particles in the produced slurry was measured and shown in Table 2 below.

2) Production of polyethylene terephthalate resin masterbatch chip After 50 parts by weight of ethylene glycol was added to 100 parts by weight of terephthalic acid in an esterification reactor, the pressure was increased to 1100 torr at 250°C for 4 hours, and water was added. An esterification reaction was carried out while flowing out of the reactor to produce a prepolymer BHET (bis-β-hydroxyethyl terephthalate). The water generated during the reaction was separated using a distillation column, and the additionally generated ethylene glycol was also separated using a distillation column after the completion of the esterification reaction.

150 ppm of magnesium acetate as an electrostatic pinning agent and 72 ppm of trimethyl phosphate as a heat stabilizer were mixed with 100 parts by weight of the resin composition into the BHET produced above, and trioxide was added as a polymerization catalyst. Together with 200 ppm of antimony, the silica slurry composition (1) was further added so that the content of particles in the masterbatch chip was 7,000 ppm, and then the temperature was gradually raised from 250°C to 285°C at a rate of 60°C/hr. At the same time, a polycondensation reaction was carried out under a high vacuum of 0.3 torr for 4 hours to produce a polyethylene terephthalate resin masterbatch chip (1) having an intrinsic viscosity (IV) of 0.615.

The number of agglomerated particles in the manufactured polyethylene terephthalate resin masterbatch chips was measured and shown in Table 3 below.

3) Production of polyethylene terephthalate film 42.5% by weight of the polyethylene terephthalate resin masterbatch chips (1) and 57.5% by weight of polyethylene terephthalate resin chips containing no particles were blended and melt-extruded with an extruder. After that, a sheet was produced. The produced sheet was stretched 3.4 times in the machine direction and 4.0 times in the transverse direction at 95° C. and heat-treated at 230° C. to produce a biaxially stretched film having a thickness of 38 μm.

The number of agglomerated particles in the produced film was measured and shown in Table 3 below.

[Example 2]
1) Preparation of silica slurry composition A silica slurry composition ( 2) was produced. The number of aggregated particles in the produced slurry was measured and shown in Table 2 below.

2) Preparation of polyethylene terephthalate resin masterbatch chips A polyethylene terephthalate resin masterbatch chip (2) was prepared in the same manner as in Example 1, except that the silica slurry composition (2) was used.

The number of agglomerated particles in the manufactured polyethylene terephthalate resin masterbatch chips was measured and shown in Table 3 below.

3) Production of polyethylene terephthalate film A film was produced in the same manner as in Example 1, except that the polyethylene terephthalate resin masterbatch chip (2) was used.

The number of agglomerated particles in the produced film was measured and shown in Table 3 below.

[Examples 3 to 7]
1) Preparation of Silica Slurry Composition A silica slurry composition was prepared in the same manner as in Example 1, except for the changes shown in Table 2 below. The number of aggregated particles in the produced slurry was measured and shown in Table 2 below.

2) Manufacture of polyethylene terephthalate resin masterbatch chips Except that the silica slurry composition (1) in Example 1 was replaced with a silica slurry composition as shown in Table 3 below. A polyethylene terephthalate resin masterbatch chip was produced in the same manner as in Example 1.

The number of aggregated particles in the manufactured polyethylene terephthalate resin masterbatch chip was measured and shown in Table 3 below.

3) Production of polyethylene terephthalate film A film was produced in the same manner as in Example 1, except that the polyethylene terephthalate resin masterbatch chip in Example 1 was changed to that produced in each example. .

The number of agglomerated particles in the produced film was measured and shown in Table 3 below.

[Comparative Examples 1 to 4]
1) Preparation of Silica Slurry Composition A silica slurry composition was prepared in the same manner as in Example 1, except for the changes shown in Table 2 below. The number of aggregated particles in the produced slurry was measured and shown in Table 2 below.

2) Manufacture of polyethylene terephthalate resin masterbatch chips Example 1 was the same as Example 1, except that instead of silica slurry composition (1) in Example 1, the silica slurry composition was changed as shown in Table 2 below. A polyethylene terephthalate resin masterbatch chip was produced in a similar manner.

The number of aggregated particles in the manufactured polyethylene terephthalate resin masterbatch chip was measured and shown in Table 3 below.

3) Production of polyethylene terephthalate film A film was produced in the same manner as in Example 1, except that the polyethylene terephthalate resin masterbatch chip in Example 1 was changed to that produced in each example. .

The number of aggregated particles in the produced film was measured and shown in Table 3 below.

As shown in Tables 2 and 3 above, the number of aggregated particles in Examples 1 and 2 was significantly reduced compared to Comparative Example 1 using a silica slurry composition containing no copolymer. confirmed. It was also confirmed that the slurry of the present invention has excellent particle dispersibility even when added during a high-temperature polycondensation reaction.

In the case of Comparative Examples 2 and 3, by using a copolymer having low affinity for ethylene glycol and low affinity for particles, the number of agglomerated particles is higher than that of Comparative Example 1, which does not use a copolymer. was confirmed to have increased.

Claims (17)

a monomer composition comprising a diol component and a dicarboxylic acid component or an oligomer of said diol component and said dicarboxylic acid component and a silica slurry composition;
The silica slurry composition contains a polyoxyalkylene compound (a) represented by the following chemical formula 1, a copolymer of an acid or an acid derivative (b) , a diol component and silica particles,
The copolymer has a saponification value of 60 to 200 mgKOH/g,
The copolymer is contained in an amount of 0.01 to 5% by weight with respect to the content of silica particles contained in the polyester polymerization composition.
A polyester polymer composition.
[Chemical Formula 1]
_{R1O (} R2O) _nR3
In the chemical formula 1, R ₁ is a C1-C4 hydrocarbon group,
The R ₂ O is an oxyethylene group alone or a mixture of an oxyethylene group and an oxypropylene group, and when mixed, the content of the oxyethylene group is greater than the content of the oxypropylene group ,
said R ₃ is selected from the group consisting of a C3-C4 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 10-40 . Examples of the acid or acid derivative (b) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, maleic anhydride, allylsulfonic acid, maleic acid alkyl ester, and vinyl acetate. , allylsulfonic acid, methallylsulfonic acid and salts thereof, or a combination of two or more thereof. The copolymer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, p-styrenesulfonic acid, indene, isobutylene, isoprene, N-phenylmaleimide, and N-cyclohexylmaleimide. 2. The polyester polymeric composition of claim 1, further comprising polymerized units derived from any one or more comonomers (c). The polyester polymeric composition of claim 1, wherein said copolymer has a viscosity of 1,000 to 20,000 cP. The polyester polymer composition according to claim 1, wherein the silica particles have an average particle size of 0.01 to 5 µm. 2. The polyester polymerization composition according to claim 1, wherein the silica particles comprise 0.001 to 3% by weight of the polyester polymerization composition. 2. The polyester polymerization composition according to claim 1, wherein the silica slurry composition has a number of aggregated particles having an average particle size of 10 [mu]m or more that satisfies the following formula (1).
[Formula 1]
_P2 < _P1
In the above formula 1, P ₁ is the number of aggregated particles having an average particle size of 10 μm or more in the silica slurry composition that does not contain the copolymer (number/15 mL), and P ₂ is the copolymer The number of aggregated particles having an average particle size of 10 μm or more (number/15 mL) in the silica slurry composition containing. 8. The polyester polymerization composition according to claim 7 , wherein the silica slurry composition has a number of agglomerated particles with an average particle size of 10 μm or more of 1/15 mL or less. 2. The polyester polymerization composition according to claim 1, further comprising any one or a combination of two or more selected from the group consisting of a catalyst, an electrostatic pinning agent and a heat stabilizer. A polyester resin masterbatch chip produced by polymerizing the polyester polymerization composition according to any one of claims 1 to 9 . 11. The polyester resin masterbatch chip according to claim 10 , wherein the polyester resin masterbatch chip has 6 or less aggregated particles having an average particle size of 10 μm or more in an area of 448 μm×336 μm. A polyester film produced by melt-extruding and stretching a resin composition comprising the polyester resin masterbatch chip according to claim 10 . 13. The polyester film according to claim 12 , wherein the polyester film has a thickness of 10-300 μm. A copolymer having a saponification value of 60 to 200 mgKOH/g, comprising a polymerized unit derived from a polyoxyalkylene compound (a) represented by the following chemical formula 1 and a polymerized unit derived from an acid or an acid derivative (b) A method for producing a polyester resin masterbatch chip, comprising adding and polymerizing a silica slurry composition containing coalescence, a diol component and silica particles in an esterification reaction step or a polycondensation reaction step.
[Chemical Formula 1]
_{R1O (} R2O) _nR3
In the chemical formula 1, R ₁ is a C1-C4 hydrocarbon group,
The R ₂ O is an oxyethylene group alone or a mixture of an oxyethylene group and an oxypropylene group, and when mixed, the content of the oxyethylene group is greater than the content of the oxypropylene group ,
said R ₃ is selected from the group consisting of a C3-C4 unsaturated hydrocarbon group, an acryloyl group and a methacryloyl group;
Said n is an integer of 10-40 . The copolymer is selected from methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, p-styrenesulfonic acid, indene, isobutylene, isoprene, N-phenylmaleimide, and N-cyclohexylmaleimide. 15. The method for producing a polyester resin masterbatch chip according to claim 14 , further comprising polymerized units derived from any one or more comonomers (c). The method for producing a polyester resin masterbatch chip according to claim 14 , wherein the copolymer has a viscosity of 1,000 to 20,000 cP. 15. The method for producing a polyester resin masterbatch chip according to claim 14 , wherein the silica slurry composition is added before the polycondensation reaction.