KR20190038017A - Composition for polymerizing polyester resin, polyester resin materbatch chip, and polyester film using the same - Google Patents

Abstract

The present invention relates to a polyester polymerization composition which further improves dispersibility of silica particles and reduces the content of aggregated particles, a polyester resin master batch chip, and a polyester film using the same. The polyester polymerization composition comprises a monomer composition including a diol component and a dicarboxylic acid component or a prepolymer composition of the monomer composition, and a silica slurry composition.

Description

TECHNICAL FIELD The present invention relates to a polyester polymer composition, a polyester resin master batch chip, and a polyester film using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a polyester polymerization composition, a polyester resin master batch chip and a polyester film using the same, wherein the dispersibility of the silica particles, more preferably the silica fine particles, is further improved and the content of the aggregated particles is reduced.

In general, polyester, especially polyethylene terephthalate (hereinafter referred to as PET), has a good heat resistance, mechanical strength, transparency and chemical resistance, And the use and the amount of use thereof are continuously expanding at a lower price than other high-functional resins. In particular, polyester films that are currently being industrially produced are widely used as base films for magnetic recording media, various packaging materials, and other industrial applications. In recent years, along with the development of various display electronic products, The market is expanding.

Recently, display electronic products have been required to have superior brightness and clarity in optical films used therein, such as prism sheets, optical acid sheets, and base films for touch panels, Lt; RTI ID = 0.0 > and / or < / RTI > surface defects.

Herein, the internal defect is a definition used in the present invention. Internal defect refers to a factor which is present in the PET and has a different refractive index to cause reflection and scattering of light, thereby lowering the transparency of the PET. The cause may be caused by inorganic metal, external water, particle aggregation, carbide, or the like. The surface defects are present on the surface of the PET film and are referred to as reflection and scattering of light as well as scratches and surface irregularities which are problematic in the subsequent process.

When a polyester is used in a film or the like, particles are added for the purpose of imparting good winding property to the obtained film. However, recently, as the film becomes thinner, there is a demand for a feature that requires a higher degree of surface flatness than the conventional one, or has few drawbacks. Particularly, in the case of using silica fine particles having a small average particle diameter for producing a thin film, the aggregation of locally occurring silica particles, specifically, the aggregation of silica particles or the silica particles and the metal component added as a catalyst Resulting in large protrusions on the surface, or defects such as fish eyes when the film is formed.

Therefore, it is required to use silica particles having a relatively small average particle diameter in the polyester composition and to uniformly disperse the particles while suppressing aggregation.

The present invention relates to a method for producing silica particles which can achieve excellent dispersibility of silica particles and which is capable of improving the dispersibility of silica particles having an average particle size of less than 5 占 퐉 and specifically decreasing the number of defects during film production, It is an object of the present invention to provide ester polymerization compositions. In other words, the object of the present invention is to provide a polyester composition in which silica particles are prevented from locally forming large agglomerations, little or no aggregation occurs, and silica particles are uniformly dispersed.

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

One aspect of the present invention includes 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 above-mentioned silica slurry composition comprises a copolymer, a diol component and a silica particle comprising a unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a unit derived from an acid or an acid derivative By weight.

[Chemical Formula 1]

R ₁ O (R ₂ O) n R ₃

In Formula 1, R ₁ is a C1-C18 hydrocarbon group,

R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,

Wherein R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,

And n is an average addition mole number of the oxyalkylene group added is 1 to 50.

Another embodiment of the present invention is a polyester resin master batch chip produced by polymerizing the above polyester polymerizing composition.

Another embodiment of the present invention is a polyester film produced by melt extrusion and stretching of a resin composition comprising the polyester resin master batch chip.

Another embodiment of the present invention includes a copolymer comprising a unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a unit derived from an acid or an acid derivative (b), a diol component and a silica particle And then adding the silica slurry composition to the polyester resin master batch chip.

The present invention can improve the dispersibility and dispersion stability of the silica fine particles in the slurry and also has an excellent effect of suppressing the re-aggregation of the silica fine particles which may occur when the silica fine particles are put into a polycondensation process at a high temperature.

In addition, the film according to the present invention can solve the drawbacks caused by agglomeration of the fine silica particles, thereby providing a film which can be applied to an optical film or the like.

Hereinafter, the present invention will be described in more detail by way of concrete 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.

One aspect of the present invention includes 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 above-mentioned silica slurry composition comprises a copolymer, a diol component and a silica particle comprising a unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a unit derived from an acid or an acid derivative By weight.

[Chemical Formula 1]

R ₁ O (R ₂ O) n R ₃

In Formula 1, R ₁ is a C1-C18 hydrocarbon group,

R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,

Wherein R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,

And n is an average addition mole number of the oxyalkylene group added is 1 to 50.

In one aspect of the invention, and in the formula 1, wherein R ₁ is a C1-C4 hydrocarbon group,

Wherein R ₂ O is an oxyethylene group alone or a mixture of an oxyethylene group and an oxypropylene group, the content of the oxyethylene group in the mixing is larger than the content of the oxypropylene group,

R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C3-C4, an acryloyl group and a methacryloyl group,

And n may be an average addition mole number of oxyalkylene groups in the range of 10 to 40.

In one embodiment of the present invention, the acid or acid derivative (b) is at least one member selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, maleic anhydride, Esters, vinyl acetate, allylsulfonic acid, methallylsulfonic acid, and salts thereof, or a mixture of two or more thereof.

In one embodiment of the present invention, the copolymer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, P- styrenesulfonic acid, , Isoprene, N-phenylmaleimide, N-cyclohexylmaleimide, and units derived from at least one comonomer (c).

In one embodiment of the present invention, the copolymer may have a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g.

In one embodiment of the present invention, the silica particles may have an average particle diameter of 0.01 to 5 mu m.

In one embodiment of the present invention, the silica particles may be contained in an amount of 0.001 to 3% by weight in the polyester polymerization composition.

In one embodiment 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 embodiment of the present invention, the silica slurry composition may be such that the number of agglomerated particles having an average particle diameter of 10 mu m or more satisfies the following formula (1).

[Formula 1]

P ₂ < P ₁

In the formula (1), P ₁ is the number of agglomerated particles having an average particle diameter of 10 탆 or more in the silica slurry composition not containing the copolymer (parts / 15 ml), and P ₂ is the number of aggregated particles in the silica slurry And the number of aggregated particles having an average particle diameter of 10 占 퐉 or more (pieces / 15 ml).

In one embodiment of the present invention, the silica slurry composition may be one in which the number of agglomerated particles having an average particle diameter of 10 mu m or more is 1/15 ml or less.

In one embodiment of the present invention, the polyester polymerizing composition may further comprise any one or a mixture of two or more selected from the group consisting of a catalyst, an electrostatic pinning agent and a heat stabilizer.

Another embodiment of the present invention is a polyester resin master batch chip produced by polymerizing the above polyester polymerizing composition.

In one embodiment of the present invention, the polyester resin master batch chip may have 6 or less agglomerated particles having an average particle diameter of 10 mu m or more in the area of 448 mu m x 336 mu m.

Another aspect of the present invention is a polyester film produced by melt extrusion and stretching of a resin composition comprising the polyester resin master batch chip.

In one embodiment of the present invention, the polyester film may have a thickness of 10 to 300 mu m.

A silica slurry composition comprising a unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a unit derived from an acid or an acid derivative (b), a diol component and silica particles is esterified To a reaction step or a polycondensation reaction step, and then polymerizing the polyester resin master batch chip.

[Chemical Formula 1]

R ₁ O (R ₂ O) n R ₃

In Formula 1, R ₁ is a C1-C18 hydrocarbon group,

R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,

R ₃ is selected from the group consisting of hydrogen, a C 2 -C 5 unsaturated hydrocarbon group, an acryloyl group, and a methacryloyl group,

And n is an average addition mole number of the oxyalkylene group added is 1 to 50.

In one embodiment of the present invention, the copolymer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, P- styrenesulfonic acid, , Isoprene, N-phenylmaleimide, N-cyclohexylmaleimide, and units derived from at least one comonomer (c).

In one embodiment of the present invention, the copolymer may have a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g.

In one embodiment of the present invention, the silica slurry composition may be added prior to the polycondensation reaction.

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

(Polyester polymerization composition)

In one aspect of the present invention, the polyester polymer composition refers to a composition that is put into a reactor to produce a polyester resin.

In one embodiment of the present invention, the polyester polymer composition comprises a copolymer comprising units derived from the polyoxyalkylene compound (a) represented by the formula (1) and units derived from an acid or an acid derivative (b) And a silica slurry composition comprising silica particles.

More specifically, the polyester polymerizing composition is a composition for producing a homopolymerized polyester or copolymerized polyester which can be produced by esterification or ester exchange reaction of a dicarboxylic acid component and a diol component, for example, a melt polycondensation process Lt; / RTI &gt;

In general, when the polyester resin is polymerized, the inorganic particles may be put in a state of a diol component, more specifically, an inorganic particle slurry dispersed in ethylene glycol or the like. When the silica slurry composition is prepared using the silica as the inorganic particles and then added to the polymerization reaction of the polyester resin, aggregation of the particles occurs and internal defects are increased during the production of the film. Particularly, when the slurry was introduced during the polycondensation reaction at a high temperature, aggregation of the particles occurred more severely.

The inventors of the present invention have found that by including a copolymer containing a unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a unit derived from an acid or an acid derivative (b) It is possible to further improve the acidity and prevent agglomeration of the particles even when the slurry is added during the polycondensation reaction at a high temperature, thereby solving the internal defects due to the re-agglomeration of the silica in the preparation of the master batch chip and the film .

In one aspect of the present invention, the first aspect of the polyester polymerizing composition comprises a monomer composition comprising a diol component and a dicarboxylic acid component; And a silica slurry composition, wherein the silica slurry composition comprises a unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a unit derived from an acid or an acid derivative (b) A copolymer, a diol component, and silica particles.

The second aspect of the polyester polymerizing composition may comprise a prepolymer composition of a monomer composition comprising a diol component and a dicarboxylic acid component, and a silica slurry composition, wherein the silica slurry composition comprises a poly A copolymer comprising a unit derived from an oxyalkylene compound (a) and a unit derived from an acid or an acid derivative (b), a diol component, and silica particles.

The third aspect of the polyester polymerizing composition may further comprise a catalyst, an electrostatic pinning agent and a heat stabilizer in the first or third aspect.

The fourth aspect of the polyester polymerizing composition of the present invention is a method for producing a polyester polymer composition according to any one of the first to third aspects of the present invention, which is a combination of an antistatic agent, an auxiliary flame retardant, a pigment, a dye, a glass fiber, a filler, And may further comprise any one or a mixture of two or more selected.

The above first to fourth aspects are merely illustrative and are not intended to be limiting.

In one embodiment of the present invention, the additives such as the electrostatic pinning agent and the heat stabilizer may be added at the time of polymerization of the polyester resin or may be added at the time of melt molding, but the particles are uniformly dispersed in the film and the terminal carboxyl group content And diethylene glycol, it is preferable to add them at the time of polymerization. When added at the time of polymerization, the addition timing may be added at any time before the transesterification reaction step in the polyester polymerization or after the end of the transesterification reaction, specifically at the initial stage of the polycondensation reaction, for example, up to an intrinsic viscosity of less than 0.3 have. It is preferable that the diol component, more specifically, ethylene glycol, is dissolved or thoroughly mixed to prepare a solution or slurry in order to prevent re-agglomeration or polymerisation. At this time, the concentration of the slurry is preferably, but not limited to, a concentration of the solid content of 3% by weight or less because it can effectively prevent re-aggregation.

In one embodiment of the present invention, the dicarboxylic acid component includes, but is not limited to, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimeric acid, There may be mentioned aliphatic dicarboxylic acids such as hydroxycarboxylic acid, pentaerythritol dicarboxylic acid, pentaerythritol dicarboxylic acid, pentaerythritol dicarboxylic acid, pentaerythritol dicarboxylic acid, pentaerythritol dicarboxylic acid, Alicyclic dicarboxylic acids such as decalin dicarboxylic acid and the like, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, , 1,8-naphthalene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylenedi dicarboxyl Acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, 9,9'-bis (4-carboxyphenyl) fluorene acid And dicarboxylic acid components such as dicarboxylic acid and dicarboxylic acid, and aromatic dicarboxylic acid, but are not limited thereto. These may be used alone or in combination of two or more. More specifically, the dicarboxylic acid component may be terephthalic acid.

In one embodiment of the present invention, the diol component includes but is not limited to ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, -Butanediol, alicyclic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, aliphatic diols such as bisphenol A, bisphenol S, 1,3-benzene dimethanol, 1,4-benzene dimethanol, Diols such as 9'-bis (4-hydroxyphenyl) fluorene and aromatic diols, and those in which a plurality of diols are connected, but the present invention is not limited thereto. These may be used alone or in combination of two or more thereof, if necessary. More specifically, the diol component may be ethylene glycol.

In one embodiment of the present invention, the polyester polymer composition includes a copolymer comprising units derived from a polyoxyalkylene compound (a) represented by the following formula (1) and units derived from an acid or an acid derivative (b) The dispersibility of the silica particles can be improved, the re-aggregation can be prevented, and the slurry can be introduced in the polycondensation step at a high temperature.

[Chemical Formula 1]

R ₁ O (R ₂ O) n R ₃

In Formula 1, R ₁ is a C1-C18 hydrocarbon group,

R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,

Wherein R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,

And n is an average addition mole number of the oxyalkylene group added is 1 to 50.

In one aspect of the invention, wherein R ₁ in Formula 1 may be selected from C1-C18 hydrocarbon group, aryl More specifically, C1-C18 alkyl, C3-C18 cycloalkyl and C6-C18. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, A decyl group, a decyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclohexyl group, a phenyl group, a benzyl group, etc. . More specifically C1-C4 hydrocarbon group, but is not limited thereto.

In one embodiment of the present invention, R ₂ O may be a mixture of at least one member selected from the group consisting of C 1 -C 10 oxyalkylene groups, and when the oxyethylene group is necessarily contained, the diol component, more specifically ethylene It is possible to further improve the dispersibility of the silica particles, to prevent agglomeration, and to prevent re-agglomeration even when added during the polycondensation reaction. In the case of two or more types, the additional form may be random or block form.

In this case, when one or more kinds of oxyalkylene groups other than oxyethylene groups are further contained, the content of oxyethylene groups is higher than that of other oxyalkylene groups, which is the diol component to be added during the preparation of the slurry, The dispersibility and miscibility with respect to the glycol are excellent, and thus the dispersibility of the particles can be further enhanced. More specifically, the content of the oxyethylene group may be 51 mol% or more, more specifically 51 to 99 mol%, and the content of the oxyalkylene group excluding the oxyethylene group may be 1 to 49 mol%.

More specifically, R ₂ O may be a mixture of at least one member selected from oxyalkylene groups of C 2 -C 4. Examples of the C 2 -C 4 oxyalkylene group include oxyethylene group, oxypropylene group, An oxybutylene group, an oxytetramethylene group, and the like.

More specifically, R ₂ O may be an oxyethylene group alone, or a mixture of any one or more selected from an oxyethylene group and an oxyalkylene group having from 3 to 4 carbon atoms.

More specifically, R ₂ O may be an oxyethylene group alone or a mixture of an oxyethylene group and an oxypropylene group, and the content of the oxyethylene group in the mixing may be greater than the content of the oxypropylene group.

In one embodiment of the present invention, R ₃ is selected from the group consisting of hydrogen, a C 2 -C 5 unsaturated hydrocarbon group, an acryloyl group, and a methacryloyl group, and more specifically, a C 2 -C 5 unsaturated hydrocarbon group, And a methacryloyl group.

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

In one embodiment of the present invention, n is 1 to 50, preferably 5 to 45, more preferably 10 to 40, in terms of an average addition mole number of the oxyalkylene group. It is possible to provide a copolymer which can exhibit a viscosity suitable for dispersing silica fine particles within the above range and more specifically satisfy a range of viscosity of 1000 to 20000 cP and more preferably 2000 to 10000 cP. But is not limited to. When the viscosity exceeds 20,000 cP, it is difficult to handle due to the high viscosity, and it may be difficult to expect improvement in the dispersibility of the silica particles. The viscosity may be measured according to a measuring method described later.

In one embodiment 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 may be an acid anhydride, a polyvalent acid obtained from an acid anhydride and a salt thereof, Or a derivative thereof.

More specifically, examples of the acid or acid derivative (b) include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, maleic anhydride, Esters, vinyl acetate, allylsulfonic acid, methallylsulfonic acid, and salts thereof, or a mixture of two or more thereof. More specifically, the acid or acid derivative (b) may be selected from maleic acid, maleic anhydride and salts thereof.

In one embodiment of the present invention, the copolymer may be prepared by copolymerizing 5 to 95 mol% of a polyoxyalkylene compound (a) and 5 to 95 mol% of an acid or an acid derivative (b) no. In addition, the weight average molecular weight of the copolymer may be 500 to 100000, more specifically 1000 to 20000, but is not limited thereto.

In one embodiment of the present invention, the copolymer is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, P- styrenesulfonic acid, , Isoprene, N-phenylmaleimide, N-cyclohexylmaleimide, and units derived from at least one comonomer (c). More specifically, the comonomer may be styrene. The content of the comonomer (c) may be 1 to 50 mol%, though not limited. More specifically, the copolymer is prepared by copolymerizing 1 to 95 mol% of a polyoxyalkylene compound (a), 1 to 95 mol% of an acid or an acid derivative (b) and 1 to 50 mol% of a comonomer (c) But is not limited thereto.

In one embodiment of the present invention, the copolymer may have a viscosity in the range of 1,000 to 20,000 cP, more preferably 1,500 to 10,000 cP, and the dispersibility of the silica particles in the above range is further improved, The compatibility with other components is improved, but the present invention is not limited thereto.

In one embodiment of the present invention, the copolymer may have a saponification value of 10 to 200 mg KOH / g, specifically 60 to 200 mg KOH / g, more particularly 100 to 150 mg KOH / g. The larger the saponification value is, the better the affinity with the particles can be. However, when the saponification value is increased to more than a certain amount, the oxyalkylene structure expected to prevent agglomeration between the particles and the particles is relatively small, have. Therefore, it is preferable because it can prevent the dispersibility and re-agglomeration among particles in the above range, but is not limited thereto.

In one embodiment of the present invention, the copolymer may be contained in an amount of 0.01 to 5% by weight, more specifically 0.1 to 3% by weight based on the content of the particles contained in the polyester polymerization composition. If the copolymer is added in an excessively large amount, it may act as an impurity to lower the color and reaction rate of the master batch chip, and may not exhibit effective dispersing performance when too little amount is added. Therefore, the amount is sufficient to improve the dispersibility of the silica particles in the above range, but is not limited thereto.

In one aspect of the present invention, the polyester polymerizing composition may include inorganic particles, more specifically silica particles, to impart antiblocking properties required in the production of a film. The average particle diameter of the silica particles is not limited, but may be an average particle diameter of 0.01 to 5 占 퐉, more specifically 0.1 to 3 占 퐉. Generally, when the fine particles in the above range are used, re-aggregation of the particles occurs and many internal defects occur. However, the polyester polymer composition of the present invention can improve the dispersibility of the silica particles by including the copolymer Therefore, even when fine particles having the above average particle size are used, it is possible to prevent re-aggregation from occurring. Also, the slurry can be introduced into the polycondensation reaction step at a high temperature at which the aggregation of the 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 in the polyester polymer composition, and the haze and slip property required in the optical film in the above range may be achieved, But is not limited thereto.

In one embodiment of the present invention, the silica slurry composition includes the copolymer and the silica particles, so that the number of aggregated particles having an average particle diameter of 10 탆 or more satisfies the following formula (1).

[Formula 1]

P ₂ < P ₁

In the above formula (1), P ₁ is the number of agglomerated particles having an average particle diameter of 10 탆 or more in the silica slurry composition not containing the copolymer (/ 15 ml), and P ₂ is a silica slurry composition And the number of aggregated particles having an average particle diameter of 10 mu m or more (pieces / 15 ml).

More specifically, the silica slurry composition may have a number of agglomerated particles having an average particle size of 10 탆 or more of 1/15 ml or less, more preferably 0.5 / 15 ml or less.

In one embodiment of the present invention, in the preparation of the silica slurry composition, the order of introduction of the copolymer is not limited. Specifically, for example, it may be a method in which the silica particles are sufficiently dispersed in a diol component, more specifically, ethylene glycol, or the silica particles are sufficiently dispersed in ethylene glycol, and then the copolymer is introduced.

In one aspect of the present invention, the polyester polymerizing composition is selected from the group consisting of a catalyst, an electrostatic pinning agent, a heat stabilizer, an auxiliary flame retardant, a pigment, a dye, a glass fiber, a filler, a heat resisting agent, And may further include any one or a mixture of two or more selected, but is not limited thereto.

In one embodiment of the present invention, the catalyst is not limited as long as it is a catalyst used in polycondensation of polyester, and more preferably, a metal catalyst such as tin or antimony can be used. Specifically, for example, an antimony compound, a tin compound, a titanium compound, and a germanium compound can be used, and they can be used alone or in combination of two or more. The content of the catalyst may be 80 to 400 ppm, more preferably 100 to 300 ppm, of the polyester polymer composition, and is preferably, but not limited to, excellent in reactivity within the above range.

In one embodiment of the present invention, the electrostatic pinning agent is not limited as long as it is ordinarily used, and more preferably, a metal-based peening agent can be used. More specifically, it is preferable to use, for example, an alkali metal compound, an alkaline earth metal compound, a manganese compound, a cobalt compound, a zinc compound or the like because of its 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 and zinc acetate. Can be used. The content of the electrostatic pinning agent may be 10 to 100 ppm, more preferably 10 to 50 ppm, in the polyester polymer composition. In this range, it is possible to solve not only the running property but also the internal defects, But is not limited thereto.

In one embodiment of the present invention, the heat stabilizer is not limited as long as it is conventionally used in the field, but specifically, for example, a phosphorus compound may be used. Specifically, for example, trimethyl phosphate, triethyl phosphate, phosphoric acid and the like can be used. The phosphorus compound can impart a peening effect to the thermal stability effect. The content of the heat stabilizer may be 10 to 150 ppm, more preferably 10 to 100 ppm, in the polyester polymerization composition, and is preferable because it is sufficient to achieve the thermal stability and peening-improving effect in the range It is not.

(Polyester resin master batch chip and its manufacturing method)

In one embodiment of the present invention, the polyester resin master batch chip means a polyester resin chip comprising inorganic particles, specifically silica particles. It is usually added during the polymerization of the polyester resin by adding inorganic particles during the production of the film, or may be added when the resin is melt-extruded. When the polyester resin is added during polymerization, the dispersibility of the inorganic particles is further improved . The present invention may further improve the dispersibility of the silica particles by adding the silica slurry composition containing the copolymer during polymerization.

In one aspect of the present invention, the polyester resin master batch chip may be one produced by polymerizing the polyester polymerization composition as described above. More specifically, it may be one comprising an ester exchange reaction step and a polycondensation reaction step. Further, it may be prepared by further comprising a solid phase polymerization step after the polycondensation reaction step.

In one embodiment of the present invention, the order of introduction of the silica slurry composition is not limited, and may be that before the transesterification step or before the polycondensation reaction step. The present invention is characterized in that the dispersibility of the particles in the silica slurry composition is very excellent by the inclusion of the above-mentioned copolymer, and it is possible to prevent re-aggregation from occurring and to be able to be introduced even at a high temperature reaction stage as in a polycondensation reaction, The re-agglomeration of the particles hardly occurs even when the particles are introduced in the reaction step.

The first aspect of producing the polyester resin master batch chip of the present invention comprises:

Mixing a dicarboxylic acid or an ester derivative thereof with a diol component and proceeding an ester reaction to prepare a prepolymer; And

Adding a catalyst, an electrostatic pinning agent, a heat stabilizer and a silica slurry composition to the preliminary polymerizate to perform a polycondensation reaction;

. &Lt; / RTI &gt;

The second aspect of producing the polyester resin master batch chip of the present invention is that,

Mixing a dicarboxylic acid or an ester derivative thereof with a diol component and proceeding an ester reaction to prepare a prepolymer;

Adding a catalyst, an electrostatic pinning agent, a heat stabilizer and a silica slurry composition to the preliminary polymerizate to perform a polycondensation reaction; And

Performing solid phase polymerization;

. &Lt; / RTI &gt;

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

The preparation of the prepolymer is not limited but may be performed at 170 to 270 ° C and may be carried out while water produced under pressure of 760 to 1500 torr is discharged out of the reactor. The reaction time may be 1 to 10 hours, though not limited.

In one embodiment of the present invention, the polycondensation reaction may be carried out at 250 to 290 캜, but not limited thereto, and may be carried out under a reduced pressure of 1 torr or less. The reaction time may be 1 to 10 hours, though not limited.

In one embodiment of the present invention, the produced polyester resin master batch chip may have an intrinsic viscosity of 0.6 to 0.9 dL / g, and is preferably, but not exclusively, excellent in film-forming stability in the production of the film within the above range.

In an embodiment of the present invention, the number of agglomerated particles contained in the polyester resin master batch chip having an average particle diameter of 10 mu m or more may be smaller than that in the case where the copolymer does not include the copolymer. More specifically, the number of agglomerated particles having an average particle diameter of not less than 10 mu m in the area of 448 mu m x 336 mu m may be 6 or less, but is not limited thereto.

(Polyester film and manufacturing method thereof)

One aspect of the present invention is a method for producing a polyester resin masterbatch comprising the steps of using a polyester resin master batch chip containing the silica particles alone or mixing a polyester resin master batch chip containing the silica particles and a polyester resin chip containing no inorganic particles To produce a film.

More specifically, the content of the polyester resin master batch chip may be such that the content of the silica particles is 0.001 to 3% by weight in the final film, and a film having excellent permeability and excellent slip property and running property is provided in the range But is not limited thereto.

In one aspect of the present invention, the polyester film may be produced by a conventional method. More specifically, a polyester resin master batch chip containing the silica particles and a polyester resin chip not containing an inorganic particle are mixed and melt-extruded in an extruder to prepare an unstretched sheet, and the unstretched sheet is stretched to form a film . &Lt; / RTI &gt; Further, the method may further include a step of heat fixation and relaxation after the stretching.

In one embodiment of the present invention, the polyester film comprises a polyester resin master batch chip comprising the silica particles or a polyester resin master batch chip including the silica particles, and a polyester resin chip not containing the inorganic particles Extruding the core layer and at least one skin layer on one or both sides of the core layer to form a multilayer film by using a polyester resin chip not containing inorganic particles as a skin layer, have. More specifically, it may be a method of producing an unoriented sheet by co-extrusion to stretch the unstretched sheet to produce a film. Further, the method may further include a step of heat fixation and relaxation after the stretching.

In one embodiment of the present invention, the stretching may be uniaxial or biaxial stretching, and the biaxial stretching may be a multi-step stretching in which the stretching is performed in the machine direction and a width direction after the stretching, or a simultaneous stretching &Lt; / RTI &gt; Although the stretching ratio is not limited, it may be 1.1 to 10 times, more specifically 2 to 5 times in the machine direction, 1.1 to 10 times in the width direction, more specifically 4 to 6 times. The thermal dimensional stability of the polymer structure in the stretching ratio is further increased to reduce heat shrinkage, which is preferable, but is not limited thereto.

In one embodiment of the present invention, the polyester film may be heat-treated at 200 to 250 ° C and 1 to 10% relaxed after biaxial stretching. Specifically, it may be one which imparts relaxation simultaneously with the heat treatment, more specifically, 1 to 10%, more specifically, 2 to 4% relaxation in the width direction. In the above range, the film is maintained in a state of being tensed in the width direction, thereby increasing the compactness of the polymer structure and reducing the deformation due to heat, but is not limited thereto.

In one aspect of the present invention, the polyester film may have a thickness of 10 to 300 占 퐉, more specifically, 15 to 200 占 퐉, but is not limited thereto.

In one embodiment of the present invention, the polyester film may be smaller than the case where the number of aggregated particles having an average particle diameter of 10 mu m or more does not include the copolymer. Specifically, the number of agglomerated particles having an average particle diameter of not less than 10 mu m in the area of 448 mu m x 336 mu m is not more than 45/10 mu m, more specifically not more than 40 mu mu / 10 mu m, but is not limited thereto.

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 measured by the following measurement methods.

1) Number of agglomerated particles in the slurry

The number of coarse particles of 10 mu m or more in the silica slurry composition was measured using a Coulter Counter (Multisizer 4e manufactured by Beckman). The measurements were repeated three times and the mean values were calculated.

The measurement conditions are as follows.

Electrolyte solution: ISOTON (0.9% NaCl aqueous solution)

Aperture Tube Size: 100㎛

Measuring Range: 2 ~ 60㎛

Sample injection amount in electrolyte: 15 μl

Measured amount / 1 time: Measured amount / 1 time

2) Number of agglomerated particles in master batch chip

A polyester resin master batch chip made in the form of a pellet was melted on a slide glass to prepare a sample having a thickness of 40 mu m and a coagulated particle was formed at a magnification of 200 times using a DIC (Differential Interference Contrast) microscope To measure the number of agglomerated particles having a size of 10 mu m or larger in the area of 448 mu m x 336 mu m. The number of defects in a total of 5 microscope photographs was averaged. Defect size can also be measured using a microscope scale bar and measured based on the major axis of the defect.

3) Number of agglomerated particles in film

An area of 10 m 2 of the prepared film was polarized using a polarizing mirror (Heidon, Type 25W), and the sample was observed while observing the polarizing plate. The shape of the internal defect was observed with a microscope (Leica DM2700M) at a magnification of 500 and the number of foreign particles was measured after sorting the foreign particles having the shape of aggregated particles.

4) Intrinsic viscosity measurement

0.4 g of PET pellet (sample) was added to 100 ml of os chlorophenol reagent and dissolved for 100 minutes. The solution was transferred to a Ubbelohde viscometer and kept in a 30 ° C thermostat for 10 minutes. Using a viscometer and an aspirator To obtain the falling seconds of the solution. The number of drops of the solvent was also determined by the same method, and then the RV value and I.V. Values were calculated.

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

5) Ethylene glycol affinity

1 g of the copolymer shown in Table 1 was added to 100 ml of ethylene glycol, stirred for 10 minutes, and the state of the solution was visually confirmed.

Good: solution is transparent and thoroughly mixed after stirring for 10 minutes

Normal: After stirring for 10 minutes, it becomes cloudy and becomes clear after stirring for 1 hour.

Defective: After 10 minutes stirring, layer separation occurred without mixing

6) Saponification value

ASTM D5558-95.

7) Viscosity

After the sample was prepared at 25 캜, a 64-spindle was mounted on a Brookfield viscometer (DV1MRVTJO), and the viscosity was measured at 50 rpm.

The physical properties of the copolymer used in the following Production Examples are as follows.

Viscosity
(cP) Saponification value
(mg KOH / g) Ethylene glycol affinity Acid or acid derivative
(b) Comonomer
(c) Formula 1
(a) R ₁ R ₂ O R ₃ n Copolymer
(One) 2000 132 Good Maleic anhydride - methyl EO Ally 11 Copolymer
(2) 10000 138 Good Maleic anhydride Styrene methyl EO Ally 32 Copolymer
(3) 2000 58.6 Bad Maleic anhydride - methyl EO / PO
50:50 mole ratio Ally 11 Copolymer
(4) 6000 56.3 Bad Maleic anhydride Styrene ethyl EO / PO
40:60 mole ratio Ally 28 Copolymer
(5) 2000 135 Good Maleic anhydride - methyl EO / PO
70:30 mole ratio Ally 13

In Table 1, EO is oxyethylene and PO is oxypropylene. EO / PO is a random addition form of oxyethylene and oxypropylene.

[Example 1]

1) Preparation of silica slurry composition

7% by weight of silica particles having an average particle diameter of 1.9 [micro] m were added to 99.23% by weight of ethylene glycol, 0.07% by weight (1% by weight based on the particle content) of the copolymer (1) And the mixture was stirred at 3500 rpm for 6 hours to prepare a silica slurry composition (1). The number of aggregated particles in the prepared slurry was measured and shown in Table 2 below.

2) Preparation of polyethylene terephthalate resin master batch chip

To 100 parts by weight of terephthalic acid, 50 parts by weight of ethylene glycol was added to the esterification reactor, and the mixture was pressurized at 250 DEG C for 4 hours under a pressure of 1100 torr to distill water out of the reactor, thereby carrying out an esterification reaction to obtain a prepolymer BHET -hydroxyethyl terephthalate). Water 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.

150 ppm of magnesium acetate as an electrostatic pinning agent and 72 ppm of trimethyl phosphate as a heat stabilizer were mixed and introduced into the prepared BHET on the basis of 100 parts by weight of the resin composition so that 200 ppm of antimony trioxide and 7,000 ppm of particles in the master batch chip After the addition of the silica slurry composition (1), the temperature was gradually raised from 250 ° C to 285 ° C at 60 ° C / hr, and the polycondensation reaction was carried out under high vacuum of 0.3 torr for 4 hours to obtain an intrinsic viscosity (IV) of 0.615 Of a polyethylene terephthalate resin master batch chip (1).

The number of aggregated particles in the prepared polyethylene terephthalate resin master batch chip was measured and shown in Table 3 below.

3) Preparation of polyethylene terephthalate film

42.5% by weight of the polyethylene terephthalate resin master batch chip (1) and 57.5% by weight of a polyethylene terephthalate resin chip containing no particles were blended and melt extruded through an extruder to prepare a sheet. The prepared sheet was stretched 3.4 times in the machine direction and 4.0 times in the transverse direction at 95 占 폚 and heat-treated at 230 占 폚 to prepare a biaxially oriented film having a thickness of 38 占 퐉.

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

[Example 2]

1) Preparation of silica slurry composition

A silica slurry composition (2) was prepared in the same manner as in Example 1, except that the copolymer (2) in Table 1 was used instead of the copolymer (1). The number of aggregated particles in the prepared slurry was measured and shown in Table 2 below.

2) Preparation of polyethylene terephthalate resin master batch chip

A polyethylene terephthalate resin master batch chip (2) was prepared in the same manner as in Example 1, except that the above silica slurry composition (2) was used.

The number of aggregated particles in the prepared polyethylene terephthalate resin master batch chip was measured and shown in Table 3 below.

3) Preparation of polyethylene terephthalate film

A film was prepared in the same manner as in Example 1, except that the polyethylene terephthalate resin master batch chip (2) was used.

The number of agglomerated particles in the prepared 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 that the composition was changed as shown in Table 2 below. The number of aggregated particles in the prepared slurry was measured and shown in Table 2 below.

2) Preparation of polyethylene terephthalate resin master batch chip

A polyethylene terephthalate resin master batch chip was prepared in the same manner as in Example 1, except that the silica slurry composition was changed in place of the silica slurry composition (1) in Example 1 as shown in Table 3 below.

The number of aggregated particles in the prepared polyethylene terephthalate resin master batch chip was measured and shown in Table 3 below.

3) Preparation of polyethylene terephthalate film

A film was prepared in the same manner as in Example 1, except that the polyethylene terephthalate resin master batch chip was changed to the one prepared in each example in Example 1.

The number of agglomerated particles in the prepared 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 that the composition was changed as shown in Table 2 below. The number of aggregated particles in the prepared slurry was measured and shown in Table 2 below.

2) Preparation of polyethylene terephthalate resin master batch chip

A polyethylene terephthalate resin master batch chip was prepared in the same manner as in Example 1, except that the silica slurry composition was changed in place of the silica slurry composition (1) in Example 1 as shown in Table 2 below.

The number of aggregated particles in the prepared polyethylene terephthalate resin master batch chip was measured and shown in Table 3 below.

3) Preparation of polyethylene terephthalate film

A film was prepared in the same manner as in Example 1, except that the polyethylene terephthalate resin master batch chip was changed to the one prepared in each example in Example 1.

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

Copolymer Slurry particle
Average particle diameter Particle content (% by weight) in the slurry Copolymer input concentration
(% By weight relative to the particles) Particle input amount in master batch chip
(ppm) Number of agglomerated particles in slurry
(ea / 15 ml, > 10 mu m) Example 1 Copolymer (1) (One) 1.9 탆 7 One 7000 0.3 Example 2 Copolymer (2) (2) 1.9 탆 7 One 7000 0.3 Example 3 Copolymer (1) (3) 1.9 탆 7 2 7000 0.3 Example 4 Copolymer (1) (4) 1.9 탆 7 5 7000 0.4 Example 5 Copolymer (1) (5) 0.6 탆 2.5 2 2000 0 Example 6 Copolymer (2) (6) 0.6 탆 2.5 2 2000 0.6 Example 7 Copolymer (5) (7) 1.9 탆 7 One 7000 0.5 Comparative Example 1 No entry (8) 1.9 탆 7 0 7000 1.3 Comparative Example 2 The copolymer (3) (9) 1.9 탆 7 One 7000 2 Comparative Example 3 Copolymer (4) (10) 1.9 탆 7 One 7000 2.3 Comparative Example 4 No entry (11) 0.6 탆 2.5 0 2000 1.5

Slurry Master batch chip film Intrinsic viscosity
(dL / g) Particle content
(ppm) Number of agglomerated particles
(Number / 0.15 mm 2) Particle content
(ppm) thickness
(탆) Number of agglomerated particles
(Pieces / 10㎡) color
(b *) Example 1 (One) 0.615 7000 0.4 850 38 14 1.5 Example 2 (2) 0.615 7000 4.2 850 38 32 1.6 Example 3 (3) 0.615 7000 0.2 850 38 12 1.7 Example 4 (4) 0.615 7000 2.5 850 38 20 2.2 Example 5 (5) 0.615 2000 3.2 850 38 18 2.0 Example 6 (6) 0.615 2000 3.5 850 38 28 1.9 Example 7 (7) 0.615 7000 2.3 850 38 22 2.2 Comparative Example 1 (8) 0.615 7000 6.2 850 38 48 1.5 Comparative Example 2 (9) 0.615 7000 7 850 38 62 1.5 Comparative Example 3 (10) 0.615 7000 7.4 850 38 70 1.6 Comparative Example 4 (11) 0.615 2000 9.4 850 38 72 1.8

As shown in Tables 2 and 3, it was confirmed that the number of agglomerated particles in Examples 1 and 2 was remarkably reduced as compared with Comparative Example 1 using a silica slurry composition to which no copolymer was added. Also, it was confirmed that the slurry of the present invention is excellent in dispersibility of particles even when added in a polycondensation reaction at a high temperature.

In the case of Comparative Example 2 and Comparative Example 3, it was confirmed that the number of agglomerated particles was rather increased as compared with Comparative Example 1 in which a copolymer was not used by using a copolymer having affinity with ethylene glycol and affinity with particles .

Claims (19)

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 above-mentioned silica slurry composition comprises a copolymer, a diol component and a silica particle comprising a unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a unit derived from an acid or an acid derivative Lt; / RTI &gt;
[Chemical Formula 1]
R ₁ O (R ₂ O) n R ₃
In Formula 1, R ₁ is a C1-C18 hydrocarbon group,
R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,
Wherein R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,
And n is an average addition mole number of the oxyalkylene group added is 1 to 50. The method according to claim 1,
In the formula (1), R ₁ is a C ₁ -C 4 hydrocarbon group,
Wherein R ₂ O is an oxyethylene group alone or a mixture of an oxyethylene group and an oxypropylene group, the content of the oxyethylene group in the mixing is larger than the content of the oxypropylene group,
R ₃ is selected from the group consisting of an unsaturated hydrocarbon group of C3-C4, an acryloyl group and a methacryloyl group,
And n is an average addition mole number of oxyalkylene groups in the range of 10 to 40. The method according to claim 1,
The acid or acid derivative (b) may be at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, maleic anhydride, allyl sulfonic acid, maleic acid alkyl ester, , Methallylsulfonic acid, and salts thereof. &Lt; RTI ID = 0.0 &gt; (1) &lt; / RTI &gt; The method according to claim 1,
The copolymer may be selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, P-styrenesulfonic acid, indene, isobutylene, A monomer derived from at least one comonomer (c) selected from N-cyclohexylmaleimide, and a unit derived from at least one comonomer (c) selected from N-cyclohexylmaleimide. The method according to claim 1,
Wherein the copolymer has a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g. The method according to claim 1,
Wherein the silica particles have an average particle diameter of 0.01 to 5 占 퐉. The method according to claim 1,
Wherein the silica particles are contained in an amount of 0.001 to 3 wt% of the polyester polymer composition. The method according to claim 1,
Wherein the copolymer is contained in an amount of 0.01 to 5% by weight based on the content of particles contained in the polyester polymerization composition. The method according to claim 1,
Wherein the number of aggregated particles having an average particle diameter of 10 mu m or more satisfies the following formula (1).
[Formula 1]
P ₂ < P ₁
In the above formula (1), P ₁ is the number of agglomerated particles having an average particle diameter of 10 탆 or more in the silica slurry composition not containing the copolymer (/ 15 ml), and P ₂ is a silica slurry composition And the number of aggregated particles having an average particle diameter of 10 mu m or more (pieces / 15 ml). 10. The method of claim 9,
Wherein said silica slurry composition has a number of agglomerated particles having an average particle diameter of 10 mu m or more of 1/15 ml or less. The method according to claim 1,
Wherein the polyester polymerizing composition further comprises any one or a mixture of two or more selected from the group consisting of a catalyst, an electrostatic pinning agent and a heat stabilizer. A polyester resin master batch chip produced by polymerizing a polyester polymerizing composition of any one of claims 1 to 11. 13. The method of claim 12,
Wherein the polyester resin master batch chip has a number of agglomerated particles having an average particle diameter of 10 mu m or more in a 448 mu m x 336 mu m area of 6 or less. A polyester film produced by melt extrusion and stretching of a resin composition comprising the polyester resin master batch chip of claim 12. 15. The method of claim 14,
Wherein the polyester film has a thickness of 10 to 300 탆. A silica slurry composition comprising a unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a unit derived from an acid or an acid derivative (b), a diol component and silica particles is esterified Adding to the reaction step or the polycondensation reaction step and polymerizing the polyester resin master batch chip.
[Chemical Formula 1]
R ₁ O (R ₂ O) n R ₃
In Formula 1, R ₁ is a C1-C18 hydrocarbon group,
R ₂ O is a mixture of at least one member selected from the group consisting of C1-C10 oxyalkylene groups and contains an oxyethylene group,
R ₃ is selected from the group consisting of hydrogen, a C 2 -C 5 unsaturated hydrocarbon group, an acryloyl group, and a methacryloyl group,
And n is an average addition mole number of the oxyalkylene group added is 1 to 50. 17. The method of claim 16,
The copolymer may be selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, P-styrenesulfonic acid, indene, isobutylene, (C) a unit derived from at least one comonomer (c) selected from the group consisting of N, N-dimethylacetamide, N, N-cyclohexylmaleimide. 17. The method of claim 16,
Wherein the copolymer has a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g. 17. The method of claim 16,
Wherein the silica slurry composition is introduced before the polycondensation reaction.