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WO2019066448A1 - Composition de polymère polyester, puce à base d'un mélange maître de résine polyester et film polyester l'utilisant - Google Patents

Composition de polymère polyester, puce à base d'un mélange maître de résine polyester et film polyester l'utilisant Download PDF

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Publication number
WO2019066448A1
WO2019066448A1 PCT/KR2018/011353 KR2018011353W WO2019066448A1 WO 2019066448 A1 WO2019066448 A1 WO 2019066448A1 KR 2018011353 W KR2018011353 W KR 2018011353W WO 2019066448 A1 WO2019066448 A1 WO 2019066448A1
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WO
WIPO (PCT)
Prior art keywords
group
acid
polyester
particles
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/011353
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English (en)
Korean (ko)
Inventor
임수진
김정순
박지용
황영남
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Kolon Industries Inc
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Kolon Industries Inc
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Publication date
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Priority to JP2020512660A priority Critical patent/JP7113074B2/ja
Priority to CN201880051232.6A priority patent/CN111032781B/zh
Publication of WO2019066448A1 publication Critical patent/WO2019066448A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • 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.
  • polyester especially polyethylene terephthalate (hereinafter referred to as PET)
  • PET polyethylene terephthalate
  • the use and the amount of use thereof are continuously expanding at a lower price than other high-functional resins.
  • 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.
  • the market is expanding.
  • 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.
  • 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 ⁇ ⁇ and specifically decreasing the number of defects during film production, It is an object of the present invention to provide ester polymerization compositions.
  • 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 silica slurry composition comprises a copolymer, a diol component and a silica particle comprising a polymerization unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a polymerization unit derived from an acid or an acid derivative (b) Based on the total weight of the composition.
  • 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 an oxyalkylene group having 1 to 10 carbon atoms and contains an oxyethylene group, and when the oxyethylene group is combined with the oxyalkylene group having 1 to 3 carbon atoms, an oxyethylene group Is more than the content of C1 and the oxyalkylene group of C3-C10,
  • R 3 is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,
  • n is an integer of 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 is a copolymer comprising a polymerization unit derived from the polyoxyalkylene compound (a) represented by the above formula (1) and a polymerization 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.
  • 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.
  • 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 silica slurry composition comprises a copolymer, a diol component and a silica particle comprising a polymerization unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a polymerization unit derived from an acid or an acid derivative (b) Based on the total weight of the composition.
  • 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 an oxyalkylene group having 1 to 10 carbon atoms and contains an oxyethylene group, and when the oxyethylene group is combined with the oxyalkylene group having 1 to 3 carbon atoms, an oxyethylene group Is more than the content of C1 and the oxyalkylene group of C3-C10,
  • R 3 is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,
  • n is an integer of 1 to 50.
  • the R 2 O may be an oxyethylene group alone, or a mixture of an oxyethylene group and an oxypropylene group.
  • the content of the oxyethylene group in the mixing may be greater 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,
  • the n may be an integer of 10 to 40, preferably.
  • 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.
  • 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, , Polymerized units derived from any one or two or more comonomers (c) selected from isoprene, N-phenylmaleimide and N-cyclohexylmaleimide.
  • the copolymer may have a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g.
  • the silica particles may have an average particle diameter of 0.01 to 5 mu m.
  • the silica particles may be contained in an amount of 0.001 to 3% by weight in the polyester polymerization composition.
  • 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.
  • 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).
  • P 1 is the number of agglomerated particles having an average particle diameter of 10 ⁇ or more in the silica slurry composition not containing the copolymer (parts / 15 ml)
  • 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 ⁇ ⁇ or more (pieces / 15 ml).
  • 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.
  • 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.
  • 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.
  • the polyester film may have a thickness of 10 to 300 mu m.
  • a silica slurry composition comprising a copolymer, a diol component and silica particles, which comprises a polymerization unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a polymerization unit derived from an acid or an acid derivative (b) An esterification reaction step or a polycondensation reaction step, followed by polymerization, to obtain a polyester resin master batch chip.
  • 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 an oxyalkylene group having 1 to 10 carbon atoms and contains an oxyethylene group, and when the oxyethylene group is combined with the oxyalkylene group having 1 to 3 carbon atoms, an oxyethylene group Is more than the content of C1 and the oxyalkylene group of C3-C10,
  • R 3 is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,
  • n is an integer of 1 to 50.
  • 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, , Polymerized units derived from any one or two or more comonomers (c) selected from isoprene, N-phenylmaleimide and N-cyclohexylmaleimide.
  • the copolymer may have a viscosity of 1000 to 20,000 cP and a saponification value of 10 to 200 mg KOH / g.
  • the silica slurry composition may be added prior to the polycondensation reaction.
  • the polyester polymer composition refers to a composition that is put into a reactor to produce a polyester resin.
  • the polyester polymer composition includes a copolymer comprising a polymerization unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a polymerization unit derived from an acid or an acid derivative (b) , A diol component, and silica particles.
  • 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 >
  • the inorganic particles 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.
  • a diol component more specifically, an inorganic particle slurry dispersed in ethylene glycol or the like.
  • 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.
  • 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 comprising a polymerization unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a polymerization unit derived from an acid or an acid derivative (b) And it is possible to prevent agglomeration of the particles even when the slurry is added during the polycondensation reaction at a high temperature. As a result, it is possible to prevent internal aggregation Can be solved.
  • 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 contains a polymerization unit derived from the polyoxyalkylene compound (a) represented by the formula (1) and a polymerization unit derived from an acid or an acid derivative (b) 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 polymerization unit derived from an oxyalkylene compound (a) and a polymerization 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 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.
  • 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.
  • the diol component more specifically, ethylene glycol
  • 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.
  • 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,
  • aliphatic dicarboxylic acids such as hydroxycarboxylic acid, pentaerythritol dicarboxylic acid, pentaerythritol dicarboxylic 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 di
  • 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.
  • the polyester polymer composition comprises a copolymer comprising a polymerization unit derived from a polyoxyalkylene compound (a) represented by the following formula (1) and a polymerization unit derived from an acid or an acid derivative (b) It is possible to improve the dispersibility of the silica particles, to prevent re-aggregation, and to enable the slurry to be introduced in the polycondensation step at a high temperature.
  • 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 an oxyalkylene group having 1 to 10 carbon atoms and contains an oxyethylene group, and when the oxyethylene group is combined with the oxyalkylene group having 1 to 3 carbon atoms, an oxyethylene group Is more than the content of C1 and the oxyalkylene group of C3-C10,
  • R 3 is selected from the group consisting of an unsaturated hydrocarbon group of C2-C5, an acryloyl group and a methacryloyl group,
  • n is an integer of 1 to 50.
  • 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
  • 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.
  • the additional form may be random or block form.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. The viscosity is good in handling within the above range, and the dispersibility of the silica particles can be further improved. The viscosity may be measured according to a measuring method described later.
  • the acid in the acid or the acid derivative (b), the acid may be a carboxylic acid or a salt thereof, and the acid derivative may be a polyvalent acid obtained from an acid anhydride, an acid anhydride, or a salt thereof.
  • 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.
  • 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.
  • the weight average molecular weight of the copolymer may be 500 to 100000, more specifically 1000 to 20000, but is not limited thereto.
  • 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, (C) selected from isoprene, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. More specifically, the comonomer may be styrene. The content of the comonomer (c) may be 1 to 50 mol%, though not limited.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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 ⁇ ⁇ , more specifically 0.1 to 3 ⁇ ⁇ .
  • 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.
  • 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.
  • 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 ⁇ or more satisfies the following formula (1).
  • P 1 is the number of agglomerated particles having an average particle diameter of 10 ⁇ 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).
  • the silica slurry composition may have a number of agglomerated particles having an average particle size of 10 ⁇ or more of 1/15 ml or less, more preferably 0.5 / 15 ml or less.
  • 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.
  • 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.
  • 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.
  • a metal catalyst such as tin or antimony
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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:
  • the second aspect of producing the polyester resin master batch chip of the present invention is that,
  • the prepolymer may be a low molecular weight material (low molecular weight oligomer), more specifically BHET (bis-beta-hydroxyethyl terephthalate).
  • low molecular weight oligomer low molecular weight oligomer
  • 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.
  • the polycondensation reaction may be carried out at 250 to 290 ⁇ , 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 . ≪ / RTI > Further, the method may further include a step of heat fixation and relaxation after the stretching.
  • 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.
  • the stretching may be uniaxial or biaxial stretching.
  • 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 ≪ / RTI >
  • 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.
  • 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.
  • the polyester film may have a thickness of 10 to 300 ⁇ ⁇ , more specifically, 15 to 200 ⁇ ⁇ , but is not limited thereto.
  • 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.
  • the number of agglomerated particles having an average particle diameter of 10 mu m or more in the area of 448 mu m x 336 mu m may be 45/10 or less, more specifically 40/10 m < 2 >
  • 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 ⁇ m
  • Measured amount / 1 time Measured amount / 1 time
  • 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.
  • 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.
  • 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.
  • the color of the film was confirmed using a color meter.
  • the film color was compared with the film thickness of b * using Konica Minolta (CM-512m3) equipment.
  • EO is oxyethylene and PO is oxypropylene.
  • EO / PO is a random addition form of oxyethylene and oxypropylene.
  • the styrene was used in an amount of 2 mol%.
  • 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.
  • terephthalic acid 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.
  • the number of aggregated particles in the prepared polyethylene terephthalate resin master batch chip was measured and shown in Table 3 below.
  • the number of agglomerated particles in the prepared film was measured and shown in Table 3 below.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 Average particle diameter Particle content (% by weight) in the slurry Copolymer input concentration (% by weight relative to the particles) Particle input amount (ppm) in master batch chip The number of aggregated particles in the slurry (ea / 15 ml, > 10 mu m)
  • Example 1 Copolymer (1) (One) 1.9 ⁇ 7 One 7000 0.3 Example 2 Copolymer (2) (2) 1.9 ⁇ 7 One 7000 0.3 Example 3 Copolymer (1) (3) 1.9 ⁇ 7 2 7000 0.3 Example 4 Copolymer (1) (4) 1.9 ⁇ 7 5 7000 0.4 Example 5 Copolymer (1) (5) 0.6 ⁇ 2.5 2 2000 0 Example 6 Copolymer (2) (6) 0.6 ⁇ 2.5 2 2000 0.6 Example 7 Copolymer (5) (7) 1.9 ⁇ 7 One 7000 0.5 Comparative Example 1 No entry (8) 1.9 ⁇ 7 0 7000 1.3 Comparative Example 2 The copolymer (3) (9) 1.9 ⁇ 7 One 7000 2 Comparative Example 3 Cop
  • Example 1 Slurry Master batch chip film Intrinsic viscosity (dL / g) Particle content (ppm) Number of aggregated particles (pieces / 0.15 mm 2) Particle content (ppm) Thickness ( ⁇ m) Number of aggregated particles (pieces / 10m2) 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
  • 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.
  • 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 .

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne : une composition de polymère polyester ayant une aptitude à la dispersion améliorée des particules de silice, en particulier, des matières particulaires de silice et comportant une quantité réduite de particules agglomérées ; une puce à base d'un mélange maître de résine polyester ; et un film polyester l'utilisant.
PCT/KR2018/011353 2017-09-29 2018-09-27 Composition de polymère polyester, puce à base d'un mélange maître de résine polyester et film polyester l'utilisant Ceased WO2019066448A1 (fr)

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CN201880051232.6A CN111032781B (zh) 2017-09-29 2018-09-27 聚酯聚合组合物，聚酯树脂母料片及使用该聚酯树脂母料片的聚酯膜

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EP4019572A1 (fr) * 2020-12-22 2022-06-29 Nan Ya Plastics Corporation Film de polyester à orientation biaxiale et son procédé de fabrication
WO2023014333A1 (fr) * 2021-08-03 2023-02-09 T.C. Erci̇yes Üni̇versi̇tesi̇ Bouteille en pet à base de silice et procédé de production

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WO2023014333A1 (fr) * 2021-08-03 2023-02-09 T.C. Erci̇yes Üni̇versi̇tesi̇ Bouteille en pet à base de silice et procédé de production

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KR102258625B1 (ko) 2021-05-28
CN111032781B (zh) 2022-03-22

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