WO2006048927A1 - Copolyester, procédé de production dudit copolyester, et film polyester - Google Patents

Copolyester, procédé de production dudit copolyester, et film polyester Download PDF

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Publication number
WO2006048927A1
WO2006048927A1 PCT/JP2004/016295 JP2004016295W WO2006048927A1 WO 2006048927 A1 WO2006048927 A1 WO 2006048927A1 JP 2004016295 W JP2004016295 W JP 2004016295W WO 2006048927 A1 WO2006048927 A1 WO 2006048927A1
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WIPO (PCT)
Prior art keywords
acid
polyester
fatty acid
copolyester
residue
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PCT/JP2004/016295
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English (en)
Japanese (ja)
Inventor
Takeshi Kanzawa
Taisei Matsumoto
Masahiro Kimura
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Toray Industries, Inc.
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Publication date
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Priority to PCT/JP2004/016295 priority Critical patent/WO2006048927A1/fr
Priority to KR1020077010164A priority patent/KR101153909B1/ko
Priority to JP2006542198A priority patent/JPWO2006048927A1/ja
Priority to CN2004800447471A priority patent/CN101090921B/zh
Publication of WO2006048927A1 publication Critical patent/WO2006048927A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/88—Post-polymerisation treatment
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • Copolyester method for producing the same, and polyester film
  • the present invention relates to a copolymerized polyester and a flexible polyester film that can form a flexible molded product, and more specifically, industrial materials and packaging that require transparency, easy moldability, and heat resistance.
  • the present invention relates to a polyester film suitable for materials and the like, and a copolymer polyester as a raw material thereof.
  • a polychlorinated bulule film is representative.
  • This polyvinyl chloride film is excellent in weather resistance, suitable for various processing, such as embossing strength, and has the advantage of being available at low cost, so it is preferably used as a flexible film. It has been.
  • the polyvinyl chloride-based film has a problem that a toxic gas is generated when the film burns due to a fire or the like, and a problem that the plasticizer easily bleeds out. For this reason, new and flexible films made of other resins have been demanded in recent years due to the need for environmental aspects.
  • an elastic film made of a resin obtained by copolymerizing polybutylene terephthalate with a long-chain polyether such as polytetramethylene glycol see, for example, Patent Document 1
  • dimer of unsaturated fatty acid with polyethylene terephthalate A long chain aliphatic dicarboxylic acid, which is a dimer of unsaturated fatty acid, and polybutylene terephthalate.
  • An elastic resin for molded products for example, see Patent Document 3
  • a copolymer of polybutylene terephthalate and polyethylene terephthalate are copolymerized with a long-chain aliphatic dicarboxylic acid that is a dimer of unsaturated fatty acids.
  • a flexible film made of coconut oil for example, see Patent Document 4-5) Yes.
  • a long-chain aliphatic dicarboxylic acid in a predetermined ratio is polymerized in a polymerization step.
  • a method for obtaining a polyester resin resin composition containing a long-chain aliphatic dicarboxylic acid as a copolymerization component in a predetermined ratio a long-chain aliphatic dicarboxylic acid in a predetermined ratio is polymerized in a polymerization step.
  • a method in which a long-chain aliphatic dicarboxylic acid copolymer polyester and an aromatic polyester are melt-mixed at a certain ratio and copolymerized (for example, Patent Document 6-7). reference).
  • an elastic film made of a resin obtained by copolymerizing a long-chain polyether with polybutylene terephthalate has good weather resistance, heat resistance, transparency, etc., although it has good flexibility and blocking resistance. Since it is inferior, it is difficult to satisfy the characteristics required for a film for replacing a polyvinyl chloride film.
  • coffin resin obtained by copolymerizing polyethylene terephthalate or polybutylene terephthalate with a long-chain aliphatic dicarboxylic acid has good characteristics as a copolyester for elastic yarns and films.
  • coffin resin obtained by copolymerizing a polybutylene terephthalate-based polyester with a long-chain aliphatic dicarboxylic acid has the advantage that it can be easily formed into fibers, films, sheets, and other molded products because of its high crystallinity.
  • Patent Documents 3 to 7 various copolymer compositions and copolymerization methods have been proposed.
  • Patent Document 1 Japanese Patent Publication No. 57-48577
  • Patent Document 2 Japanese Patent Publication No.42-8709
  • Patent Document 3 Japanese Patent Publication No. 54-15913
  • Patent Document 4 Japanese Patent No. 3151875
  • Patent Document 5 Japanese Patent No. 3200848
  • Patent Document 6 JP-A-6-73277
  • Patent Document 7 JP 2002-12749 A
  • the main object of the present invention is to eliminate the drawbacks of the prior art described above, that is, to greatly reduce the production cost of a polyester resin film excellent in transparency and flexibility. And providing a flexible polyester film that can be produced at low cost, and a flexible polyester resin suitable for the flexible polyester film. Furthermore, a flexible polyester resin film having excellent whitening resistance over time, heat resistance, and bleed-out resistance can be produced at low cost.
  • the present invention uses a relatively low-purity product, not a high-purity product, as the dimeric fatty acid or derivative thereof.
  • a relatively low-purity dimerized fatty acid or derivative thereof a copolymer having a composition such as the content of fatty acid dimer, the content of fatty acid trimer, etc. within a specific range is used.
  • Adopting specific conditions such as setting the melt viscosity within a specific range to produce copolymerized polyester resin having excellent transparency and flexibility even when using low-purity products of dimerized fatty acids and their derivatives
  • the inventors have obtained the knowledge that it is possible to produce a copolyester film excellent in transparency, flexibility and the like, and have made the present invention.
  • the copolymer polyester of the present invention contains a small amount of fatty acid or a derivative thereof containing 15 to 95% by weight of fatty acid dimer and 5 to 85% by weight of fatty acid trimer.
  • the present invention in order to overcome the problem of high cost, dimerized fatty acids having a purity of 95% by weight or less that can be produced without going through multiple distillation and refining steps after the dimerization reaction and derivatives thereof. Even if a conductor is used, a flexible polyester resin that is excellent in transparency and flexibility and can be put into practical use can be made into a flexible film. Therefore, according to the present invention, it is possible to remarkably reduce the raw material cost when producing a copolyester and a polyester film excellent in flexibility, transparency, etc., which is excellent in cost and suitable for practical use. Flexible polyester bag Fats and films can be produced. Taking advantage of this advantage, the flexible film obtained by the present invention is preferable for applications such as industrial materials and packaging materials that require flexibility, easy moldability, etc., and as an alternative to polysalt-bulb flexible films. Can be used.
  • the copolymer polyester of the present invention is a copolymer polyester synthesized from a glycol component and an acid component containing a weighted fatty acid or a derivative thereof containing a fatty acid dimer and a fatty acid trimer in a specific ratio. is there. That is, it is a copolyester containing a soft segment whose main constituent is a residue composed of a weighted fatty acid or its derivative as an essential structural unit, and other acid components (for example, aromatic dicarboxylic acid, etc.) as necessary. It contains a hard segment whose main component is the residue.
  • the aromatic dicarboxylic acid residue constituting the hard segment is preferably formed from an aromatic dicarboxylic acid and an ester-forming derivative thereof.
  • an aromatic dicarboxylic acid and an ester-forming derivative thereof for example, isophthalic acid, terephthalic acid, diphenyl 4, 4'-dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid, naphthalene 2, 7-dicarboxylic acid, naphthalene 1, 5-dicarboxylic acid, diphenyl Enoxetane 4 4′-dicarboxylic acid, diphenyl sulfone 4, 4′-dicarboxylic acid, diphenyl ether 4, 4′-dicarboxylic acid, and ester-forming derivatives thereof.
  • terephthalic acid isophthalic acid
  • naphthalene dicarboxylic acid and ester-forming derivatives thereof are preferable.
  • these aromatic dicarboxylic acid components may be used alone or in combination of two or more.
  • the content of the aromatic dicarboxylic acid residue is preferably 50 to 99 mol% of the acid component residue. More preferably, it is 55-95 mol%, and still more preferably 60-93 mol%. If the content of the aromatic dicarboxylic acid residue is less than 50 mol%, the heat resistance of the copolyester is lowered, and the mechanical properties of the resulting film may be lowered.
  • the dimeric fatty acid and its derivative residue constituting the soft segment in the copolyester are produced by a dimeric reaction of an unsaturated fatty acid having 10 to 30 carbon atoms represented by the following formula. It is preferable that the dimeric fatty acid or its derivative is formed.
  • This dimerized fatty acid or derivative thereof (hereinafter referred to as dimerized fatty acid component)
  • dimerized fatty acid component contains dimer fatty acid obtained by diluting unsaturated fatty acid or an ester formation derivative thereof.
  • R is a hydrogen atom or an alkyl group
  • m is an integer from 1 to 25
  • k is an integer from 1 to 5
  • n is an integer from 0 to 25
  • m, k, and n are 8 ⁇ m + (The relational expression of 3k + n ⁇ 28 is satisfied.)
  • Examples of the unsaturated fatty acid include linoleic acid having 18 carbon atoms, linolenic acid, oleic acid and the like, erucic acid having 22 carbon atoms, docosapentaenoic acid, docosahexaenoic acid, and the like.
  • the dimerization reaction product obtained by the dimerization reaction is used as it is without further purification. It can also be used as a component.
  • the reaction conditions should be adjusted so that the content ratio of the dimer and trimer is 15 to 95% by weight and 5 to 85% by weight, respectively, or if necessary, separation or purification, etc. It is necessary to process.
  • the dimer content is 70-92% by weight and the trimer content is 6-30% by weight. More preferably, the dimer content is 70-90% by weight and the trimer content is 13-30% by weight.
  • the unreacted monomer remaining in the dimerized fatty acid component used as a polymerization raw material is preferably as small as possible in order to sufficiently increase the degree of polymerization during polymerization, that is, dimer and trimer. It is preferable that the total content with the body is as much as possible.
  • the total content of dimer and trimer is preferably 90-100% by weight, more preferably 97-100% by weight.
  • the dimer content and the trimer content are within the ranges specified in the present invention
  • the high-purity fatty acid that has been used in the prior art for example, the dimer content is 98% by weight.
  • By achieving a markedly low cost it becomes possible to expand to low-priced flexible film applications that have been difficult to apply in terms of manufacturing costs. This is an industrially promising alternative to flexible films.
  • the dimerized fatty acid component used in the production of the copolyester of the present invention includes a dimer and a trimer (hereinafter collectively referred to as a trimer) as described above.
  • a dimer and a trimer (hereinafter collectively referred to as a trimer) as described above.
  • a dimeric fatty acid component in which unsaturated bonds have been removed by hydrogenation.
  • dimerized fatty acid component dimer acid which is a dimerized fatty acid having 36 carbon atoms and an ester-forming derivative thereof are preferable.
  • the dimer acid is obtained by diluting an unsaturated fatty acid having 18 carbon atoms such as linoleic acid or linolenic acid oleic acid.
  • a high-purity dimer acid Yukema International Co., Ltd. "PRI POL" (registered trademark) made by the company is commercially available.
  • PRI POL registered trademark
  • Various ester-forming derivatives of dimerized fatty acids are also commercially available.
  • the dimerized fatty acid component used in the present invention may be prepared using these commercially available products.
  • the amount of the residue of the dimeric fatty acid component is preferably 50 mol% of the acid component residue in the copolymerized polyester, more preferably 5 45%, more preferably 7-40 mol%.
  • the amount of residues of dimerized fatty acid component exceeds 50 mol% and the amount of residues of aromatic dicarboxylic acid is less than 50 mol%, The heat resistance of the reester may decrease, and the mechanical properties of the resulting film may decrease.
  • the dimerized fatty acid component used as a polymerization raw material in the present invention is obtained by subjecting an unsaturated fatty acid to a dimerization reaction by a usual method, so that a dimer and a trimer are contained in desired levels, respectively.
  • the reaction product may be prepared as it is or by treating it as necessary.
  • the raw material for the unsaturated fatty acid is an oil derived from a natural product such as crude tall oil or crude soybean oil
  • it is purified by a conventional method to obtain a purified fatty acid.
  • a conventional method to carry out the dimerization reaction of this purified unsaturated fatty acid.
  • 2 to 10 parts by weight of clay and, if necessary, 0.2 to 2.0 parts by weight of water as a polymerization catalyst with respect to 100 parts by weight of the purified fatty acid is carried out at about 200-280 ° C and pressure 2-lOkgZcm 2 for about 0.5-8 hours. Then add 0.1-2 parts by weight of phosphoric acid, about 60-150.
  • the reaction product obtained by this dimerization reaction usually contains about 70-80% by weight of the dimer. This reaction product may be purified by molecular distillation or the like, if necessary.
  • the dimerized fatty acid component is a dimerized fatty acid ester obtained by mixing dimerized fatty acid and various alcohols and then esterifying it under an ester exchange reaction catalyst such as an acid. It may be used as a component.
  • the glycol component of the copolymer polyester of the present invention preferably contains a 1,4 butanediol residue, the following formula It may contain a glycol residue other than 1,4-butanediol (hereinafter referred to as other darlicol residues).
  • X in the formula is an alkylene group other than a tetramethylene group, or an alkylene group in the alkylene group, or a group having a side chain composed of a cycloalkyl group, or a group having a cycloalkylene group and an alkylene group).
  • glycol components for other glycol residues include, for example, ethylene glycol, 1, 3 propanediol, 1, 2- Propanediol, 2-Methylenole 1,3 Propanediol, 1,3 Butanediole, 1,2 Butanediol, 1,5-pentylglycol, 2,2 Dimethyl-1,3 Propandiol, 2-Ethyluol 1 , 3 Propanediol, 1,6-xanthdiol, 2-methyl-2-ethyl- 1,3 propanediol, 1,8 octanediol, 1,10 decanediol, 1,3-cyclobutanediol, 1,3-cyclobutanedimethanol 1, 3-cyclopentanediethanol, 1,4-cyclohexanedimethanol and the like.
  • the combination of these glycol components is not particularly limited, but in particular, the combined use of 1,4 butanediol with ethylene glycol and Z or 1,3 propanediol is particularly effective for controlling the crystallization rate of the polyester. I like it.
  • the amount of 1,4 butanediol residue is preferably 10-100 mol% of the glycol residue, more preferably 20-90 mol%, preferably 45- 85 mol 0/0.
  • the amount of other glycol residues is preferably 90 to 80 mol%, more preferably 10 to 80 mol%, and still more preferably 15 to 55 mol%. If the amount of 1,4 butanediol residue is less than 10 mol%, the crystallization rate of the polyester will decrease, making it difficult to form due to sticking during molding, or the transparency of the resulting molded product will be reduced. There is.
  • copolymerized polyester of the present invention in addition to the above-mentioned acid component and glycol component, other components may be copolymerized within the range not impairing the object of the present invention, or other component strengths are obtained. It is also possible to mix rosin.
  • other copolymerizable acid components include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, trisodium 5-sulfoisophthalate.
  • the copolymerized polyester of the present invention needs to have a melt viscosity of 1000-3000 poise at 250 ° C, more preferably 1300-2300 poise.
  • a melt viscosity of polyester exceeds 3000 poise, when extruding polyester into a film or the like, the extruded state is not stable, and a film or molded product with a non-uniform film thickness tends to be obtained. Furthermore, the partially thickened part tends to whiten and become spotted.
  • the melt viscosity is less than 10 OOpoise, it is difficult to form or form a film due to insufficient viscosity.
  • the polymerization degree and intrinsic viscosity (IV) may be controlled to appropriate levels.
  • the range of the intrinsic viscosity is preferably 0.5 to 1.5, more preferably 0.5 to 1.2, and particularly preferably 0.7 to 0.9.
  • the melt viscosity level may be adjusted by blending a compatibilizing agent at the time of polymerization or at the time of polymer melt kneading.
  • the method for producing the above-described copolymer polyester of the present invention is not particularly limited, and can be produced by a method similar to a usual polyester polymerization method.
  • two or more kinds of polymers and Z or a copolymer may be melt-kneaded in an extruder and copolymerized to obtain a predetermined polymerization composition.
  • the latter method by melt-kneading includes an aromatic polyester that is overlapped with an aromatic dicarboxylic acid and a dallicol component, an aliphatic dicarboxylic acid, a dimerized fatty acid component, and a glycol component. And a method of melting and kneading a group 1 aromatic polyester copolymer in an extruder to obtain a copolymer polyester having the specific polymerization composition described above.
  • a general-purpose aromatic polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) can be used. Further, mixing of the aromatic polyester and the copolymer is possible.
  • the constituent components are mainly selected from the group power of terephthalic acid residues and / or isophthalic acid residues, and ethylene glycol residues, 1,3 propanediol residues, and 1,4 butanediol residues.
  • At least one kind of aromatic polyester mainly composed of terephthalic acid residue and dimerized fatty acid component, ethylene glycol residue, 1,3 propandiol residue, and 1,4 butanediol residue More preferred is a method in which an aliphatic monoaromatic polyester copolymer comprising at least one selected from the group of polymers is melt-kneaded in an extruder to obtain a copolymerized polyester having the specific polymerization composition described above.
  • aromatic polyester terephthalic acid residues and Z or isophthalic acid residues, and those having power with ethylene glycol residues are particularly preferred.
  • PET polyethylene terephthalate
  • PETZl ethylene terephthalate isophthalate copolymer Combined
  • aliphatic monoaromatic polyester copolymer those having a terephthalic acid residue, a dimerized fatty acid component, and a 1,4 butanediol residue are particularly preferable.
  • the copolymerized polyester obtained by the method as described above may contain a compatibilizer such as the following during copolymerization or resin melt-kneading. It is sometimes preferred to add it.
  • Examples of the compatibilizer include various glycidyl compounds such as diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl phthalate, bisphenol S diglycidyl ether, and polyethylene glycol diglycidyl ether.
  • Various oxazolines such as phe-lenbioxoxazoline, 1,3-phenol-lenbisoxazoline, various ester compounds of various fatty acids such as stearic acid, oleic acid, lauric acid and polyether, and hydrochloric acid, sulfuric acid, nitric acid, ⁇
  • Organic acids such as toluenesulfonic acid can be mentioned.
  • bisoxazoline or an organic acid it is preferable to use bisoxazoline or an organic acid.
  • the melt viscosity is an amount sufficient to provide the desired viscosity level and the desired transparency. Is preferably 0.1 to 5% by weight.
  • the copolyester in the present invention has a glass transition point (Tg) of preferably 25 ° C or less, more preferably 20 ° C or less, More preferably, it is 15 ° C or less.
  • the polyester film of the present invention is formed into a film by an ordinary method after various particles and additives are added to the copolymer polyester having the above-described polymerization composition and melt viscosity as necessary.
  • it can be produced by melt-extrusion, cooling, solidification, and stretching or heat treatment as necessary.
  • the particles to be added to the polyester film are appropriately selected depending on the purpose and application, and are not particularly limited as long as the effects of the present invention are not impaired.
  • Inorganic particles, organic particles, bridged polymer particles, polymerization Examples thereof include internal particles generated in the system. Two or more of these particles may be added.
  • the amount of addition of the strong particles is preferably 0.01 to 10% by weight, more preferably 0.02 to 1% by weight.
  • the average particle diameter of the particles to be added is preferably 0.001 to 10 ⁇ m, and more preferably Preferably it is 0. 01—. If the average particle size is within a preferred range, it is difficult to cause deterioration of transparency and moldability, which are difficult to cause defects in the resin composition and film.
  • the type of inorganic particles is not particularly limited.
  • various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, and various composites such as kaolin and talc.
  • Various oxides such as oxide, lithium phosphate, calcium phosphate, and magnesium phosphate, various oxides such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, lithium fluoride, etc. It is possible to use fine particles having various salt isotropic forces.
  • organic particles fine particles having strength such as calcium oxalate and terephthalates such as calcium, norlium, zinc, manganone and magnesium can be used.
  • the cross-linked polymer particles include fine particles having dibutylbenzene, styrene, acrylic acid, and methacrylic acid butyl monomers alone or having copolymer power.
  • organic fine particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin can be used.
  • Examples of the internal particles generated in the polymerization system include particles generated by a known method in which an alkali metal compound, an alkaline earth metal compound, or the like is added to the reaction system, and a phosphorus compound is added. It is done.
  • the polyester film of the present invention does not impair the effects of the present invention! /, As long as it is within the range, known additives such as flame retardants, heat stabilizers, antioxidants, ultraviolet rays Absorbers, antistatic agents, plasticizers, tackifiers, organic lubricants such as fatty acid esters and waxes or antifoaming agents such as polysiloxanes, and coloring agents such as pigments or dyes may be blended in appropriate amounts! .
  • known additives such as flame retardants, heat stabilizers, antioxidants, ultraviolet rays Absorbers, antistatic agents, plasticizers, tackifiers, organic lubricants such as fatty acid esters and waxes or antifoaming agents such as polysiloxanes, and coloring agents such as pigments or dyes may be blended in appropriate amounts! .
  • the layer structure of the film may be a single layer, or a layer for imparting new functions such as slipperiness, adhesiveness, tackiness, heat resistance, and weather resistance to the surface is formed.
  • a laminated structure may be used.
  • a layer obtained by copolymerization of dimer and fatty acid components, and layers having different compositions of resin or additives (B layer and C layer) are laminated, Three-layer configuration such as BZAZB, B / A / C, or AZBZC
  • the lamination thickness ratio of each layer may be set arbitrarily, even if it has a laminated structure of more than three layers.
  • the polyester film in the present invention preferably has an elastic modulus of 25 ° C and a range of 1 lOOOMPa.
  • the elastic modulus is strong and within the range, when used in the form of a film, there is no problem in handling due to small deformation and excellent low-temperature formability.
  • a method of optimizing the copolymerization amount of the dimerized fatty acid component or using a dimerized fatty acid component having a high softening effect Is mentioned.
  • the polyester film of the present invention may be an unstretched film or a stretched film.
  • the stretched film may be either a uniaxially stretched film stretched in either the longitudinal direction or the width direction of the film, or a biaxially stretched film stretched in both the longitudinal direction or the width direction of the film. .
  • the thickness of the film may be an optimum thickness according to the intended use.
  • the thickness is usually in the range of 0.5-1000 / zm, and the surface stability of film formation is preferably 1/500 / ⁇ ⁇ , and more preferably 5-200 ⁇ m.
  • the polyester film of the present invention may be improved in adhesion and printability by performing a surface treatment such as a corona discharge treatment as necessary.
  • a surface treatment such as a corona discharge treatment
  • Various coatings may be applied, and the type, coating method, and thickness of the coating compound are not particularly limited as long as the effects of the present invention are not impaired. Furthermore, if necessary, it can be used after being subjected to molding calo such as embossing and printing.
  • the polyester film of the present invention can be used as various industrial materials and packaging materials that require easy moldability with a single sheet or a composite sheet.
  • the composite sheet can be used by being bonded to a base material such as metal, wood, paper, a resin sheet, or a resin board.
  • Specific applications include applications in which conventional flexible films and easily molded films have been used, for example, packaging materials such as packaging films, wrap films, stretch films, partition films, wall paper, and plywood decorative sheets.
  • packaging materials such as packaging films, wrap films, stretch films, partition films, wall paper, and plywood decorative sheets.
  • the force that can be used for the film is not limited to this.
  • composition ratio (content) of the monomer, dimer and trimer was determined from the peak areas of the respective components.
  • Polyester was dissolved in orthochlorophenol and measured at 25 ° C.
  • the copolyester was vacuum dried at 150 ° C for 5 hours or more, and then measured at 250 ° C using a melt index.
  • Stability at the time of forming a polyester film was determined according to the following criteria.
  • the transparency of the polyester film was determined according to the following criteria from the haze value measured using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
  • the haze value was measured using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. The whitening property was determined.
  • Good Haze value 15% or more, less than 40%
  • the elastic modulus was measured at 25 ° C using a bow I tension tester ("Tensilon" manufactured by Orientec Co., Ltd.). For a sample with a width of 10 mm and a specimen length of 50 mm after holding the film at the measurement temperature for 30 seconds, measure the elastic modulus (MPa) in the film longitudinal direction and the width direction at 10 points each at a pulling speed of 300 mmZmin, and obtain the average value. It was.
  • a mixture of 83 parts by weight of dimethyl terephthalate, 17 parts by weight of dimethyl isophthalate and 60 parts by weight of ethylene glycol was mixed with 0.09 parts by weight of magnesium acetate and anti-dioxide trioxide. After adding 0.03 part by weight of mon and conducting a transesterification by heating and raising by a conventional method, 0.026 part by weight of trimethyl phosphate was added, and the same polycondensation reaction as in the case of PET was performed.
  • An ethylene terephthalate 'isophthalate copolymer (PETZl) having an intrinsic viscosity of 0.65 was prepared.
  • a mixture of 100 parts by weight of dimethyl terephthalate and 87 parts by weight of 1,3 propanediol is charged with 0.06 part by weight of tetrabutyl titanate and heated by a conventional method, and finally heated to 220 ° C for transesterification. Reaction was performed. After the transesterification reaction, add 0.05 parts by weight of trimethyl phosphate and 0.04 parts by weight of tetrabutyl titanate, gradually increase the temperature and reduce the pressure, and finally at 260 ° C at lTorr or less.
  • a polycondensation reaction was performed to produce polypropylene terephthalate (PPT) having an intrinsic viscosity of 0.70.
  • Dimer acid (“PRIPOL 1025” (“PRIPOL1025") (manufactured by Yukema International)) Add 3 parts by weight of sulfuric acid to a mixture of 50 parts by weight and 50 parts by weight of methanol, reflux for 10 hours, and then dry Thus, dimethyl dimerate having 36 carbon atoms composed of 2.2% monomer, 78.6% dimer, and 19.2% trimer was prepared.
  • the copolymerized polyester 7 has a viscosity outside the present invention (comparative example).
  • the acid component dimethyl terephthalate and dimethyl dimer acid having 36 carbon atoms obtained above were used.
  • glycol component butanediol and 1,4-cyclohexanedimethanol or 2,2 dimethyl-1,3 propanediol were used. Polymerization is carried out until the intrinsic viscosity shown in Table 1 is reached using the same method as for Copolyester 1, except that the composition is mixed in the proportions shown in Table 1. V. Copolyesters with the viscosity levels shown in Table 1 were synthesized.
  • the raw material is crude rapeseed oil containing erucic acid at a high concentration, and it is refined by the usual method and dimerized and reacted. Dimer 82.3% and trimer 15.2%) and dimethyl terephthalate as the acid component, ethylene glycol and butanediol as the glycol component, and the composition shown in Table 2 Polymerization was carried out until the intrinsic viscosity shown in Table 2 was obtained in the same manner as in copolymer polyester 1 except that the polyesters were mixed in proportions, and a copolymer polyester having the viscosity level shown in Table 2 was synthesized.
  • Dimethyl dimerate having a carbon number of 36 produced by the same method as in the case of copolymer polyester 11 (the composition ratio of the monomer, dimer and trimer is shown in Table 2), and dimethyl terephthalate Is used as an acid component, ethylene glycol and butanediol are used as glycol components, and mixed in the proportions shown in Table 2 in the same manner as in copolymer polyester 2, using the intrinsic viscosity shown in Table 2. Polymerization was carried out until the viscosity reached, and a copolyester having a viscosity level shown in Table 2 was synthesized. However, in the case of the copolyester 15, the degree of polymerization in the polymerization process did not increase, and the polymer could not be obtained.
  • copolymer polyesters 14 and 15 are those having a copolymer composition other than those specified in the present invention (comparative example). [0084] [Table 2]
  • the slit-shaped die force was also extruded into a sheet shape, adhered to the casting drum by an electrostatic application method, and solidified by cooling to obtain an unstretched film.
  • An unstretched film can be stably produced, and the physical properties of the obtained film show good transparency as shown in Table 3.
  • the addition of bisoxazoline to the copolyester 1 allows flexibility and It was also excellent in aging resistance.
  • Unstretched films were prepared in the same manner as in Example 1 except that the above-described copolymer polyesters 2, 3, 8, and 9 were used. Table 3 shows the physical properties of the unstretched film obtained.
  • Example 2 The film of Example 2 was excellent in transparency.
  • Example 3 The film of Example 3 was slightly inferior in film formation stability and transparency as compared with Example 2, but was at a practical level and had relatively good flexibility properties! /.
  • the film of Example 4 and the film of Example 5 showed good film forming stability, flexibility and excellent transparency.
  • a film was formed in the same manner as in Example 2 except that the above-described copolymerized polyester 4 was used.
  • the physical properties of the obtained unstretched film are as shown in Table 3.
  • the film exhibited good transparency and had good softness properties immediately after film formation. However, whitening progressed over time.
  • Copolyester 4 and Copolyester 5 described above were blended in the proportions of 20 wt% and 80 wt%, and 2 parts by weight of 1,4 phen-lenbisoxazoline was added to 100 parts by weight of this resin composition and melted. Blended to make a copolyester.
  • This An unstretched film was produced in the same manner as in Example 2 except that the copolymer polyester was used. The properties of the obtained film are as shown in Table 3, showing good film forming stability, transparency and flexibility.
  • Respective unstretched films were prepared in the same manner as in Example 2 except that the above-described copolymer polyester 10-13 was used.
  • Table 4 shows the physical properties of the obtained unstretched film.
  • Example 8 The film of Example 8 exhibited good film forming stability and transparency.
  • Example 9 was slightly inferior in film formation stability as compared with Example 2, but was at a practical level and had good flexibility properties.
  • Example 10 showed good film forming stability and flexibility, and particularly excellent transparency compared to Example 2.
  • Example 11 The film of Example 11 was slightly inferior in film formation stability and transparency as compared with Example 2, but was at a practical level and had relatively good flexibility characteristics.
  • a film was formed in the same manner as in Example 2 except that the copolyester 7 was used, and the viscosity of the molten polymer was too low to form a film stably.
  • the flexible copolyester and the flexible film obtained in the present invention can be preferably used for industrial materials and packaging materials that require flexibility, transparency, easy moldability, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention décrit un procédé de production peu onéreux d’une résine ou d’un film polyester dont les propriétés de transparence, de flexibilité, etc. sont excellentes. La présente invention décrit également un film polyester flexible pouvant être produit à coût réduit, ainsi qu’une résine polyester flexible pouvant être employée dans la production dudit film. Ladite résine est un copolyester synthétisé à partir d’un composant acide qui inclut soit un acide gras oligomérisé, comprenant entre 15 et 95 % en masse de dimère d’acide gras et entre 5 et 85 % en masse de trimère d’acide gras, ou un dérivé dudit acide gras oligomérisé, ainsi qu’un composant de type glycol. Ladite résine présente une viscosité à l’état fondu à 250 °C comprise entre 1 000 et 3 000 P. Ledit film polyester flexible est obtenu à partir de ce copolyester par mise en forme à l’état fondu.
PCT/JP2004/016295 2004-11-04 2004-11-04 Copolyester, procédé de production dudit copolyester, et film polyester WO2006048927A1 (fr)

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PCT/JP2004/016295 WO2006048927A1 (fr) 2004-11-04 2004-11-04 Copolyester, procédé de production dudit copolyester, et film polyester
KR1020077010164A KR101153909B1 (ko) 2004-11-04 2004-11-04 공중합폴리에스테르, 그 제조방법 및 폴리에스테르 필름
JP2006542198A JPWO2006048927A1 (ja) 2004-11-04 2004-11-04 共重合ポリエステル、その製造方法、及びポリエステルフィルム
CN2004800447471A CN101090921B (zh) 2004-11-04 2004-11-04 共聚聚酯、其制造方法和聚酯薄膜

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WO2011134872A1 (fr) * 2010-04-28 2011-11-03 Dsm Ip Assets B.V. Film barrière renouvelable
WO2013041552A1 (fr) * 2011-09-23 2013-03-28 Dsm Ip Assets B.V. Composition de polymère contenant un élastomère de polyester thermoplastique
JP2013091686A (ja) * 2011-10-24 2013-05-16 Teijin Ltd ポリエステル樹脂およびそれを用いたポリエステルフィルム

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WO2012080163A2 (fr) * 2010-12-13 2012-06-21 Dsm Ip Assets B.V. Composition de polymère contenant un polymère, ledit polymère contenant des unités monomères d'un acide gras dimérisé
KR101951009B1 (ko) * 2011-05-18 2019-02-22 석명호 식물성 지방산을 함유하는 플라스틱 제품 및 그 제조방법
CN103665353B (zh) * 2012-09-19 2017-08-04 上海杰事杰新材料(集团)股份有限公司 一种生物可降解共聚酯及其制备方法
CN105199085B (zh) * 2015-09-16 2017-06-06 常州大学 一种二聚酸改性聚丁二酸丁二醇共聚酯及其制备方法
KR102619518B1 (ko) * 2017-09-22 2023-12-29 미쯔비시 케미컬 주식회사 공중합 폴리에스테르 필름
CN110685037A (zh) * 2019-11-11 2020-01-14 南通新帝克单丝科技股份有限公司 高强耐磨型拉链单丝及其生产方法

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WO1996025642A1 (fr) * 1995-02-14 1996-08-22 Bismuth Cartridge, L.L.C. Procede de fabrication de plombs de chasse

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011134872A1 (fr) * 2010-04-28 2011-11-03 Dsm Ip Assets B.V. Film barrière renouvelable
WO2013041552A1 (fr) * 2011-09-23 2013-03-28 Dsm Ip Assets B.V. Composition de polymère contenant un élastomère de polyester thermoplastique
JP2014526596A (ja) * 2011-09-23 2014-10-06 ディーエスエム アイピー アセッツ ビー．ブイ． 熱可塑性ポリエステルエラストマーを含有するポリマー組成物
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JP2013091686A (ja) * 2011-10-24 2013-05-16 Teijin Ltd ポリエステル樹脂およびそれを用いたポリエステルフィルム

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CN101090921B (zh) 2011-07-06

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