Classifications

• • 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
• • 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
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • 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
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • 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
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
• • 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
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
• • 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
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
  • B29K2067/003—PET, i.e. poylethylene terephthalate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
  • B29L2007/008—Wide strips, e.g. films, webs
• • 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
• • 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
  • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• a composition for forming a heat shrinkable film comprising a polyethylene terephthalate resin and a copolymerized polyester resin, and a heat shrinkable film
• the present invention relates to a composition for forming a heat shrinkable film comprising a polyethylene terephthalate resin and a copolyester resin, and more particularly, to form a heat shrinkable film having an excellent shrinkage rate and a heat shrinkable film capable of heat shrinking at a low temperature. It relates to a composition for.
• Heat shrinkable plastic products utilize the property of shrinking with heating and are widely used in film applications such as shrink wrap, shrink labels, and the like.
• polyvinyl chloride (PVC), polystyrene, polyester (p yester) -based plastic film, etc. have been used for the purpose of labeling, cap seal, or direct packaging of various containers. .
• a film made of polyvinyl chloride has a problem of generating a substance which causes hydrogen chloride gas and dioxins at the time of incineration and is therefore subject to regulation.
• this product is used as a shrink label of a PET container, there is a hassle to separate the label from the container when the container is recycled.
• the polystyrene-based film has a good work stability according to the shrinkage process, the appearance of the product is good, but the chemical resistance is not good to print In this case, there is a problem that an anchor of a special composition must be used.
• the present invention provides a composition for forming a heat shrinkable film which is excellent in shrinkage rate and can provide a heat shrinkable film that can be heat shrinked at a low temperature. [Measures of problem]
• composition for forming a heat shrinkable film according to an aspect of the present invention, polyethylene terephthalate (PET) resin having an intrinsic viscosity of about 0.50 to 1.2 dl / g; And dicarboxylic acid-derived residues of residues derived from aromatic dicarboxylic acids, 4- (hydroxymethyl) cyclonuxylmethyl 4'-
• PET polyethylene terephthalate
• dicarboxylic acid-derived residues of residues derived from aromatic dicarboxylic acids 4- (hydroxymethyl) cyclonuxylmethyl 4'-
• the intrinsic viscosity of the copolyester resin may be about 0.60 to 0.90 dl / g, or about 0.70 to 0.87 dl / g.
• the polyethylene terephthalate (PET) resin is about 1 to 99 mol 0 /.
• the copolyester resin may be included in about 1 to 99 mol 0 /.
• the diol-derived residues are 1,4-cyclonucleodimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1 , 6-nucleic acid diol, 1,2-cyclonucleic acid di, 1,4-cyclonucleic acid diol, 1,2-cyclonucleic acid dimethanol, 1,3—cyclonucleic acid dimethanol, 2,2-dimethylpropane-1,3 Residues derived from one or more other diols selected from the group consisting of diols (neopentyl glycol), ethylene glycol and diethylene glycol. And the 4- (hydroxymethyl) cyclonucleomethylmethylmethyl
• Residues derived from (hydroxymethyl) cyclonucleic acid carboxylate, residues derived from 4,4- (oxybis (methylene) bis) cyclonucleic acid methane, and diol derived residues of the other diol derived residues are acid 100 mole 0/0 contrast, may be about 10 to 80 mole 0 /.
• the aromatic dicarboxylic acid is terephthalic acid (terephthalic acid), dimethyl terephthalate (dimethyl terephthalate), cyclic dicarboxylic acid, isophthalic acid (isophthalic acid), adipic acid (adipic acid), azelaic acid (azelaic acid), naphthalene di It may be at least one selected from the group consisting of carboxylic acid (naphthalenedicarboxylic acid), and succinic acid.
• the copolyester resin is a dicarboxylic acid containing the aromatic dicarboxylic acid and 4- (hydroxymethyl) cyclonucleomethylmethyl 4 ′-(hydroxymethyl) cyclonucleic acid carramide represented by the formula (1).
• a diol containing a carboxylate and 4,4- (oxybis (methylene) bis) cyclohexane methanol represented by Formula 2 is reacted to cause esterification reaction and polycondensation reaction. It can be produced including the step of doing.
• esterification reaction is a diol with respect to the dicarboxylic acid in a molar ratio of about 1.2 to 3.0, the reaction temperature of about 230 to 265 ° C, and about 100 to under a pressure of about 1.0 to 3.0 kg / cuf It can be performed for 300 minutes.
• an additive including a catalyst, a stabilizer, and a colorant may be used.
• the polycondensation reaction is about 260 ⁇ 290 ° C reaction temperature and about
• the method for producing a heat shrinkable film according to another aspect of the present invention includes the step of extruding and extruding a composition for forming a heat shrinkable film according to the above.
• Heat shrink film according to another aspect of the present invention polyethylene terephthalate (PET) resin having an intrinsic viscosity of about 0.50 to 1.2dl / g; And dicarboxylic acid-derived residues of residues derived from aromatic dicarboxylic acids, and 4- (hydroxymethyl) cyclonucleomethylmethyl 4′- represented by the following general formula (1):
• the composition for forming a heat shrinkable film according to the present invention has better shrinkage than conventional copolymerized polyester and is capable of heat shrinking at a low temperature similar to PVC to prevent deformation or turbidity of the PET container caused by the heat shrinkage process of the film.
• the manufacturing method of the heat-shrink film according to the present invention has the effect of controlling the shrinkage rate and the shrinkage onset temperature by adjusting the content of the polyester resin as desired.
• the present invention provides a polyethylene terephthalate (PET) resin having an intrinsic viscosity of about 0.50 to 1.2 dl / g; And dicarboxylic acid-derived residues of residues derived from aromatic dicarboxylic acids, and 4- (hydroxymethyl) cyclonucleomethylmethyl 4′- represented by the following general formula (1): Residues derived from (hydroxymethyl) cyclonucleic acid carboxylate, and
• composition for forming a heat shrinkable film comprising a copolyester resin comprising a di-derived residue of a residue derived from 4,4- (oxybis (methylene) bis) cyclonucleic acid methane represented by 2.
• a method for producing a heat shrink film comprising the step of injecting, extruding and stretching the composition for forming a heat shrink film.
• a composition for forming a heat shrinkable film according to a specific embodiment of the present invention will be described in detail.
• the 'residue' is a certain compound included in the result of the chemical reaction and derived from the specific compound when the specific compound participates in the chemical reaction Means part or unit.
• each of the 'residue' derived from dicarboxylic acid or 'residue' derived from di is derived from a part or diol component derived from a dicarboxylic acid component in a polyester formed by an esterification reaction or a polycondensation reaction. Means part.
• composition for forming a heat shrinkable film according to an aspect of the present invention, polyethylene terephthalate (PET) resin having an intrinsic viscosity of about 0.50 to 1.2 dl / g; And dicarboxylic acid-derived residues of residues derived from aromatic dicarboxylic acids, and 4- (hydroxymethyl) cyclonucleomethylmethyl 4′- represented by the general formula (1).
• PET polyethylene terephthalate
• Conventional polyester film has a problem that wrinkles or non-uniform shrinkage occurs frequently during molding due to a sudden change in shrinkage behavior, and also inferior in shrinkage at low temperatures when compared to polyvinyl chloride film or polystyrene film In order to compensate for this, it must shrink at a high temperature, and in this case, there was a problem that deformation or cloudiness of the PET container occurs.
• the present inventors have prepared 4- (hydroxymethyl) cyclonucleomethylmethyl 4 ′-(hydroxymethyl) cyclonucleic acid carboxylate, and 4,4- (oxybis (methylene) bis) cyclonucleic acid in preparing a copolyester resin.
• diols containing methanol the shrinkage of PET containers, which has been excellent in shrinkage, and is capable of heat shrinking at low temperatures similar to PVC, resulting in the film's heat shrinking process or It is possible to prevent cloudiness, and to easily control the shrinkage rate to reduce molding defects, and when the co-polyester resin and PET are blended at a specific composition ratio, the shrinkage is excellent, and heat shrinkage is possible at low silver.
• the heat shrink film can be produced through experiments confirmed that the olol to complete the invention.
• diol compound used to improve the moldability or other physical properties of the copolyester examples include 4- (hydroxymethyl) cyclonucleomethylmethyl 4 ′-(hydroxymethyl) cyclonucleic acid carboxylate, 4,4- (oxy Bis (methylene) bis) cyclonucleic acid methane, 1,4-cyclonucleic acid dimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3 -Propanediol, 1,6-nucleic acid diol, 1,2-cyclonucleic acid diol, 1,4-cyclonucleic acid diol, 1,2-cyclonucleic acid dimethanol, and 1,3-cyclonucleic acid dimethanol; Diol compounds used to improve the physical properties of the polymer include 4- (hydroxymethyl) cyclonucleomethylmethyl 4'- (hydroxymethyl) cyclonucleic acid carboxylate and 4,4- (oxybis)
• 4- (hydroxymethyl) cyclonucleomethylmethyl 4'- (Hydroxymethyl) cyclohexanecarboxylate is represented by the following general formula (1)
• 4,4- (oxybis (methylene) bis) cyclonucleic acid methanol is represented by the following general formula (2).
• the amount of 4- (hydroxymethyl) cyclonucleomethylmethyl 4 ′-(hydroxymethyl) cyclonucleic acid carboxylate and 4,4 '(oxybis (methylene) bis) cyclonucleic acid methanol used in the present invention is used in the final polymer.
• a quantity approximated to the desired mole% is added, preferably from about 2 to 17 mole% of the total di-component to prevent formability defects due to crystallization. This is because if it is less than about 2 mole%, it is difficult to confirm the effect of improving the shrinkage rate, and when it exceeds about 17 mole%, there is a problem in that the use of the heat shrink film is lowered due to the occurrence of whitening due to overstretching.
• the intrinsic viscosity of the copolyester resin may be about 0.60 to 0.90 dl / g, black is about 0.70 to 0.87 dl / g.
• the copolymerization When the intrinsic viscosity of the polyester resin is less than about 0.60 dl / g, mechanical properties are expected to be lowered due to the low molecular weight.
• the intrinsic viscosity When the intrinsic viscosity is about 0.9 dl / g, when the blending and molding are required, high pressure and temperature are required to reduce efficiency. Occurs.
• the composition for forming a heat shrinkable film according to the present invention uses a polyethylene terephthalate (PET) resin having an intrinsic viscosity of about 0.50 to 1.2 dl / g.
• PET polyethylene terephthalate
• the PET resin is usually polymerized from dicarboxylic acids and diols, as known in the art.
• the dicarboxylic acid and its derivatives used in the polymerization of the PET resin include terephthalic acid (TPA), isophthalic acid (1PA), naphthalene 2,6-dicarboxylic acid (2, 6-naphthalenedicarboxylic acid; 2, 6-NDA), dimethylterephthalic acid (DMT), dimethylisophthalate (DMI), dimethyl naphthalene 2,6-dicarboxylic acid (dimethyl 2,6-naphthalenedicarboxylate; 2,6-NDC), DMCD (1,4 -Dimethyl cyclohexanedicarboxylate), but the present invention is not limited thereto.
• the diols used in the polymerization of the PET resin may be ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), neopentyl glycol (NPG), cyclonucleic acid Dimethane (cyclohexanedimethan; CHDM) and the like, but is not particularly limited to all diols known in the art in the manufacture of PET resin, EG may be preferred.
• the PET resin is a high temperature and high pressure dicarboxylic acid and a die It is introduced into the reactor, and the reaction catalyst, stabilizer, colorant, and the like are added to the oligomer produced therein to react in a high-temperature vacuum state and polymerized, and is not particularly limited, and PET is known as known in the art. It is possible to polymerize the resin.
• the amount of each of the PET resin and the transparent co-polyester resin prepared as described above can be adjusted in various ratios to adjust the content of the cyclonucleodimethanol compounds in the polymer as desired after the total blending
• the polyethylene terephthalate (PET) resin is about 1 to 99 mole 0 /.
• the copolymer polyester resin may comprise from about 1 to 99 mole 0/0.
• the di-derived residue is 1,4-cyclonucleodimethane, 1,2-propanedi, 1,3-propanedi, 1,4-butanedi, 2,2-dimethyl -1,3-propanediol, 1,6-nucleic acid diol, 1,2-cyclonucleic acid diol 1,4- cyclonucleic acid diol, 1,2-cyclonucleic acid dimethanol, 1,3-cyclonucleic acid dimethanol, 2, It may further comprise residues derived from one or more other diols selected from the group consisting of 2- dimethylpropane-1,3-diol (neopentyl glycol), ethylene glycol and diethylene glycol.
• Residues derived from (hydroxymethyl) cyclonucleic acid carboxylate, residues derived from 4,4- (oxybis (methylene) bis) cyclonucleic acid methanol, and 1,4-cyclonucleic acid dimethane described above are ethylene glycol Or other such as diethylene glycol Dieul derived moiety, such as a diol-derived moieties may be in the dicarboxylic acid than 100 mol%, about 10 to 80 mole 0/0.
• the copolymerized polyester resin is the 4- (hydroxymethyl) cyclonucleomethylmethyl 4'- based on 100 mol 0 /. Of the residue derived from the dicarboxylic acid.
• the aromatic dicarboxylic acid is terephthalic acid (terephthalic acid), dimethyl terephthalate (dimethyl terephthalate), cyclic dicarboxylic acid, isophthalic acid (isophthalic acid), adipic acid (adipic acid), azelaic acid (azelaic acid), naphthalene di It may be at least one selected from the group consisting of carboxylic acid (naphthalenedicarboxylic acid), and succinic acid.
• the co-polyester resin is the aromatic dicarboxylic acid Containing dicarboxylic acid, 4- (hydroxymethyl) cyclonucleomethylmethyl 4 ′-(hydroxymethyl) cyclonucleic acid carboxylate represented by the formula (1), and 4,4- (oxybis represented by the formula (2) (Methylene) bis) may be prepared by reacting a diol comprising cyclonucleic acid methanol to perform an esterification reaction and a polycondensation reaction.
• other diols such as 1,4-cyclonucleodimethanol, ethylene glycol, or diethylene glycol may be further reacted, thereby preparing a copolyester resin further comprising the other diol-derived residue.
• the copolyester resin is prepared through esterification reaction, and polycondensation reaction.
• the first step of esterification reaction may be carried out in a batch or continuous manner, and each raw material may be added separately, but preferably, dicarboxylic acid may be added in a slurry to slurry. .
• the esterification reaction is carried out with a diol to the dicarboxylic acid in a molar ratio of about 1.2 to 3.0, the reaction temperature of about 230 to 265 ° C., more preferably about 245 to 255 ° C., and about 1.0 To 3.0 kg / cuf.
• the esterification time is typically about 100 to 300 minutes, which is not limited to this because it can be appropriately changed depending on the reaction temperature, pressure, and the molar ratio of glycol to dicarboxylic acid used.
• the esterification reaction does not require a catalyst, it is also possible to selectively add a catalyst in order to shorten the reaction time.
• a polycondensation reaction is performed, and a catalyst, a stabilizer, a coloring agent, etc. can be selectively used as a component generally used in the polycondensation reaction of the resin of polyester.
• Examples of the polycondensation catalyst usable in the present invention include titanium, germanium and antimony compounds, but are not particularly limited thereto.
• the titanium catalyst is a catalyst used as a polycondensation catalyst of a polyester resin copolymerized with cyclohexane dimethyl methane derivatives by at least about 15% by weight of terephthalic acid. In addition, it has the advantage of lower cost than the germanium catalyst.
• titanium catalysts that can be used include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylnuclear siltitanate and octylene glycol. Titanate, lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide and silicon dioxide co-precipitates, and titanium dioxide and zirconium dioxide covalent And soaks.
• the amount of the polycondensation catalyst may vary depending on the desired color and the stabilizer and colorant used.
• the polycondensation catalyst is about 1 to about 1 based on the amount of titanium based on the weight of the final polymer. 100 ppm, more preferably about 1 to 50 ppm is good, silicon Up to about 10 ppm may be desirable based on the amount of elements. This is because if the amount of the titanium element is less than about 1 ppm, the desired degree of polymerization cannot be reached. If the amount of the titanium element exceeds about 100 ppm, the color of the final polymer becomes yellow and a desired color cannot be obtained.
• Stabilizers usable in the present invention include phosphoric acid, trimethyl phosphate, triethyl phosphate, triethyl phosphonoacetate, and the like.
• the amount of the stabilizer is preferably about 10 to 100 ppm relative to the weight of the final polymer. This is because if the addition amount of the stabilizer is less than about 10 ppm, it is difficult to obtain the desired bright color, and if it exceeds about 100 ppm, there is a problem that the desired high polymerization degree is not reached.
• the colorant that can be used to improve the color in the present invention includes a colorant such as cobalt acetate and cobalt propionate, the addition amount is preferably about 100ppm or less relative to the final polymer weight.
• a colorant such as cobalt acetate and cobalt propionate
• conventionally known organic compounds may be used as the colorant.
• the polycondensation reaction carried out after the addition of these components is preferably carried out under reduced pressure of about 260 to 290 ° C and about 400 to 100 mmHg, but is not limited thereto.
• the polycondensation step is carried out for the required time until the desired intrinsic viscosity is reached, the reaction temperature is generally about 260 to 290 ° C, It is preferably about 260 to 28C C, more preferably about 265 to 275 ° C.
• a method for producing a heat shrink film comprising the step of injecting, extruding and stretching the composition for forming a heat shrink film.
• PET polyethylene terephthalate
• copolyester resin chips having an intrinsic viscosity of about 0.50 to 1.2 dl / g prepared as described above are prepared, dried, and then mixed in a stirrer. Thereafter, the film may be brought into close contact with a through an injection and extrusion process to obtain an unstretched film, and then stretched to produce a heat shrinkable film.
• PET is carried out at about 120 to 160 ° C
• copolyester is carried out at about 55 to 75 ° C can be used by changing the ratio to suit the desired shrinkage and shrinkage start temperature.
• the composition including the PET resin and the copolyester resin of the present invention prepared as described above may be molded through a conventional molding process known in the art, and may be manufactured into a molded article having a suitable shape as needed.
• PET resin chip having an intrinsic viscosity of 0.80 dl / g
• cyclohexane dimethanol compound (4- (hydroxymethyl) cyclonucleomethylmethyl 4'- (hydroxymethyl) cyclo in the polymer having an intrinsic viscosity of 0.75 dl / g
• Nucleic acid carboxylate, 4,4- (oxybis (methylene) bis) cyclonucleic acid methanol, and 1,4-cyclonucleic acid dimethane as raw materials are copolymerized polyester resin chips having a content of 30 mol 0 /.
• the PET resin and the copolyester resin were mixed in a 1: 9 ratio in a rotary stirrer, and then introduced into an injection machine hopper, and the film was extruded with an extruder and the film was adhered to To obtain an unstretched film, and then stretch the unstretched film to prepare a heat shrink film.
• Example 4 A heat shrinkable film was manufactured in the same manner as in Example 1, except that the PET resin chip and the copolymerized polyester resin chip were blended in a 7: 3 ratio.
• Example 3 A heat shrinkable film was manufactured in the same manner as in Example 1, except that the PET resin chip and the copolymerized polyester resin chip were blended in a 9: 1 ratio.
• Example 4
• a heat shrinkable film was manufactured in the same manner as in Example 4, except that the PET resin chip and the copolymerized polyester resin chip were blended in a 4: 6 ratio. Comparative Example 1
• a heat shrinkable filmol was prepared in the same manner as in Example 1, except that the copolymerized polyester resin chip was not used and only the PET resin chip was used. Test Example 1 Heat Shrinkage
• Thermal Shrinkage (%) 100x (length before shrinking-length after shrinking) / (length before shrinking)
• Test Example 2 Transmittance (transparency)
• the heat-shrink film prepared according to the above Examples and Comparative Examples was measured in the UV / Vis Spectrophotometer (Spectrophotometer / JASCO V530) by measuring the transmittance (%) at 400nm wavelength is shown in Table 1 below.
• the mixing ratio of polyethylene terephthalate (PET) and the copolymerized polyester of the invention it is possible to change the shrinkage rate and the shrinkage start temperature to the desired level, generally 1,4-cyclo Shrinkage starts higher and lower than when copolyester resin containing 30 mol% of nucleic acid dimethanol monomer compared to terephthalic acid is applied Because of the temperature, the shrinkage rate is slow and smooth process control is possible, thereby reducing the defective rate. Therefore, the heat shrinkable film forming composition may be molded through an extrusion and stretching process to obtain a heat shrinkable film product having excellent moldability.
• PET polyethylene terephthalate
• the copolymerized polyester of the invention it is possible to change the shrinkage rate and the shrinkage start temperature to the desired level, generally 1,4-cyclo Shrinkage starts higher and lower than when copolyester resin containing 30 mol% of nucleic acid dimethanol monomer compared to terephthalic acid is applied Because of the temperature, the shrinkage rate is

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• 2014
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