JP5619314B1 - Aluminum-deposited polyester film manufacturing treatment agent, aluminum-deposited polyester film manufacturing method, and packaging film - Google Patents

Abstract

[PROBLEMS] To produce an aluminum-deposited polyester film treatment agent and an aluminum-deposited polyester film that can be formed into a multilayer packaging film having excellent appearance and adhesion even when contacted with high-temperature steam or hot water. Methods and packaging films are provided. As a treating agent for producing an aluminum vapor-deposited polyester film, a treatment agent comprising a polyester resin having a number average molecular weight of 5,000 to 15000 composed of the following structural units A to D and an oxazoline-based crosslinking agent is used. . Structural unit A: aromatic dicarboxylic acid having 8 to 12 carbon atoms, ester-forming derivative of aromatic dicarboxylic acid having 8 to 12 carbon atoms, aliphatic dicarboxylic acid having 4 to 22 carbon atoms and aliphatic having 4 to 22 carbon atoms Constituent unit constitutional unit B formed from one or two or more selected from ester-forming derivatives of dicarboxylic acid: constitutional unit constitution formed from a trivalent or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms Unit C: a structural unit formed from an alkanediol having 2 to 10 carbon atoms, a structural unit D: a structural unit formed from a diol compound represented by the following chemical formula 1 (in the chemical formula 1, X1: in the molecule) Residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group composed of 2 to 30 oxybutylene units) [Selection] None

Description

  The present invention relates to a treatment agent for producing an aluminum vapor-deposited polyester film, a method for producing an aluminum vapor-deposited polyester film, and a packaging film. In recent years, a multilayer packaging film provided with an aluminum vapor deposition layer has been widely used for food packaging films in order to impart gas barrier properties. Such packaging film is also widely used in retort foods because it can be cooked while food is packaged. Generally, aluminum film is vapor-deposited on polyester film, and polyolefin film is laminated on the aluminum vapor-deposited surface. It has a structure. In such a multi-layer packaging film, in order to enhance the adhesion between the polyester film and the aluminum vapor deposition layer, a treatment agent for easy adhesion is generally applied to the polyester film.

  Conventionally, examples of using polyester and polyurethane at a predetermined ratio as a processing agent for producing an aluminum-deposited polyester film as described above (for example, refer to Patent Document 1), examples using polyurethane and / or polyester and an epoxy compound. (For example, refer patent document 2), The example (for example, refer patent document 3) using polyester and a melamine compound is proposed. However, for these conventional treatment agents, a multilayer packaging film is produced using the resulting aluminum vapor-deposited polyester film, and when this is brought into contact with high-temperature steam or hot water such as sterilization, the multilayer packaging film There are problems that interference fringes are generated on the film and the appearance is deteriorated, and the adhesion between the polyester film and the aluminum vapor deposition layer is deteriorated.

Japanese Patent Laid-Open No. 02-50837 Japanese Patent Laid-Open No. 04-176858 Japanese Patent Application Laid-Open No. 08-311221

  The problem to be solved by the present invention is a treatment agent for an aluminum vapor-deposited polyester film that can be formed into a multilayer packaging film having excellent appearance and adhesion even when contacted with high-temperature steam or hot water. The present invention provides a method for producing an aluminum-deposited polyester film and a packaging film.

  As a result of researches to solve the above-mentioned problems, the inventors of the present invention include a specific polyester resin composed of four specific structural units and an oxazoline-based crosslinking agent as a treatment agent for producing an aluminum vapor-deposited polyester film. It has been found that it is correctly preferred to use

That is, the present invention is to apply the treatment agent to the polyester film, by performing aluminum evaporation on its coated surface, a treatment agent used in producing aluminum-deposited polyester film, the structural unit A below reporting, configuration unit B The present invention relates to a treatment agent for producing an aluminum vapor-deposited polyester film, comprising a polyester resin having a number average molecular weight of 5000 to 15000, which is composed of structural unit C and structural unit D, and an oxazoline-based crosslinking agent. The present invention also relates to a method for producing an aluminum vapor-deposited polyester film using such a treatment agent for producing an aluminum vapor-deposited polyester film. It concerns on the packaging film bonded together.

  Structural unit A: aromatic dicarboxylic acid having 8 to 12 carbon atoms, ester-forming derivative of aromatic dicarboxylic acid having 8 to 12 carbon atoms, aliphatic dicarboxylic acid having 4 to 22 carbon atoms and aliphatic having 4 to 22 carbon atoms Structural units formed from one or more selected from ester-forming derivatives of dicarboxylic acids

  Structural unit B: a structural unit formed from a trivalent or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms

  Structural unit C: a structural unit formed from an alkanediol having 2 to 10 carbon atoms

  Structural unit D: a structural unit formed from a diol compound represented by the following chemical formula 1

In chemical formula 1,
X ¹ : a residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group composed of 2 to 30 oxybutylene units in the molecule

  First, the processing agent for aluminum vapor deposition polyester film manufacture (henceforth the processing agent of this invention) concerning this invention is demonstrated. The treatment agent of the present invention comprises a specific polyester resin and an oxazoline-based crosslinking agent, and the polyester resin used for the treatment agent of the present invention comprises the above-mentioned structural unit A, structural unit B, and structural unit. The number average molecular weight (gel permeation chromatography: polystyrene-equivalent number average molecular weight) composed of C and the structural unit D is 5000 to 15000. Such a polyester resin forms the structural unit D, the compound that forms the structural unit A, the compound that forms the structural unit B, the compound that forms the structural unit C, and the structural unit D. It is obtained by subjecting a compound to a condensation polymerization reaction. The number average molecular weight of such a polyester resin is 5,000 to 15,000, with 7000 to 10,000 being particularly preferable.

  The compounds that form the structural unit A include 1) carbon such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids of formula 8-12 2) Dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 1,4-naphthalenedicarboxylate Bis-2-hydroxyethyl phthalate, bis-2-hydroxyethyl isophthalate, bis-2-hydroxyethyl terephthalate, bis-2-hydroxyethyl-2,6-naphthalate, bis-2-hydroxyethyl-1,4 -Aromatic dicarboxylic acids having 8 to 12 carbon atoms such as naphthalate Ester-forming derivatives, 3) C4-C22 aliphatic such as succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecenylsuccinic acid, octadecenyldicarboxylic acid, cyclohexanedicarboxylic acid, etc. 4) Dicarboxylic acid, 4) Dimethyl succinate, Dimethyl adipate, Dimethyl azelate, Dimethyl sebacate, Dimethyl α, ω-Dodecane dicarboxylate, Dimethyl dodecenyl succinate, Dimethyl octadecenyl dicarboxylate, Dimethyl cyclohexanedicarboxylate, Bis succinate 2-hydroxyethyl, bis-2-hydroxyethyl adipate, bis-2-hydroxyethyl azelate, bis-2-hydroxyethyl sebacate, α, ω-dodecane dicarboxylic acid bis-2-hydroxyethyl, dodecenyl succinate 2-hydroxyethyl, octadecane Seni distearate acid bis-2-hydroxyethyl, ester forming derivatives of aliphatic dicarboxylic acids having a carbon number of 4-22 such as cyclohexane dicarboxylic acid bis-2-hydroxyethyl and the like.

  Examples of the compound that forms the structural unit B include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 3,3 ′. , 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 1,2,4-benzenetricarboxylic acid anhydride, 1,2,4,5-benzenetetracarboxylic acid 3 or 4 having 9 to 20 carbon atoms such as dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Valent aromatic polycarboxylic acid, and 1,2,4-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid are preferable.

  Examples of the compound that forms the structural unit C include 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octane. Examples thereof include alkanediols having 2 to 10 carbon atoms such as diol and 1,10-decanediol.

The compound that forms the structural unit D is a diol compound represented by the above-described chemical formula 1. X ^{1 in} Chemical Formula ¹ is a residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group composed of 2 to 30 oxybutylene units in the molecule. The case where it is a residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group composed of 10 to 20 oxybutylene units is preferable.

  The polyester resin used in the treatment agent of the present invention is composed of the structural units A to D described above, and there is no particular limitation on the structural ratio, but the structural unit A is 45 to 49.7 mol%, What has unit B in 0.3-5 mol%, 45-49.7 mol% of structural unit C, and 0.3-5 mol% (total 100 mol%) of structural unit D is preferable.

  The acid value of the polyester resin used in the treatment agent of the present invention is not particularly limited, but is preferably 10 to 20 KOHmg / g.

  The polyester resin used for the treatment agent of the present invention can be synthesized by the following method. 1) The structural unit C is formed with an ester-forming derivative of an aromatic dicarboxylic acid having 8 to 12 carbon atoms and an ester-forming derivative of an aliphatic dicarboxylic acid having 4 to 22 carbon atoms, which will form the structural unit A. A polybutylene having a polyoxybutylene group composed of 2 to 30 oxybutylene units in the molecule represented by Chemical Formula 1 which will form a structural unit D and an alkanediol having 2 to 10 carbon atoms. Carbon undergoes a transesterification reaction with glycol in the presence of a known polymerization catalyst, then conducts a condensation polymerization reaction while distilling off the low molecular weight compound under high temperature and high vacuum, and then forms the structural unit B. A method of depolymerization reaction with a tri- or tetravalent aromatic polycarboxylic acid of formula 9 to 20, transesterification-condensation polymerization-depolymerization method, 2) forming the structural unit A Forming a structural unit D with an aromatic dicarboxylic acid having 8 to 12 carbon atoms and an aliphatic dicarboxylic acid having 4 to 22 carbon atoms, an alkanediol having 2 to 10 carbon atoms to form the structural unit C After the polybutylene glycol having a polyoxybutylene group composed of 2 to 30 oxybutylene units in the molecule represented by Chemical Formula 1 is esterified in the presence of a known polymerization catalyst, A condensation polymerization reaction is performed while distilling off the low molecular weight compound under high vacuum, and then a depolymerization reaction is performed with a trivalent or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms that will form the structural unit B. , Esterification reaction-condensation polymerization-depolymerization method and the like.

  The treatment agent of the present invention comprises a polyester resin as described above and an oxazoline-based crosslinking agent. The oxazoline-based crosslinking agent is not particularly limited as long as it has an oxazoline group as a functional group in the molecule, but is preferably made of a polymer having an oxazoline group in the molecule. Such a polymer is synthesized by homopolymerization of a monomer having an oxazoline group in the molecule or copolymerization of a monomer having an oxazoline group in the molecule with another monomer. Monomers having an oxazoline group in the molecule include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like can be mentioned, and one or a mixture of two or more thereof can also be used. Of these, 2-isopropenyl-2-oxazoline is preferable as the oxazoline-based crosslinking agent. In addition, other monomers that will be copolymerized with a monomer having an oxazoline group in the molecule are not particularly limited as long as they are copolymerizable monomers. For example, 1) methyl acrylate, methyl methacrylate Acrylates and methacrylates such as ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylate-2-ethylhexyl, methacrylate-2-ethylhexyl, etc. 2) Acrylic acid, methacrylic acid, itacon Unsaturated carboxylic acids such as acid and maleic acid, 3) Unsaturated nitriles such as acrylonitrile and methacrylonitrile, 4) Unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide, 5 ) Vinyl acetate, propion Vinyl esters such as vinyl, 6) Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, 7) α-olefins such as ethylene and propylene, 8) Halogen-containing α and β such as vinyl chloride, vinylidene chloride and vinyl fluoride -Unsaturated monomers, 9) α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene. These can be used alone or as a mixture of two or more.

  In the treatment agent of the present invention, the content ratio of the polyester resin and the oxazoline crosslinking agent as described above is not particularly limited, but the polyester resin is 80 to 99.9% by mass and the oxazoline crosslinking agent is 0.1 to 20 mass. % (Total 100% by mass) is preferable.

  The treatment agent of the present invention is preferably one containing a nonionic surfactant in addition to the polyester resin and oxazoline-based crosslinking agent described above. Examples of such nonionic surfactants include 1) an alkylene oxide adduct of an aliphatic monohydric alcohol having 8 to 22 carbon atoms, 2) an alkylene oxide adduct of an alkylphenol having 4 to 18 carbon atoms in an alkyl group, and 3) carbon. Examples include alkylene oxide adducts of fatty acids of formula 8 to 22, and 4) a mixture of two or more selected from the above 1) to 3).

  In the treatment agent of the present invention, as the nonionic surfactant, 1) an aliphatic monohydric alcohol having 8 to 22 carbon atoms added with one or more alkylene oxides having 2 to 4 carbon atoms, 2 1) One or two or more of alkylene oxides having 2 to 4 carbon atoms added to alkylphenols having 4 to 18 carbon atoms in the alkyl group, 3) C2-4 alkylene to fatty acids having 8 to 22 carbon atoms What added 1 type or 2 types or more of an oxide etc. are mentioned.

  Examples of the aliphatic monohydric alcohol having 8 to 22 carbon atoms used for the synthesis of the above alkylene oxide adduct include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, and tetradecyl. Examples include alcohol, pentadecyl alcohol, hexadecyl alcohol, hexadecenyl alcohol, heptadecyl alcohol, octadecyl alcohol, and octadecenyl alcohol. The alkylphenol having 4 to 18 carbon atoms in the alkyl group used for the synthesis of the alkylene oxide adduct as described above includes butylphenol, hexylphenol, octylphenol, nonylphenol, decylphenol, undecylphenol, dodecylphenol, tridecyl. Phenol, tetradecylphenol, pentadecylphenol, hexadecylphenol, hexadecenylphenol, heptadecylphenol, octadecylphenol, octadecenylphenol, 2-ethylhexylphenol, 3,5,5-trimethylhexylphenol, etc. It is done. Further, the fatty acid having 8 to 22 carbon atoms used for the synthesis of the alkylene oxide adduct as described above includes octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, decane. Examples include acid, hexadecenoic acid, heptadecanoic acid, octadecanoic acid, octadecenoic acid, nonadecanoic acid, eicosanoic acid, eicosenoic acid, docosanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and the like.

  Examples of the alkylene oxide having 2 to 4 carbon atoms used for the synthesis of the alkylene oxide adduct include ethylene oxide, propylene oxide, 1,2-butylene oxide, and 1,4-butylene oxide. When two or more of these alkylene oxides are used, examples of the addition form of alkylene oxide include random addition, block addition, and random block addition.

  Nonionic surfactants to be used in the treatment agent of the present invention include those described above. Among them, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, hexadecenyl alcohol A compound having a number average molecular weight of 100 to 1500 obtained by adding ethylene oxide to an aliphatic monohydric alcohol having 12 to 18 carbon atoms such as heptadecyl alcohol, octadecyl alcohol, octadecenyl alcohol or the like is preferable.

  In the treatment agent of the present invention, the content ratio of the polyester resin, the oxazoline crosslinking agent and the nonionic surfactant described above is not limited, but the polyester resin is 80 to 99.8% by mass, and the oxazoline crosslinking agent is 0.00. What comprises 1-10 mass% and a nonionic surfactant in the ratio of 0.1-10 mass% (total 100 mass%) is preferable.

  In the treatment agent of the present invention, known additives can be used in combination as long as the effects of the present invention are not impaired. Examples of such additives include antioxidants, inorganic particles, organic particles, lubricants, antistatic agents, weathering agents, heat resistance agents, dyes, and pigments.

  The method for preparing the treatment agent of the present invention is not particularly limited. For example, when the treatment agent of the present invention is used with the above-described polyester resin, the above-described nonionic surfactant is dissolved in a mixed solvent of a hydrophilic organic solvent and water, and the hydrophilic organic solvent is distilled off from the solution. Then, an oxazoline compound can be added and mixed to prepare an aqueous dispersion. Examples of hydrophilic organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, lower alcohols such as ethylene glycol and diethylene glycol, ketones such as acetone and methyl isobutyl ketone, ethers such as butyl cellosolve, methyl cellosolve, and tetrahydrofuran. Among them, isopropyl alcohol is preferable. In addition, the aqueous dispersion of the treating agent of the present invention to be prepared preferably has a solid content concentration of 5 to 40% by mass in order to maintain stability for a long period of time. The average particle size is preferably 1 μm or less, more preferably 0.5 μm or less.

Next, the manufacturing method (henceforth the manufacturing method of this invention) of the aluminum vapor deposition polyester film which concerns on this invention is demonstrated. The production method of the present invention is a method in which the treatment agent of the present invention is applied to a polyester film so that the polyester resin in the treatment agent of the present invention is 5 to 500 mg / m ² and aluminum is deposited on the coated surface. is there.

  Examples of the polyester film used in the production method of the present invention include polyester films formed from polyesters such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, and polyethylene naphthalate, or copolymerized polyesters thereof.

  In the production method of the present invention, the polyester film to which the treatment agent of the present invention is applied is preferably the one before the crystal orientation is completed, and therefore the treatment agent of the present invention is applied in the production process of the polyester film. In this case, it is preferable to apply the polyester resin to an unstretched polyester film that has been cast by melting and extrusion, or to a polyester film that has been stretched in either the vertical or horizontal direction. When applying the treatment agent of the present invention to a polyester film, it is preferable to dry the applied coating, and then heat-set the coating by heating at a temperature of at least 200 ° C. for 2 seconds or more. Examples of methods for applying the treatment agent of the present invention to the polyester film include known roll coating methods, gravure coating methods, roll brush methods, spray coating methods, air knife coating methods, impregnation methods, curtain coating methods, and the like. It is done.

  In the production method of the present invention, as a method for depositing aluminum on the coated surface of the polyester film coated with the treating agent of the present invention, a known method such as a vacuum deposition method can be used. For example, in a high vacuum container, aluminum can be heat-deposited on the coated surface of the polyester film coated with the treatment agent of the present invention. Such aluminum vapor deposition is a small batch type or rolled polyester. It can be carried out by a continuous method in which vapor deposition is continuously performed on a film. Examples of the heating means for depositing aluminum include an electron beam heating method, a resistance heating method, and an induction heating method. The thickness of the deposited aluminum is preferably in the range of 20 angstroms to 1000 angstroms, more preferably 500 angstroms or less.

  Finally, the packaging film according to the present invention (hereinafter referred to as the packaging film of the present invention) will be described. The packaging film of the present invention is obtained by bonding a polyolefin film to an aluminum vapor-deposited surface of a polyester film obtained by the production method of the present invention via an adhesive.

In the packaging film of the present invention, the polyolefin film is a single layer or multilayer film made of a polyolefin resin. The polyolefin resin is obtained from 1) one selected from α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene-1, 1-octene and the like. Homopolymers such as polyethylene and polypropylene, 2) ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene obtained from two or more selected from α-olefins having 2 to 8 carbon atoms Α-olefin copolymers such as 1-hexene copolymer, 3) copolymers obtained from ethylene and vinyl acetate, and 4) copolymers obtained from ethylene and vinyl alcohol. The α-olefin copolymer of 2) above is a copolymer of ethylene and an α-olefin having 4 to 8 carbon atoms, and the content of units formed from the α-olefin having 4 to 8 carbon atoms. Is preferably from 3.5 to 50% by mass. In addition, the α-olefin copolymer of 2) can be obtained by a vapor phase method, a solution polymerization method, etc. using a known high activity Ziegler catalyst, a homogeneous catalyst such as a metallocene catalyst, etc. Those having a density of 0.86 to 0.94 g / cm ³ and an MFR of 0.01 to 20 g / 10 min are preferred. As the copolymer of 3), the content of units formed from vinyl acetate is 1 to 30% by weight, the density is 0.90 to 0.95 g / cm ³ , and the MFR is 0.1 to 10 g. What is / 10 minutes is preferable. The copolymer of 4) has a copolymerization ratio of ethylene of 20 to 50 mol%, a density of 1.1 to 1.3 g / cm ³ , and an MFR of 0.5 to 20 g / 10 minutes. Is preferred. The polyolefin resin described above may be used by mixing two or more kinds of polyolefin resins.

In the packaging film of the present invention, known adhesives can be used. Examples thereof include a polyurethane adhesive, an organic titanium anchor coating agent, an isocyanate anchor coating agent, and an adhesive resin, and among them, a polyurethane adhesive is preferable. The method for laminating the aluminum vapor-deposited polyester film and the polyolefin film with an adhesive is not particularly limited, and can be performed by a known laminating method. For this, for example, an adhesive is applied to a polyolefin film so that the coating amount is 0.1 to 10 g / m ² (solid content), and bonded with an aluminum vapor deposition surface of an aluminum vapor deposition polyester film with a nip roll, The method of leaving still at 30-50 degreeC for 12 to 60 hours and hardening an adhesive agent is mentioned.

  According to the present invention described above, there is an effect that even when contacted with high-temperature steam or hot water, a multilayer packaging film having excellent appearance and excellent adhesion can be obtained.

  Hereinafter, examples and the like will be given to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following examples and the like, parts indicate parts by mass, and% indicates mass%.

Test category 1 (synthesis of polyester resin)
Synthesis of polyester resin (P-1) 100.6 g of terephthalic acid (A-1), 83.9 g of isophthalic acid (A-2), 25.5 g of sebacic acid (A-3), neopentyl glycol (C-1 ) 63.1 g, ethylene glycol (C-2) 39.2 g, polybutylene glycol 27.8 g and zinc acetate (II) dihydrate 0.0645 g as an esterification catalyst were charged into the reaction vessel. After replacing with nitrogen, the reaction vessel was sealed and heated to 200 ° C. over 2 hours. Further, the temperature was raised to 240 ° C. over 2 hours while removing by-product water in the reaction vessel out of the system. Thereafter, the pressure in the reaction vessel was gradually returned to normal pressure, the temperature was raised to 250 ° C., and esterification was performed for 1 hour to obtain an esterified product. Next, after the temperature was raised to 270 ° C., the pressure inside the reaction vessel was gradually reduced to 100 Pa after 15 minutes, and after performing the condensation polymerization reaction for 2 hours under the same reduced pressure, the pressure was returned to normal pressure with nitrogen and cooled to 250 ° C. did. After cooling, 5.3 g of 1,2,5-benzenetricarboxylic acid (B-1) was added, the reaction vessel was sealed, pressurized to 0.3 MPa with nitrogen, and depolymerized for 1 hour with stirring. The polyester resin 300g was obtained. When this polyester resin was analyzed, 49.0 mol% of the structural unit A formed from terephthalic acid / isophthalic acid / sebacic acid and 1.0% of the structural unit B formed from 1,2,5-benzenetricarboxylic acid were analyzed. Mol%, having 49 mol% of the structural unit C formed from neopentyl glycol / ethylene glycol and 1.0 mol% of the structural unit D formed from polybutylene glycol, and having a number average molecular weight of 8000, The acid value was 16 KOHmg / g. This was designated as polyester resin (P-1).

Synthesis of polyester resins (P-2) to (P-12) and (rp-1) to (rp-4) In the same manner as the synthesis of polyester resin (P-1), polyester resins (P-2) to (P-12) and polyester resins (rp-1) to (rp-4) were synthesized. The above contents are summarized in Table 5.

In Table 1,
A-1: Terephthalic acid A-2: Isophthalic acid A-3: Sebacic acid A-4: Bis-2-hydroxyethyl terephthalate A-5: Adipic acid A-6: Dimethyl terephthalate A-7: Dimethyl isophthalate A-8: Dimethyl sebacate A-9: Dimethyl adipate B-1: 1,2,5-benzenetricarboxylic acid B-2: 1,2,4,5-benzenetetracarboxylic acid C-1: Neopentyl glycol C-2: ethylene glycol C-3: 1,3-propanediol C-4: 1,8-octanediol C-5: 1,4-butanediol D-1: oxytetramethylene D-2: oxytetramethylene D-3: Oxytetramethylene rd-1: Oxytrimethylene

Test category 2 (Preparation of aqueous dispersion of treatment agent for aluminum-deposited polyester film production)
Example 1 {Preparation of treating agent (S-1)}
54 parts of the polyester resin (P-1) synthesized in Test Category 1, 1.6 parts of 25% aqueous ammonia corresponding to 1.5 equivalents of an acid value of 16 KOHmg / g of the polyester resin (P-1), 2- A reaction vessel was charged with 54 parts of propanol, 154 parts of water, and 6.0 parts of ethylene oxide adduct of tetradecyl alcohol (number average molecular weight 600) (N-1), and heated to 80 ° C. with stirring to obtain a solution. It was. While stirring this solution, the inside of the reaction vessel was heated to distill off 93.6 parts of water and 2-propanol under normal pressure. (K-1) 24 parts was added to obtain an aqueous dispersion of the treatment agent (S-1) containing 27.0% polyester resin, 3.0% crosslinking agent and 3.0% nonionic surfactant. .

Examples 2 to 13 and Comparative Examples 1 to 6 {Preparation of aqueous dispersions of treatment agents (S-2) to (S-13) and (rs-1) to (rs-6)}
In the same manner as the preparation of the treating agent (S-1) of Example 1, the treating agents (S-2) to (S-13) of Examples 2 to 13 and the treating agent (rs-1) of Comparative Examples 1 to 6 were used. ) To (rs-6) aqueous dispersions and the like were prepared. The above contents are summarized in Table 2.

In Table 2,
P-1 to P-12, rp-1 to rp-4: Polyester resin synthesized in Test Category 1 K-1: Oxazoline-based crosslinking agent (trade name Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd.)
rk-1: Epoxy crosslinking agent (trade name Denacol EM-160 manufactured by Nagase ChemteX Corporation)
rk-2: Melamine-based crosslinking agent (trade name Nicalak MX-035 manufactured by Sanwa Chemical Co., Ltd.)
N-1: Ethylene oxide adduct of tetradecyl alcohol (number average molecular weight 600)
N-2: Dodecyl alcohol ethylene oxide adduct (number average molecular weight 450)
N-3: Ethylene oxide adduct of octadecyl alcohol (number average molecular weight 700)
N-4: Ethylene oxide adduct of hexadecyl alcohol (number average molecular weight 500)

Test category 3 (Production and evaluation of packaging film)
Example 14
After stretching an unstretched polyester film having a thickness of 200 μm 3.5 times in the longitudinal direction, the treatment agent (S-1) prepared in Test Category 2 was treated with 50 mg / kg of the polyester resin in the treatment agent (S-1). It was applied as a m ^2. After drying at 95 ° C. for 10 seconds, the film was stretched 4 times in the transverse direction and heat fixed at 220 ° C. for 10 seconds. Aluminum deposition was performed on the coating surface of the treatment agent (S-1) to a thickness of 500 angstroms, and urethane adhesive (Takelac A-626 / Takenate A-65 (both manufactured by Mitsui Chemicals, Inc.) was formed on the aluminum deposition surface. Product name) = 8/1 (mass ratio) was applied so that the solid content was 3 g / m ^2, and dried at 60 ° C. for 1 minute. Thereafter, an ethylene / propylene copolymer (density 0.900 g / cm ³ , MFR 8.0 g / 10 min) (H-1) with a thickness of 50 μm was bonded via an adhesive and allowed to stand at 40 ° C. for 50 hours. The adhesive was cured to obtain a packaging film. About the obtained packaging film, the external appearance and adhesiveness were evaluated by the following method.

-Appearance The appearance of the packaging film was visually observed and evaluated according to the following criteria. The packaging film was immersed in water at 100 ° C. for 30 minutes or 1 hour, dried at room temperature for 24 hours, and then the appearance after the hot water treatment was evaluated according to the same criteria.
◎: No change after immersion for 1 hour ○: No change after immersion for 30 minutes, but interference fringes occurred after immersion for 1 hour ×: Interference fringes occurred after immersion for 30 minutes

・ Easy adhesion The packaging film is cut into a 1.5cm wide strip, and peeled off between the treatment agent-coated surface and the aluminum vapor-deposited surface using Autograph AG-G (trade name, manufactured by Shimadzu Corporation). The force required for measurement was measured and evaluated according to the following criteria. Further, the packaging film was immersed in water at 100 ° C. for 30 minutes and dried at room temperature for 24 hours, and then the adhesion after the hot water treatment was evaluated according to the same criteria.
◎: 5 N / 1.5 cm or more ○: 3.5 N / 1.5 cm or more, less than 5 N / 1.5 cm Δ: 2 N / 1.5 cm or more, less than 3.5 N / 1.5 cm ×: less than 2 N / 1.5 cm

Examples 15 to 26 and Comparative Examples 7 to 12
In the same manner as in the production and evaluation of the packaging film of Example 14, the packaging films of Examples 15 to 26 and Comparative Examples 7 to 12 were produced and evaluated. The above contents are summarized in Table 3.

In Table 3,
S-1 to S-13, rs-1 to rs-6: Treatment agent prepared in Test Category H-1: Ethylene / propylene copolymer (density 0.900 g / cm ³ , MFR 8.0 g / 10 min)
H-2: ethylene / 1-hexene copolymer (density 0.930 g / cm ³ , MFR 1.0 g / 10 min)
H-3: Ethylene / 1-butene copolymer (density 0.920 g / cm ³ , MFR 2.1 g / 10 min)
H-4: Polyethylene (density 0.927 g / cm ³ , MFR 4.0 g / 10 min)
*: The polyester resin was not dispersed in the treatment agent and could not be applied to the polyester film.

Claims (11)

Applying a treatment agent to a polyester film, by performing aluminum evaporation on its coated surface, a treatment agent used in producing aluminum-deposited polyester film, the structural unit A below reporting, configuration unit B, the structural unit C and A treating agent for producing an aluminum vapor-deposited polyester film, comprising: a polyester resin having a number average molecular weight of 5000 to 15000 composed of a structural unit D; and an oxazoline-based crosslinking agent.
Structural unit A: aromatic dicarboxylic acid having 8 to 12 carbon atoms, ester-forming derivative of aromatic dicarboxylic acid having 8 to 12 carbon atoms, aliphatic dicarboxylic acid having 4 to 22 carbon atoms and aliphatic having 4 to 22 carbon atoms Structural unit formed from one or more selected from ester-forming derivatives of dicarboxylic acid Structural unit B: Structural unit formed from a trivalent or tetravalent aromatic polycarboxylic acid having 9 to 20 carbon atoms Unit C: a structural unit formed from an alkanediol having 2 to 10 carbon atoms Structural unit D: a structural unit formed from a diol compound represented by the following chemical formula 1

(In chemical formula 1,
X ¹ : a residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group composed of 2 to 30 oxybutylene units in the molecule)
  The treatment agent for producing an aluminum vapor-deposited polyester film according to claim 1, wherein the polyester resin has an acid value of 10 to 20 KOHmg / g.   The polyester resin contains 45 to 49.7 mol% of the structural unit A, 0.3 to 5 mol% of the structural unit B, 45 to 49.7 mol% of the structural unit C, and 0.3 to 5 mol of the structural unit D. % (Total 100 mol%). The treatment agent for producing an aluminum vapor-deposited polyester film according to claim 1 or 2.   The structural unit B of the polyester resin is a structural unit formed from 1,2,4-benzenetricarboxylic acid and / or 1,2,4,5-benzenetetracarboxylic acid. The processing agent for aluminum vapor deposition polyester film manufacture of description. The structural unit D of the polyester resin is a residue obtained by removing all hydroxyl groups from polybutylene glycol having a polyoxybutylene group in which X ^{1 in} Chemical Formula ¹ is composed of 10 to 20 oxybutylene units in the molecule. The treatment agent for producing an aluminum-deposited polyester film according to any one of claims 1 to 4, which is a case.   The aluminum according to any one of claims 1 to 5, comprising 80 to 99.9% by mass of a polyester resin and 0.1 to 20% by mass (total of 100% by mass) of an oxazoline-based crosslinking agent. Treatment agent for vapor deposition polyester film production.   Furthermore, the processing agent for aluminum vapor deposition polyester film manufacture containing a nonionic surfactant.   The treatment agent for producing an aluminum vapor-deposited polyester film according to claim 7, wherein the nonionic surfactant is one having a number average molecular weight of 100 to 1500 obtained by adding ethylene oxide to an aliphatic monohydric alcohol having 12 to 18 carbon atoms.   80 to 99.8% by mass of the polyester resin, 0.1 to 10% by mass of the oxazoline-based crosslinking agent, and 0.1 to 10% by mass (total of 100% by mass) of the nonionic surfactant. The processing agent for aluminum vapor deposition polyester film manufacture of Claim 7 or 8. The treatment agent for producing an aluminum vapor-deposited polyester film according to any one of claims 1 to 9, wherein the polyester resin in the treatment agent for producing an aluminum-deposited polyester film is 5 to 500 mg / m ² with respect to the polyester film. A method for producing an aluminum vapor-deposited polyester film, characterized in that aluminum is vapor-deposited on the coated surface.   A packaging film, wherein a polyolefin film is bonded to an aluminum vapor-deposited surface of an aluminum vapor-deposited polyester film obtained by the production method according to claim 10 with an adhesive.