JP2016011324A - Polyester resin composition for barrier material and barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition for a barrier material having solubility in a general-purpose solvent such as ethyl acetate, methylethyl ketone or the like and mainly containing a polyester resin with excellent gas barrier properties, and a barrier material film where the resin composition is applied to a film.SOLUTION: The problem is solved by providing a polyester resin composition for barrier material containing bifunctional isocyanate group-containing curing agent having a specific structure and a molecular weight of 600 or more and polyester polyol.

Description

  The present invention relates to a resin composition capable of providing a film having excellent gas barrier properties, and a barrier film formed by curing the resin composition.

  Packaging materials used for packaging food and beverages have functions such as strength, resistance to cracking, retort resistance, and heat resistance to protect the contents from various distribution, storage such as refrigeration and heat sterilization. In addition to this, a wide variety of functions are required such as excellent transparency so that the contents can be confirmed. On the other hand, when the bag is sealed by heat sealing, an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material. In particular, a high barrier property is required for the purpose of maintaining the quality of the contents. Such a barrier packaging material is usually used as a composite flexible film in which different polymer materials are laminated.

  When imparting a barrier function to a multilayer film, unstretched polyolefin films used for the inner layer (sealant side) have poor gas barrier properties and are difficult to impart a barrier function by coating or vapor deposition. Therefore, a barrier function is often imparted to various films (polyester resins such as polyethylene terephthalate (hereinafter abbreviated as PET), polyamide resins, stretched polyolefin resins) used on the outer layer side.

  In the case of providing a barrier function to these outer layer side films by coating, vinylidene chloride having high retort resistance and gas barrier properties has been frequently used as a barrier coating material, but there are problems such as generation of dioxin during disposal firing. is there. In addition, when a polyvinyl alcohol resin or ethylene-polyvinyl alcohol copolymer is used as a barrier coating material, the gas barrier property is high at low humidity, but the gas barrier property is remarkably lowered at high humidity, after boil treatment or after retort treatment. there were. In addition, a film provided with a vapor deposition layer of a metal oxide such as silica or alumina as a gas barrier layer is expensive and has a problem that the flexibility is poor and the barrier performance varies due to cracks and pinholes.

  As a gas barrier material, for example, in Patent Document 1, a gas barrier property using an aqueous dispersion containing a gas barrier polyurethane resin having a urethane group and a urea group and having a total of a urethane group concentration and a urea group concentration of 15% by mass or more. A polyurethane resin and a gas barrier film containing the same are described. However, since the aqueous dispersion has no water resistance, there is a problem in using it in foods, beverages and the like containing water.

  Further, for example, in Patent Document 2, a thermosetting gas barrier polyurethane resin containing a cured resin obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B), The skeleton structure derived from meta-xylene diisocyanate is contained in an amount of 20% by mass or more, and the ratio of the trifunctional or higher compound in the (A) and (B) is based on the total amount of (A) and (B). And a gas barrier composite film using a thermosetting gas barrier polyurethane resin characterized by being 7 mass% or more.

  However, since the composition must use a highly polar solvent, the workability is poor. For example, when a highly soluble solvent such as acetone is used, there is a problem that the viscosity of the preparation is likely to increase due to the reaction between water and isocyanate because the boiling point is low and the water in the outside air is easily taken up.

Japanese Patent No. 4524463 Japanese Patent No. 4054972

  In view of the above prior art, the problem to be solved by the present invention is a polyester resin composition for a barrier material mainly composed of a polyester resin that is soluble in general-purpose solvents in ethyl acetate, methyl ethyl ketone, and the like, and is excellent in gas barrier properties. And a barrier material film in which the resin composition is applied to the film.

  The present inventors have solved the above problems with a polyester resin composition for a barrier material comprising a bifunctional isocyanate group-containing curing agent and a polyester polyol.

  That is, the present invention provides a polyester resin composition for a barrier material comprising a bifunctional isocyanate group-containing curing agent having a molecular weight of 600 or more represented by the general formula (A) and a polyester polyol.

In formula (A), R ₁ is represented by general formula (1).

(In the formula, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3- An arylene group selected from the group consisting of an anthraquinonediyl group and a 2,3-anthracenediyl group, or a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group which may have a substituent Represents a group obtained by a hydrogenation reaction of an arylene group selected from the group consisting of 2,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms) Represents a group represented by
The present invention includes a gas barrier material having a barrier property against a gas that is a gas at normal temperature and pressure, and a water vapor barrier material having a barrier property to water vapor as a barrier material, but the barrier effect against gas or water vapor is confirmed. If it is done, the barrier material to the object considered to express barrier property naturally is also included.

  According to the present invention, it is possible to provide a polyester resin composition for a barrier material that is excellent in solubility in a general-purpose solvent in ethyl acetate, methyl ethyl ketone, and the like and excellent in gas barrier properties.

  The present invention also includes a gas barrier film composed of a resin layer obtained by curing the polyester resin composition for a barrier material. This film is not limited as long as it is a gas barrier composite film having at least a layer formed by curing the polyester resin composition for a barrier material and a base film layer.

(Bifunctional isocyanate group-containing curing agent)
Curing agent for use in the present invention, the entire serial formula (A), R ₁ is represented by the general formula (2).

In formula (A), R ₁ is represented by general formula (1).

  (In the formula, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3- An arylene group selected from the group consisting of an anthraquinonediyl group and a 2,3-anthracenediyl group, or a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group which may have a substituent Represents a group obtained by a hydrogenation reaction of an arylene group selected from the group consisting of 2,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms) Represents a group represented by

In formula (A), R ₂ is selected from the group consisting of a tolylene group, a phenylene group, a phenylenediyl group, a methylenediphenylene group, a naphthylene group, an anthraquinonediyl group, and an anthracenediyl group, which may have a substituent. Hydrogenation reaction of an arylene group selected from the group consisting of an arylene group or an optionally substituted tolylene group, phenylene group, phenylenediyl group, naphthylene group, methylenediphenylene group, anthraquinonediyl group, and anthracenediyl group In particular, aromatic groups are preferably a tolylene group, a xylylene group, a diphenylmethane group, a naphthylene group, an aliphatic hydrogenated xylylene group, a hydrogenated diphenylmethane group (dicyclohexylmethane group), a hydrogenated naphthylene group, and the like. desirable.

  More specifically, a bifunctional polyester and an isocyanate compound can be reacted to form a bifunctional curing agent.

  As the isocyanate compound, either aromatic or aliphatic diisocyanate may be used. For example, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate can be used.

Moreover, you may mix the following well-known hardening | curing agents with the hardening | curing agent used by this invention.
The curing agent is not particularly limited as long as it can react with the hydroxyl group of the polyester resin, and a known curing agent such as polyisocyanate or epoxy compound can be mixed.

  Examples of the polyisocyanate compound that can be mixed include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amounts and, for example, ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, sorbitol, ethylenediamine, monoethanolamine, Diethanolamine, triethanol Examples include adducts obtained by reacting low molecular active hydrogen compounds such as amines and metaxylylenediamines and their alkylene oxide adducts, various polyester resins, polyether polyols, and high molecular active hydrogen compounds of polyamides. .

  It is preferable that the curing agent is the bifunctional isocyanate group-containing curing agent. When the curing agent further includes a metaxylene skeleton or a tolylene skeleton, gas barrier properties are improved by π-π stacking of aromatic rings as well as hydrogen bonding of urethane groups. It is preferable because it can be used.

  The isocyanate compound may be a blocked isocyanate. As the isocyanate blocking agent, for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam, and other aromatic amines, imides, acetylacetate. , Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, and also such as diaryl compounds sodium bisulfite. The blocked isocyanate can be obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.

(Bifunctional polyester resin compound)

(In the formula, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3- An arylene group selected from the group consisting of an anthraquinonediyl group and a 2,3-anthracenediyl group, or a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group which may have a substituent Represents a group obtained by a hydrogenation reaction of an arylene group selected from the group consisting of 2,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms) Represents a group represented by

(Polyester resin compound having glycerol skeleton)

In the general formula (2), R _{3 to} R ₅ are each independently a hydrogen atom or the general formula (3).

(However, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinone. Represents an arylene group selected from the group consisting of a diyl group and a 2,3-anthracenediyl group, Y represents an alkylene group having 2 to 6 carbon atoms), and R _{1 to} R ₃ At least one of them represents a group represented by the general formula (3). )
It is group represented by these.

In the general formula (2), at least one of R ₃ , R ₄ and R ₅ needs to be a group represented by the general formula (3). Among them, it is preferable that all of R ₃ , R ₄ and R ₅ are groups represented by the general formula (3).

In addition, a compound in which any one of R ₃ , R ₄ and R ₅ is a group represented by the general formula (3), and any _{two of} R ₁ , R ₂ and R ₃ are the general formula (3). Any two or more compounds of the compound represented by the formula and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (3) are mixed. Also good.

  X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, The arylene group which may have is represented. When X is substituted with a substituent, it may be substituted with one or more substituents, which are attached to any carbon atom on X that is different from the free radical. Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  In the general formula (3), Y represents ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl-1,5-pentylene group, 1,6-hexylene group, methylpentylene. Represents an alkylene group having 2 to 6 carbon atoms, such as a len group or a dimethyl butylene group; Among them, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

  The polyester resin compound having a glycerol skeleton represented by the general formula (2) includes glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position, or an anhydride thereof, and a polyhydric alcohol component. Obtained by reacting as a component.

  The aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position or its anhydride include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its An anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, 2,3-anthracene carboxylic acid or its anhydride, etc. are mentioned. These compounds may have a substituent on any carbon atom of the aromatic ring. Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

  Examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms. For example, diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, etc. Can be illustrated.

  As such a polyester resin compound having a glycerol skeleton represented by the general formula (2), a polyester resin (orthophthalic anhydride as an aromatic polyvalent carboxylic acid and ethylene glycol as a polyhydric alcohol ( GLY (oPAEG) m, where m represents the total number of groups in parentheses contained in the polyester resin composition of the present invention), naphthalene 2,3-dicarboxylic acid is used as the aromatic polyvalent carboxylic acid, Polyester resin using ethylene glycol as alcohol (abbreviated as GLY (oNAEG) m, m is as defined above) and the like.

(Method for calculating mass of solid content of polyester resin composition for barrier material)
The mass excluding the mass of the diluent solvent, the mass of the volatile component contained in the curing agent, and the inorganic component from the mass part of the polyester resin composition for a barrier material is defined as the mass of the total solid content of the adhesive resin.

  On the other hand, the aromatic polyvalent carboxylic acid in which the acyl group as the raw material of the polyester component is substituted in the ortho position or its anhydride has an asymmetric structure. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and thus it is presumed that the gas barrier property is excellent. In addition, it is presumed that due to this asymmetric structure, the crystallinity that inhibits the adhesion to the substrate is low, so that it exhibits high solubility in solvents such as ethyl acetate and methyl ethyl ketone and is excellent in gas barrier properties.

(Polyhydric alcohol)
In the polyester resin compound used in the present invention, a polyhydric alcohol component other than an alkylene diol having 2 to 6 carbon atoms may be copolymerized as a polyhydric alcohol as long as the effects of the present invention are not impaired. Specifically, aliphatic polyhydric alcohols such as glycerol, erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, Cycloaliphatic polyhydric alcohols such as cyclohexanedimethanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or the like Examples thereof include ethylene oxide elongated products and hydrogenated alicyclic groups.

(Polyvalent carboxylic acid)
The polyester resin of the present invention essentially comprises an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position or an anhydride thereof as the polyvalent carboxylic acid component, but within the range not impairing the effects of the present invention, A polyvalent carboxylic acid component may be copolymerized. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polyvalent carboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its anhydride, 1,2-bis ( Phenoxy) ethane-p, p′-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; Polybasic acids such as droxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.

  Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid, and diphenic acid are preferable.

  As a specific example of the production method, glycerol used as a raw material, an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component are collectively charged, The temperature is raised while stirring and mixing to cause a dehydration condensation reaction. 1 mgKOH / g or less by the acid value measurement method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measurement method described in JIS-K0070 is the value on the right side of the following formula (b) (mgKOH / The desired polyester resin can be obtained by continuing the reaction until it is within ± 5% of g).

(In formula (a), Mn represents the theoretical number average molecular weight of a predetermined bifunctional polyester resin)

(In formula (b), Mn represents a theoretical number average molecular weight of a predetermined N (N is a natural number of 1 or more) functional polyester resin)
Alternatively, each raw material may be reacted in multiple stages. Moreover, you may prepare so that a hydroxyl value may enter into less than +/- 5%, adding the diol component which volatilized at reaction temperature.

  Examples of the catalyst used in the reaction include acids such as tin-based catalysts such as monobutyltin oxide and dibutyltin oxide, titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate, and zirconia-based catalysts such as tetra-butyl-zirconate. A catalyst is mentioned. It is preferable to use a combination of the titanium-based catalyst such as tetra-isopropyl-titanate and tetra-butyl-titanate, which has high activity for ester reaction, and the zirconia catalyst. The catalyst amount is used in an amount of 1 to 1000 ppm, more preferably 10 to 100 ppm, based on the total mass of the reaction raw material used. If it is less than 1 ppm, it is difficult to obtain an effect as a catalyst, and if it exceeds 1000 ppm, the subsequent urethanization reaction tends to be inhibited.

  The number average molecular weight of the polyester resin compound having a glycerol skeleton is preferably 450 to 5,000, more preferably 450 to 2,000.

  As the curing agent, the above-mentioned bifunctional isocyanate is preferable, can give an appropriate reaction time, and is particularly excellent in solubility, barrier ability, and adhesion ability. The urethane group concentration at this time is preferably in the range of 1.0 to 6.0 mmol / g.

  The bifunctional polyester resin compound or the polyester resin compound having a glycerol skeleton used in the present invention preferably has a glass transition temperature in the range of −30 ° C. to 70 ° C. More preferably, it is −20 ° C. to 50 ° C. When the glass transition temperature is too higher than 70 ° C., the flexibility of the polyester resin near room temperature tends to be low, and the adhesion to the substrate tends to be poor. On the other hand, when the temperature is too low at -30 ° C, there is a possibility that sufficient gas barrier properties may not be obtained due to the intense molecular motion of the polyester resin near room temperature.

  Moreover, when carboxylic acid remains at the terminal of the polyester resin used in the present invention, an epoxy compound can be mixed as an auxiliary curing agent. Examples of epoxy compounds include diglycidyl ether of bisphenol A and oligomers thereof, diglycidyl ether of hydrogenated bisphenol A and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride. Glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether , Pentaerythritol tetraglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like.

  When an epoxy compound is used as an auxiliary curing agent, a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing within a range that does not impair the gas barrier property that is the object of the present invention.

  The polyester resin compound having the glycerol skeleton and the curing agent are such that the ratio of the polyester resin compound having the glycerol skeleton and the curing agent is 1 / 0.0. It is preferable to mix | blend so that it may become 5/5 (equivalent ratio), More preferably, it is 1 / 1-1 / 3. If the curing agent component is excessive beyond this range, the surplus curing agent component may remain and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.

  The said hardening | curing agent can also use together the well-known hardening | curing agent or accelerator selected according to the kind. Examples of the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.

(Other ingredients)
The polyester resin composition of the present invention may contain various additives as long as the gas barrier property is not impaired. Examples of additives include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, Examples thereof include an antistatic agent, a lubricant, an antiblocking agent, a colorant, a filler, and a crystal nucleating agent. Examples of swellable inorganic layered compounds include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), antigolite group clay minerals (anti Golite, chrysotile, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (white mica, Mica such as phlogopite, margarite, tetrasilic mica, teniolite, etc.). These minerals may be natural clay minerals or synthetic clay minerals. The swellable inorganic layered compounds are used alone or in combination of two or more.

  Moreover, a well-known acid anhydride can also be used together as a method of improving the acid resistance of a cured coating film. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.

  Moreover, you may add the compound etc. which have an oxygen trap function further as needed. Examples of the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, and a rosin resin, as needed. When adding these, the range of 0.01-5 mass parts is preferable with respect to 100 mass parts of total amounts of a polyester resin and a bifunctional diisocyanate group containing hardening | curing agent.

(Form of gas barrier film obtained by curing polyester resin composition)
The gas barrier film obtained by curing the polyester resin composition of the present invention can be obtained by applying and curing a polyester resin composition coating liquid on a film serving as a substrate. The coating liquid may be either a solvent type or a solventless type. In the case of the solvent type, the solvent is used as a reaction medium during the production of the polyester resin and the curing agent, and is further used as a diluent during coating. Examples of solvents that can be used include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. In particular, since the polyester resin composition of the present invention is excellent in solubility in ethyl acetate or methyl ethyl ketone solvent, it is preferable to use ethyl acetate or methyl ethyl ketone.

  The method for applying the polyester resin of the present invention is not particularly limited, and may be performed by a known method. For example, in the case of a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method or the like. Moreover, when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating. When using a roll coater, the coating is preferably performed in a state of being heated from room temperature to about 120 ° C. so that the viscosity of the polyester resin composition for a barrier material of the present invention is about 500 to 2500 mPa · s.

  The polyester resin composition of the present invention can also be used as a polyester resin composition for barrier materials for various applications that require gas barrier properties against polymers, paper, metals, etc. as a polyester resin composition for barrier materials. Hereinafter, a polyester resin composition for a barrier material for film lamination will be described as one specific application.

  The gas barrier film obtained by curing the polyester resin composition of the present invention can be used as a gas barrier film for film lamination.

  The film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application. For food packaging, for example, PET film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched polypropylene film, OPP: Polyolefin film such as biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.

  Moreover, you may perform various surface treatments, such as a flame treatment and a corona discharge treatment, as needed so that the adhesive layer without defects, such as a film | membrane piece and a repellency, may be formed in the film surface.

A gas barrier obtained by curing the polyester resin composition for a barrier material of the present invention obtained by applying a polyester resin composition for a barrier material of the present invention to one of the thermoplastic resin films and then passing through a drying step and an aging step. A gas barrier film can be obtained by laminating the other thermoplastic resin film and laminating them by lamination using a known dry laminate adhesive. As the lamination method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used. Specifically, the dry lamination method is such that the polyester resin composition for a barrier material of the present invention is applied to one of the base films by a gravure roll method, and then the other base film is stacked to dry lamination (dry lamination method). ). The temperature of the laminate roll is preferably about room temperature to 60 ° C. Non-solvent lamination is applied immediately after applying the polyester resin composition for a barrier material of the present invention, which has been heated to room temperature to about 120 ° C., on a base film with a roll such as a roll coater heated to room temperature to about 120 ° C. A laminate film can be obtained by attaching a new film material to the surface. The laminating pressure is preferably about 10 to 300 kg / cm ² .

  In the case of the extrusion laminating method, an organic solvent solution of the polyester resin composition for a barrier material of the present invention is applied to a base film as an adhesion aid (anchor coating agent) by a roll such as a gravure roll, and the temperature is from room temperature to 140 ° C. A laminate film can be obtained by laminating a polymer material melted by an extruder after drying and curing the solvent. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.

  The gas barrier film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging conditions are from room temperature to 80 ° C. and for 12 to 240 hours. During this time, the polyester resin and the curing agent react to produce adhesive strength.

  In the present invention, in order to provide a higher barrier function, a film in which a vapor-deposited layer of metal or metal oxide is laminated may be used as necessary. In particular, the cured resin of the present invention is characterized by excellent adhesion to a metal or metal oxide surface and compatibility with gas barrier properties. Although any metal can be used for metal vapor deposition or metal oxide vapor deposition, aluminum, tin, silicon, zirconium, magnesium, gold, silver, copper, or an oxide containing these oxides is preferable.

  The polyester resin composition for a barrier material of the present invention can be preferably used as a polyester resin composition for a barrier material for a laminated film formed by bonding a plurality of the same or different resin films. The resin film may be appropriately selected depending on the purpose. For example, when used as a packaging material, the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene. (Hereinafter abbreviated as CPP), a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP A three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP A composite film composed of four layers using a thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material, particularly as an oxygen and water vapor barrier film. Thus, the use of the polyester resin composition for a barrier material of the present invention is not limited to PET / CPP films and can be widely used.

  Since the polyester resin composition for a barrier material of the present invention is characterized by having a high gas barrier property, a laminate film formed from the polyester resin composition for a barrier material is a PVDC coating layer or a polyvinyl alcohol (PVA) coating. Without using commonly used gas barrier materials such as layers, ethylene-vinyl alcohol copolymer (EVOH) film layers, metaxylylene adipamide film layers, inorganic vapor deposited film layers deposited with alumina, silica, etc. A very high level of gas barrier properties is manifested. Moreover, the gas barrier property of the obtained film can also be remarkably improved by using together as the polyester resin composition for barrier materials which bonds these conventional gas barrier materials and sealant materials together.

  Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on mass.

<Example of polyester production>
Production Example 1 Production Method of Polyester Resin “GLY (oPAEG) 1” Composed of Glycerol, Orthophthalic Acid, and Ethylene Glycol , 148.1 parts of phthalic anhydride, 64.57 parts of ethylene glycol, and 0.03 part of titanium tetraisopropoxide, and gradually heat the inner temperature of the rectifying tube so that the temperature does not exceed 100 ° C. Maintained at 220 ° C. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated. ) 1 ”was obtained. The mass% of glycerol contained in this polyester resin was 89.07 / 284.26 = 31.33%.

Production Example 2 Production Method of Polyester Resin “GLY (oPAEG) 2” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, 92.09 parts of glycerol , 296.2 parts of phthalic anhydride, 124.1 parts of ethylene glycol and 0.05 part of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectifying tube does not exceed 100 ° C. Maintained at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY having a theoretical number average molecular weight of 476.43 calculated from the designed functional group number N = 3, hydroxyl value = 353.3, and hydroxyl value was obtained. (OPAEG) 2 ”was obtained. The mass% of glycerol contained in this polyester resin was 18.69%.

Production Example 3 Production Method of Polyester Resin “GLY (oPAEG) 3” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, 92.09 parts of glycerol , 443.36 parts of phthalic anhydride, 186.21 parts of ethylene glycol, and 0.07 part of titanium tetraisopropoxide, and gradually heat the inner temperature of the rectifying tube so that the upper temperature does not exceed 100 ° C. Maintained at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY having a theoretical number average molecular weight of 668.60 calculated from the designed functional group number N = 3, hydroxyl value = 251.7, and hydroxyl value. (OPAEG) 3 ”was obtained. The mass% of glycerol contained in this polyester resin was 13.32%.

(Production Example 4) Polyester resin composed of glycerol, orthophthalic acid, and ethylene glycol “GLY (oPAEG) 6” production method 92.09 parts of glycerol in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, snider pipe, and condenser , 888.72 parts of phthalic anhydride, 372 parts of ethylene glycol, and 0.13 part of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. Held on. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated. A polyester resin “GLY” having a designed functional group number N = 3, a hydroxyl value = 13.5, and a theoretical number average molecular weight of 1244.510 calculated from the hydroxyl value. (OPAEG) 6 ”was obtained. The mass% of glycerol contained in this polyester resin was 7.15%.

Production Example 5 Production Method of Polyester Resin “GLY (oNAEG) 2” Consisting of Glycerol, 2,3-Naphthalenedicarboxylic Acid, and Ethylene Glycol Into a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, glycerol 90.09 parts, 396.34 parts of 2,3-naphthalenedicarboxylic anhydride, 124.14 parts of ethylene glycol, and 0.06 parts of titanium tetraisopropoxide, and the upper temperature of the rectification tube does not exceed 100 ° C The internal temperature was kept at 220 ° C. by gradually heating. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY having a theoretical number average molecular weight of 592.59 calculated from the designed functional group number N = 3, hydroxyl value = 284.0, and hydroxyl value. (ONAEG) 2 ”was obtained. The mass% of glycerol contained in this polyester resin was 15.03%.

Production Example 6 Production Method of Polyester Resin “EGoPA” Composed of Orthophthalic Acid and Ethylene Glycol In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, snider pipe, condenser, 396.34 parts of phthalic anhydride, ethylene glycol 173. 73 parts and 0.05 part of titanium tetraisopropoxide were charged, and the inner temperature was kept at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester resin “oPAEG” having a design functional group number N = 2, a hydroxyl value = 187.0, and a theoretical number average molecular weight 600 calculated from the hydroxyl value was obtained. Obtained. The mass% of glycerol contained in this polyester resin was 0.0%.

Production Example 7 Glycerol, Isophthalic Acid, and Ethylene Glycol Polyester Resin “GLY (iPAEG) 3” Manufacturing Method In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser, 92.09 parts of glycerol and isophthal Acid 498.39 parts, ethylene glycol 186.21 parts, and titanium tetraisopropoxide 0.07 parts are charged, and the inner temperature of the rectifying tube is gradually increased to 220 ° C. so that the upper temperature of the rectification tube does not exceed 100 ° C. Retained. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY having a theoretical number average molecular weight of 668.6 calculated from the designed functional group number N = 3, hydroxyl value = 251.7, and hydroxyl value. (IPAEG) 3 ”was obtained. The mass% of glycerol contained in this polyester resin was 13.32%.

(Production Example 8) Polyester polyol consisting of trimethylolpropane, orthophthalic anhydride and ethylene glycol “TMP (oPAEG) 3” production method Except for replacing glycerol 92.09 in Production Example 3 with 134.17 parts of trimethylolpropane In the same manner as in Production Example 3, a number average molecular weight 710.68 polyester polyol “TMP (oPAEG) 3” was obtained.
The mass% of glycerol contained in this polyester polyol was 0.0%.

(Production Example 9) Polyester polyol “TMP (oPAEG) 6” composed of trimethylolpropane, orthophthalic anhydride and ethylene glycol Production method Production Example 4 was replaced with 134.17 parts of trimethylolpropane instead of 92.09 parts of glycerol. The polyester polyol “TMP (oPAEG) 6” having a theoretical number average molecular weight of 1287.18 calculated from the design functional group number N = 3, the hydroxyl value = 236.8, and the hydroxyl value was obtained in the same manner as in Production Example 4. .
The mass% of glycerol contained in this polyester polyol was 0.0%.

(Production Example 10) Production Method of Polyester Resin “GLY3oPA4EG2” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol 276.27 parts of glycerol, phthalic anhydride in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser 592.4 parts, 130.2 parts of ethylene glycol, and 0.09 parts of titanium tetraisopropoxide are charged, and the inner temperature is kept at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube does not exceed 100 ° C. did. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated. A polyester resin “GLY3oPA4EG2” having a designed functional group number N = 5, a hydroxyl value = 304.6, and a theoretical number average molecular weight 920.89 calculated from the hydroxyl value. " Since this polyester resin has an average of 3 glycerols per molecule, the glycerol mass% this resin has was (89.07 × 3) /920.89=29.02%.

Production Example 11 Production Method of Polyester Resin “GLY3oPA7EG5” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol 276.27 parts of glycerol, phthalic anhydride in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser Charge 1036.84 parts, ethylene glycol 325.87 parts, and titanium tetraisopropoxide 0.16 parts, and gradually heat the rectifying tube so that the upper temperature does not exceed 100 ° C, and keep the internal temperature at 220 ° C. did. When the acid value reached 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY3oPA7EG5 having a theoretical number average molecular weight of 1497.46 calculated from the designed functional group number N = 5, hydroxyl value = 187.3, and hydroxyl value. " Since this polyester resin has an average of 3 glycerols per molecule, the glycerol mass% possessed by this resin was (89.07 × 3) /1497.46=17.84%.

Production Example 12 Production Method of Polyester Resin “GLY5oPA8EG4” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol 460.45 parts of glycerol and phthalic anhydride in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, snider pipe, and condenser 1185 parts, 260.09 parts of ethylene glycol, and 0.19 part of titanium tetraisopropoxide were charged, and the inner temperature was kept at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester resin “GLY5oPA8EG4 having a theoretical number average molecular weight of 1749.70 calculated from the designed functional group number N = 7, hydroxyl value = 224.4, and hydroxyl value. " Since this polyester resin has an average of 3 glycerols per molecule, the glycerol mass% possessed by this resin was (89.07 × 5) /1749.70=25.45%.

Production Example 13 Production Method of Polyester Resin “GLY3oHHPA4EG2” Consisting of Glycerol, Hexahydrophthalic Acid, and Ethylene Glycol 276.27 parts of glycerol in an anhydrous polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser Charge 616.64 parts of hexahydrophthalic acid, 130.2 parts of ethylene glycol, and 0.19 parts of titanium tetraisopropoxide, and gradually heat the inner temperature of the rectifying tube so that the upper temperature does not exceed 100 ° C. Maintained at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and the polyester resin “GLY3oHHPA4EG2” had a designed functional group number N = 5, a hydroxyl value = 296.8, and a theoretical number average molecular weight of 945.05 calculated from the hydroxyl value. " Since this polyester resin has an average of 3 glycerols per molecule, the glycerol mass% possessed by this resin was (89.07 × 3) /945.05=28.27%.

Production Example 14 Production Method of Polyester Resin “GLY3oMHPA4EG2” Consisting of Glycerol, 4-Methylhexahydrophthalic Acid, and Ethylene Glycol Glycerol is 276.27 in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a Snyder tube, and a condenser. Part, 4-methylhexahydrophthalic anhydride 672.76 parts, ethylene glycol 130.2 parts, and titanium tetraisopropoxide 0.19 parts, and gradually the rectifier top temperature does not exceed 100 ° C The internal temperature was kept at 220 ° C. by heating. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester resin “GLY3oMHPA4EG2” having a designed functional group number N = 5, a hydroxyl value = 280.2, and a theoretical number average molecular weight of 1001.17 calculated from the hydroxyl value. " Since this polyester resin has an average of 3 glycerols per molecule, the glycerol mass% possessed by this resin was (89.07 × 3) /1001.17=26.553%.

Production Example 15 Production Method of Polyester Resin “GLY (oPAPG) 3” Consisting of Glycerol, Orthophthalic Acid, and 1,3-Propanediol 186.21 parts of ethylene glycol used in Production Example 3 is replaced with 1,3-propanediol part Except for the change, the same as in Production Example 3,
A polyester resin “GLY (oPAPG) 3” having a designed functional group number N = 3, a hydroxyl value = 236.8, and a theoretical number average molecular weight of 710.68 calculated from the hydroxyl value was obtained. The mass% of glycerol contained in this polyester resin was 12.53%.

Production Example 16 Production Method of Polyester Resin “GLY (oPAHG) 3” Consisting of Glycerol, Orthophthalic Acid, and 1,6 Hexanediol 186.21 parts of ethylene glycol used in Production Example 3 is 389.96 of 1,6-hexanediol In the same manner as in Production Example 3 except that
A polyester resin “GLY (oPAHG) 3” having a designed functional group number N = 3, a hydroxyl value = 201.1, and a theoretical number average molecular weight of 668.60 calculated from the hydroxyl value was obtained. The mass% of glycerol contained in this polyester resin was 10.64%.

(Production Example 17) Polyester solution A production method of polyester resin “EGoPA” composed of orthophthalic acid and ethylene glycol A polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, condenser, 396.34 parts of phthalic anhydride, 173.73 parts of ethylene glycol and 0.05 parts of titanium tetraisopropoxide were charged, and the inner temperature was kept at 220 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated. A polyester resin “oPAEG” having a designed functional group number N = 2, a hydroxyl value = 14.6, and a theoretical number average molecular weight 900 calculated from the hydroxyl value was obtained. Obtained. The mass% of glycerol contained in this polyester resin was 0.0%. Polyester solution A was obtained by adding and dissolving 40 parts of ethyl acetate to 160 parts of the obtained resin.

Production Example 18 Production Method of Polyester Solution B of Polyester Resin “PGoPA” Consisting of Orthophthalic Acid and 1,3-Propylene Glycol Phthalic Anhydride 396 in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser .34 parts, 1,3-propylene glycol 271.58 parts, and titanium tetraisopropoxide 0.05 parts, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. Held at 0C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester resin “oPAPG” having a design functional group number N = 2, a hydroxyl value = 14.6, and a theoretical number average molecular weight 900 calculated from the hydroxyl value was obtained. Obtained. The mass% of glycerol contained in this polyester resin was 0.0%. Polyester solution B was obtained by adding and dissolving 40 parts of ethyl acetate to 160 parts of the obtained resin.

(Production Example 19) Method for producing polyester solution C of polyester resin “HGoPA” composed of orthophthalic acid and 1,6-hexanediol Phthalic anhydride 396 was added to a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a snider tube, and a condenser. .34 parts, 1,6-hexanediol 389.96 parts, and titanium tetraisopropoxide 0.05 parts were charged, and the inner temperature was adjusted to 220 by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. Held at 0C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated, and a polyester resin “oPAHG” having a designed functional group number N = 2, a hydroxyl value = 187.0, and a theoretical number average molecular weight 900 calculated from the hydroxyl value was obtained. Obtained. The mass% of glycerol contained in this polyester resin was 0.0%. Polyester solution C was obtained by adding and dissolving 40 parts of ethyl acetate to 160 parts of the obtained resin.

<Example of production of terminal isocyanate resin composition>
(Production Example 20) Production Example of Terminal Isocyanate Resin Composition “(EGoPA) nXDI2” (1) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser (A) 1125 parts, 188 parts of xylylene diisocyanate (abbreviated as XDI) and 235 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was 630, which was almost the theoretical equivalent, it was cooled to 50 ° C. to obtain a terminal isocyanate composition having a nonvolatile content of 80% and a number average molecular weight of 1276. Hereinafter, this composition is referred to as a curing agent (1).

(Production Example 21) Production Example of Terminal Isocyanate Resin Composition “(EGoPA) nTDI2” (2) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser 1125 parts of a polyester solution (A), 174 parts of tolylene diisocyanate (abbreviated as TDI) and 44 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was 620, which was almost the theoretical equivalent, it was cooled to 50 ° C. to obtain a terminal isocyanate resin composition having a nonvolatile content of 80% and a number average molecular weight of 1248. Hereinafter, this composition is referred to as a curing agent (2).

(Production Example 22) Production Example of Terminal Isocyanate Resin Composition “(EGoPA) nMDI2” (3) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser 1125 parts of polyester solution (A), 250 parts of 4-4′diphenylmethane diisocyanate (abbreviated as MDI) and 63 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was almost the theoretical equivalent of 700, it was cooled to 50 ° C. to obtain a terminal isocyanate resin composition having a number average molecular weight of 1400. Hereinafter, this composition is referred to as a curing agent (3).

(Production Example 23) Production Example of Terminal Isocyanate Resin Composition “(PGoPA) nXDI2” (4) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser 1125 parts of polyester solution (B), 188 parts of xylylene diisocyanate (abbreviated as XDI) and 47 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was 625, which was almost the theoretical equivalent, it was cooled to 50 ° C. to obtain a terminal isocyanate composition having a nonvolatile content of 80% and a number average molecular weight of 1276. Hereinafter, this composition is referred to as a curing agent (4).

(Production Example 24) Production Example of Terminal Isocyanate Resin Composition “(PGoPA) nH12MDI2” (5) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser 1125 parts of the polyester solution (A), 262 parts of 4-4 ′ dicyclohexylmethane diisocyanate (abbreviated as H12MDI) and 66 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was a theoretical equivalent of 715, it was cooled to 50 ° C. to obtain a terminal isocyanate resin composition having a number average molecular weight of 1424. Hereinafter, this composition is referred to as a curing agent (5).

(Production Example 25) Production Example of Terminal Isocyanate Resin Composition “(PGoPA) nH6XDI2” (6) Synthesis Example 6: a) Terminal Isocyanate Resin Composition (6)
Into a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser, polyester solution (B) 1125 parts and cyclohexane-1,2-diylbis (methylene) diisocyanate (H6XDI and (Omitted) 194 parts and 49 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was 647, which was almost the theoretical equivalent, it was cooled to 50 ° C. to obtain a terminal isocyanate composition having a nonvolatile content of 80% and a number average molecular weight of 1288. Hereinafter, this composition is referred to as a curing agent (6).

(Production Example 26) Production Example of Terminal Isocyanate Resin Composition “(HGoPA) nXDI2” (7) Polyester solution in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser (C) 750 parts, 188 parts of xylylene diisocyanate (abbreviated as XDI) and 235 parts of ethyl acetate were charged and reacted at 75 ° C. for 3 hours under a nitrogen stream. Since the NCO equivalent was 488, which was almost the theoretical equivalent, it was cooled to 50 ° C. to obtain a terminal isocyanate composition having a nonvolatile content of 80% and a number average molecular weight of 976. Hereinafter, this composition is referred to as a curing agent (7).

<Commercially available isocyanate curing agent>
"Takenate 500" (xylylene diisocyanate non-volatile component 100% NCO% 44.7%) manufactured by Mitsui Chemicals was used as the curing agent a.
(Curing agent k)
“Takenate 600” (hydrogenated xylylene diisocyanate non-volatile component 100% NCO% 43.2%) manufactured by Mitsui Chemicals was used as the curing agent b.

“Takenate D-110N” manufactured by Mitsui Chemicals (trimethylolpropane adduct of metaxylylene diisocyanate nonvolatile component 75.0% NCO% 11.5%) was used as the curing agent c.

“Takenate D-120N” manufactured by Mitsui Chemicals (trimethylolpropane adduct of hydrogenated metaxylylene diisocyanate nonvolatile component 75.0% NCO% 11%) was used as a curing agent d.
“Desmodur N3200” (hexuremethylene diisocyanate burette body) made by Sumika Bayer Urethane was used as the curing agent e.

(Methods for producing polyester resin coating solutions of Examples 1 to 15 and Comparative Examples 1 to 5)
The polyester polyol obtained by the above production method is diluted with methyl ethyl ketone to obtain a resin solution having a nonvolatile content of 50%. Further, the terminal isocyanate resin composition “(EGoPA) nXDI2” (curing agent 1), “(EGoPA) nTDI2” ( Curing agent 2), “(EGoPA) nMDI2” (curing agent 3), “(PGoPA) nXDI2” (curing agent 4), “(EGoPA) nH12MDI” (curing agent 5), “(PGoPA) nH6XDI” (curing agent) 6) The curing agents a, b, c, d and e were blended as shown in Tables 1, 2 and 5 to obtain a polyester resin coating solution used in the coating method described later.

(Coating method)
Using a bar coater, apply the polyester resin coating solution to a 12 μm thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) so that the coating amount is 5.0 g / m ² (solid content). Then, the diluting solvent was volatilized and dried with a drier set at a temperature of 70 ° C., and then the composite film was cured over 40 ° C./3 days to obtain the water vapor barrier film of the present invention.

(Lamination method 1)
Using a bar coater, apply the polyester resin coating solution to a 12 μm thick PET film (“E-5100” manufactured by Toyobo Co., Ltd.) so that the coating amount is 5.0 g / m ² (solid content). Then, the diluted solvent is volatilized and dried with a dryer set at a temperature of 70 ° C., and then this composite film and an unstretched PP film (“ZK-93KM” manufactured by Toray Film Processing Co., Ltd.) are heated at a temperature of 40 ° C. and a pressure of 0.4 MPa. Then, dry lamination was performed at a lamination speed of 40 m / min to obtain a PET / polyester resin composition / CPP laminate.

(Lamination method 2)
Using a bar coater, a 15 μm thick nylon (Ny) film (“Emblem ON-BC” manufactured by Unitika Ltd.) is used to apply a polyester resin coating solution to a coating amount of 5.0 g / m ² (solid content). The composite film and the unstretched LLDPE film (TUX-HC 60μ manufactured by Tosero Co., Ltd.) are heated at a temperature of 40 ° C., a pressure of 0.4 MPa, Dry lamination was performed at a lamination speed of 40 m / min to obtain a Ny / polyester resin composition / LLDPE laminate.

(Lamination method 3)
Using a bar coater, the polyester resin coating solution is a 12 μm thick aluminum-deposited polyester (VM-PET) film (manufactured by Toray Film Processing Co., Ltd.) with a coating amount of 5.0 g / m ² (solid content) “1310”), and the solvent is volatilized and dried with a dryer set at a temperature of 70 ° C. Then, this composite film and an unstretched PP film (“ZK-93KM” manufactured by Toray Film Processing Co., Ltd.) are heated to a temperature of 40 Dry lamination was performed at 0 ° C., a pressure of 0.4 MPa, and a lamination speed of 40 m / min to obtain a VM-PET / polyester resin composition / CPP laminate.

(Lamination method 4)
Using a bar coater, the polyester resin coating liquid is a 12 μm thick polyester (PET) film (“E-5100” manufactured by Toyobo Co., Ltd.) so that the coating amount is 5.0 g / m ² (solid content). The composite film and an aluminum-deposited unstretched CPP film (“2203” manufactured by Toray Film Processing Co., Ltd.) (VM-CPP) Was dry laminated at a temperature of 40 ° C., a pressure of 0.4 MPa, and a lamination speed of 40 m / min to obtain a PET / polyester resin composition / VM-CPP laminate.

(Lamination strength evaluation method)
The aging-finished laminated film is cut to a width of 15 mm parallel to the coating direction, and between the PET film and the CPP film, or between the Ny film and the LLDPE film, Tensilon universal testing machine manufactured by Orientec Co., Ltd. Was used, the atmospheric temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeled by the 180 ° peeling method was defined as the laminate strength. The unit of laminate strength was N / 15 mm.
When the film was broken during the measurement, F and the peak value were described in the result.

  When VM-PET and VM-CPP having aluminum vapor deposition were used, the laminate strength was measured in the same manner as the PET film or CPP film.

(Oxygen permeability)
The water vapor barrier film after aging is used in an atmosphere of 23 ° C., 0% RH and 90% RH according to JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. It was measured.

Moreover, the oxygen barrier property of the resin coating film single-piece | unit which hardened the polyester resin composition was computed using Formula (a) from the measurement result of the barriering laminated film, PET film, and nylon film. About the measurement result, it converted as a transmittance | permeability of 5 g / m < ² > of application amounts.

P: Oxygen permeability of barrier laminated film P1: Oxygen permeability of coating film alone P2: Oxygen permeability of 12 μm PET film (0% RH: 130 cc / m ² · 24 hours · atm, 90% RH: 100 cc / m ²・ Calculated as 24 hours / atm)
P3: Water vapor transmission rate of 15 μm nylon film (calculated as 0% RH: 50 cc / m ² · 24 hours · atm, 90% RH: 74 cc / m ² · 24 hours · atm)
(Water vapor transmission rate)
The laminated film after the aging was evaluated in an atmosphere of 40 ° C. and 90% RH using a measuring device manufactured by Illinois in accordance with the water vapor permeability test method conductivity method “ISO-15106-3”. Note that RH represents humidity.

Moreover, the water vapor barrier property of the resin coating film which hardened | cured the polyester resin composition was computed using Formula (a) from the measurement result of the water vapor barrier laminated film, PET film, and nylon film. About the measurement result, it converted as a transmittance | permeability of 5 g / m < ² > of application amounts.

P: Water vapor transmission rate of water vapor barrier laminate film P1: Water vapor transmission rate of coating film alone P2: Water vapor transmission rate of 12 μm PET film (calculated as 46 g / m ² · 24 hours)
P3: Water vapor permeability of 15 μm nylon film (calculated as 260 g / m ² · 24 hours)

(Reference example)
The oxygen transmission rate of a PET (biaxially stretched polyethylene terephthalate) film (E-5100 manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm was measured and converted to a transmission rate of a film thickness of 5 g / m ² . As a result, it was 240 cc / m ² · day · atm.
The results of Examples and Comparative Examples are shown in Tables 3, 4 and 6.

*: Insoluble in solvent As a result, the resin layer 5 g / m ² thickness obtained by curing the resin compositions of Examples 1 to 14 and 16 to 18 had a water vapor transmission rate of 70 g / m ² · day or less and 12 μm stretching. It was significantly lower than 110 g / m ² · day of the PET film.

Further, in Examples 1 to 18 of the resin composition of the resin layer 5 g / ^{m 2} thick cured, both oxygen transmission rate (23 ℃ 0% RH) is 80cc ^/ m 2 · day · atm or less, the oxygen permeability (23 ° C., 90% RH) was 60 cc / m ² · day · atm or less, which was significantly below the 240 cc / m ² · day · atm of the 12 μm stretched PET film of the reference example.

PET film and CPP film, nylon (Ny) film and LLDPE film, or aluminum vapor-deposited PET (VM-PET) film and CPP film using the resin obtained by curing the resin composition of Examples 1 to 18 as an adhesive for dry lamination Alternatively, when the PET film and the aluminum vapor-deposited CPP (VM-CPP) film are bonded together, the resin adhesive exhibiting the adhesive performance and in particular curing the resin compositions of Examples 3 and 4 and Examples 6 to 18 is PET. In the configuration and the Ny configuration, the film breakage, the VM-PET configuration, and the VM-CPP configuration also exhibited very good adhesion.
As described above, the resin compositions of Examples 1 to 18 can achieve both good barrier performance and good laminate adhesive strength.

On the other hand, Comparative Examples 1 to 4 have a water vapor barrier water vapor transmission rate of 49-65 g / m ² · day and an oxygen transmission rate (23 ° C. 90% RH, 23 ° C. 0% RH) of 70 cc / m ² · day · atm or less. However, in the VM-PET configuration and the VM-CPP configuration, the laminate strength is less than 0.5 N / 15 mm, and the adhesion is poor.
On the other hand, in Comparative Example 5, the laminate strength is good in the PET / CPP configuration, the Ny / LLDPE configuration, the VM-PET configuration, and the VM-CPP configuration, but the water vapor barrier water vapor permeability is 205 g / m ² · day, The oxygen permeability (23 ° C., 0% RH) is 225 cc / m ² · day · atm, and the oxygen permeability (23 ° C., 90% RH) is 199 cc / m ² · day · atm.

On the other hand, Comparative Examples 6 to 8 did not use the curing agent of the present invention, and as a result, the water vapor transmission rate remained at 153 to 190 g / m ² · day. Further, in Comparative Example 9, when the phthalic acid of the polyester resin was changed to isophthalic acid, a phenomenon that it did not dissolve in methyl ethyl ketone and ethyl acetate occurred and the solvent solubility was lost, so that it could not be applied to the film.
Even in the VM-PET configuration and the VM-CPP configuration of Comparative Examples 6 to 8, the laminate strength is less than 1 N / 15 mm, resulting in poor adhesion.

  Since the polyester resin composition for a barrier material of the present invention has a barrier property against gas or water vapor, in addition to the film laminating primer for the packaging material, for example, an adhesive for a protective film for a solar cell or a display element A coating agent for electronic materials such as a coating agent for a water vapor barrier substrate, a coating material for building materials, a coating for industrial materials, and the like can be suitably used as long as barrier properties are desired.

Claims (8)

A polyester resin composition for a barrier material comprising a bifunctional isocyanate group-containing curing agent having a molecular weight of 600 or more represented by the general formula (A) and a polyester polyol.

[In formula (A), R ₁ represents a group represented by general formula (1).

(In the formula, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3- An arylene group selected from the group consisting of an anthraquinonediyl group and a 2,3-anthracenediyl group, or a 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group which may have a substituent , 2,3-anthraquinonediyl group, and a group obtained by hydrogenation reaction of an arylene group selected from the group consisting of 2,3-anthracenediyl group, Y represents an alkylene group having 2 to 6 carbon atoms. )
In the formula (A), R ₂ may have a substituent, from the group consisting of a tolylene group, a phenylene group, a phenylenediyl group, a methylenediphenylene group, a naphthylene group, an anthraquinonediyl group, and an anthracenediyl group. Arylene group selected or hydrogen of an arylene group selected from the group consisting of an optionally substituted tolylene group, phenylene group, phenylenediyl group, methylenediphenylene group, naphthylene group, anthraquinonediyl group, and anthracenediyl group The group obtained by the addition reaction is represented. ] The polyester resin composition for barrier materials according to claim 1, wherein the polyester polyol contains the general formula (2) or the general formula (3).

(In Formula (2), R < ₃ > -R < ₅ > is respectively independently a hydrogen atom or General formula (3).

(However, n represents an integer of 1 to 5, and X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinone. An arylene group selected from the group consisting of a diyl group and a 2,3-anthracenediyl group, or an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, This represents a group obtained by a hydrogenation reaction of an arylene group selected from the group consisting of a 2,3-anthraquinonediyl group and a 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms.
And at least one of R _{1 to} R ₃ is a group represented by the general formula (3). )   The polyester resin composition for a barrier material according to claim 1 or 2, wherein the polyester polyol has an acid value of 5 mgKOH / g or less.   The polyester resin composition for barrier materials according to claim 2 or 3, wherein the glycerol residue of the polyester polyol represented by the general formula (2) is contained in the water vapor barrier material polyester resin composition in an amount of 5% by mass or more. The R ₂ is a tolylene group, a xylenediyl group, a methylenediphenylene group, a naphthylene group, or a group obtained by hydrogenating a tolylene group, a xylenediyl group, a methylenediphenylene group, or a naphthylene group. The polyester resin composition for barrier materials in any one.   The coating material for barrier materials formed by hardening | curing the polyester resin composition for barrier materials in any one of Claims 1-5.   The water vapor | steam barrier film which has a resin layer which hardened | cured the polyester resin composition for barrier materials in any one of Claims 1-5.   The gas barrier film which has a resin layer which hardened the polyester resin composition for barrier materials in any one of Claims 1-5.