WO2013005767A1

WO2013005767A1 - Multi-layer film with gas barrier properties, adhesive, and coating material

Info

Publication number: WO2013005767A1
Application number: PCT/JP2012/067067
Authority: WO
Inventors: 武田　博之; 下口　睦弘; 圭一尾薗
Original assignee: Dic株式会社
Priority date: 2011-07-06
Filing date: 2012-07-04
Publication date: 2013-01-10

Abstract

The present invention relates to a multilayer film having gas barrier properties, an adhesive, and a coating material, and further relates to a polyester resin composition that makes it possible to provide the multilayer film having gas barrier properties, the adhesive, and the coating material. The problem of the present invention is to provide a multilayer gas barrier film with excellent gas barrier properties. An additional problem is to provide the following: a polyester resin composition with gas barrier properties which has as its primary component the polyester resin that is used as the gas barrier layer in the multilayer film having gas barrier properties; a multilayer film with gas barrier properties comprising film coated with the resin composition; and a coating material. By providing a multilayer film with gas barrier properties having a gas barrier layer that is obtained by hardening a polyester resin composition formed by reacting polyester polyol with a hardening agent, this problem is solved by means of a polyester resin composition having a specific structure.

Description

Gas barrier multilayer film, adhesive, and coating material

The present invention relates to a gas barrier multilayer film, an adhesive, and a coating material, and further relates to a polyester resin composition that can provide the gas barrier multilayer film, the adhesive, and the coating material.

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, the composition has poor workability because a highly polar solvent must be used. 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.

Patent Document 3 discloses that an oxygen-absorbing resin component having a carbon-carbon unsaturated bond and a reactive functional group, and reacting with the reactive functional group to form a cross-linked structure with the oxygen-absorbing resin component. An oxygen-absorbing paint containing the resulting cross-linking agent is described. In this cited reference, the purpose of the present invention is the same as that of the present invention in the sense that the contents are protected from deterioration, but this cited reference is a technique for preventing deterioration of the contents by absorbing oxygen, and blocks the oxygen of the present application. It is different from the method. Furthermore, in order to carry out the cited document, a film having an oxygen barrier property is indispensable, and deterioration of contents cannot be prevented without a film having a high oxygen barrier property. Furthermore, there is a problem in that deterioration of the contents cannot be prevented after the oxygen absorption performance is saturated.

In Patent Document 4, an organic polymer polyol compound selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol and polyurethane polyol, and a carboxylic acid anhydride is added to one end of the organic polymer polyol compound. There is described a solventless composite laminate adhesive composition characterized by comprising an organic polymer polyol compound having a carboxyl group introduced at one end and a polyisocyanate compound.

However, Patent Document 4 has a description on workability and adhesiveness, but does not have a description on oxygen barrier properties and does not have oxygen barrier properties.

Japanese Patent No. 4524463 Japanese Patent No. 4054972 JP 2003-268310 A Japanese Unexamined Patent Publication No. 7-97557

The problem to be solved by the present invention is to provide a gas barrier multilayer film having excellent gas barrier properties. Another object of the present invention is to provide a gas barrier polyester resin composition mainly comprising a polyester resin used as a gas barrier layer in the gas barrier multilayer film, a gas barrier multilayer film in which the resin composition is applied to the film, and a coating material. .

As a result of intensive investigations to solve the above problems, the present inventors have found that a gas barrier multilayer film having a gas barrier layer obtained by curing a polyester resin composition obtained by reacting a polyester polyol and a curing agent. For the purpose of provision, it has been found that a polyester resin composition having a specific structure solves the problems of the present invention, and the present invention has been completed.

That is, the present invention
In a gas barrier multilayer film having a gas barrier layer obtained by curing a polyester resin composition obtained by reacting a polyester polyol and a curing agent,
The present invention provides a gas barrier multilayer film in which the polyester resin composition is any one selected from the following (I) to (III).
(I) A polyester resin composition obtained by reacting a polyester polyol represented by the general formula (1) with a curing agent.

(In the formula (1), R ₁ to R ₃ each independently represents a hydrogen atom, or a compound represented by the general formula (2)

(In the formula (2), 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 Represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms. However, at least one of R ₁ to R ₃ represents a group represented by the general formula (2). )
(II) containing a polyester polyol (A) having a polymerizable carbon-carbon double bond in the molecule and having two or more hydroxyl groups, and a polyisocyanate (B) having two or more isocyanate groups. A resin composition for an oxygen barrier adhesive.
(III) A resin composition for an oxygen barrier adhesive comprising a polyester polyol (C) and a polyisocyanate (D) having two or more isocyanate groups,
The polyester polyol (C) has at least one carboxy group and two or more hydroxyl groups obtained by reacting a carboxylic anhydride or a polyvalent carboxylic acid with a polyester polyol having three or more hydroxyl groups. Resin composition for oxygen barrier adhesive.

According to the present invention, a gas barrier multilayer film having excellent gas barrier properties is provided. Also provided are a gas barrier polyester resin composition mainly composed of a polyester resin excellent in gas barrier properties used as a gas barrier layer in the gas barrier multilayer film, a gas barrier multilayer film in which the resin composition is applied to the film, and a coating material. can do.

The present invention is described in detail below.
1) Polyester resin composition according to (I) (polyester resin compound having a glycerol skeleton)
In the general formula (1) having a glycerol skeleton according to the resin composition (I), R ₁ to R ₃ are a hydrogen atom or a general formula (2)

(In the formula (2), 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 Represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms. However, at least one of R ₁ to R ₃ represents a group represented by the general formula (2). ).

In the general formula (1), at least one of R ₁ , R ₂ and R ₃ needs to be a group represented by the general formula (2). Among them, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2).

_Further, R 1, any one of _{R 2} and _{R 3} is a group represented by the general formula (2) _compound, R 1, _{R _2,} and any two of the general formula _{R 3} (2) Any two or more compounds of the compound represented by the general formula (2) and the compound in which all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (2) 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 (2), Y represents an 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 (1) is essential for glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in 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 includes 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.

Also, 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 (1), a polyester resin (orthophthalic anhydride as an aromatic polycarboxylic 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 of the present invention), naphthalene 2,3-dicarboxylic acid as an aromatic polycarboxylic acid, and polyhydric alcohol as Examples thereof include polyester resins using ethylene glycol (abbreviated as GLY (oNAEG) m, where m is as defined above).

In the present application, the content of the glycerol skeleton is the residue (C ₃ H ₅ O ₃ = 89) excluding R ₁ to R ₃ in the general formula (1) with respect to the total solid content of the adhesive resin of the present application. .07) is included using equation (a).

P: represents a polyester resin compound having a glycerol skeleton.

The present invention is characterized by having a glycerol residue of 5% by mass or more in the polyester resin composition in order to express a high barrier property.

(Gas barrier polyester resin composition solid content mass calculation method)
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 gas barrier polyester resin composition 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 preferred.

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 measuring method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measuring method described in JIS-K0070 is the numerical 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 the formula (b), Mn represents a set number average molecular weight of a predetermined trifunctional 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.

Catalysts 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 or tetra-butyl-titanate, which has high activity for ester reaction, and the zirconia catalyst. The amount of the catalyst is 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. However, a catalyst is not essential if the reaction can proceed without catalyst.

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

As the curing agent, the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in solubility and oxygen barrier ability. The urethane group concentration at this time is preferably in the range of 1.0 to 6.0 mmol / g.

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, if the temperature is too low at about -30 ° C., there is a risk that sufficient gas barrier properties may not be obtained due to the intense molecular motion of the polyester resin near room temperature.

2) Regarding the polyester resin composition according to (II) The resin composition according to (II) is obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, and is a component of polyvalent carboxylic acid and polyhydric alcohol. As a component having a polymerizable carbon-carbon double bond, a polymerizable carbon double bond is introduced into the molecule of the polyester polyol (A).

(Polyvalent carboxylic acid)
The polyester polyol (A) of the present invention is a polyvalent carboxylic acid component, specifically, an aliphatic polyvalent carboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. as aromatic polycarboxylic acids, and orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic as aromatic polycarboxylic acids Acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid And anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2 Polyhydroxy acids such as -hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more. These acid anhydrides can also be used. Among these, in order to obtain barrier properties, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable.

(Polyvalent carboxylic acid having a polymerizable carbon-carbon double bond)
Maleic anhydride, maleic acid, fumaric acid, 4-cyclohexene-1,2-dicarboxylic acid and acid anhydrides thereof as polyvalent carboxylic acids having a polymerizable carbon-carbon double bond in the polyvalent carboxylic acid, 3-methyl- Examples thereof include 4-cyclohexene-1,2-dicarboxylic acid and its anhydride. Of these, maleic anhydride, maleic acid, and fumaric acid are preferred because it is presumed that the smaller the number of carbon atoms, the less the molecular chain becomes excessively flexible and the less oxygen permeates.

(Polyhydric alcohol component)
Specifically, the polyhydric alcohol used in the present invention includes, as the aliphatic diol, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic. In particular, the smaller the number of carbon atoms between oxygen atoms, the less likely the molecular chain to become excessively flexible and less oxygen permeation. Therefore, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane Methanol is preferable, and ethylene glucol is more preferable.

(Polyhydric alcohol with polymerizable carbon-carbon double bond)
Examples of the polyhydric alcohol having a polymerizable carbon-carbon double bond in the polyhydric alcohol include 2-butene-1,4-diol.

In the polyester polyol (A), a polymerizable double bond is introduced into the polyester polyol (A) by using a polyvalent carboxylic acid having a polymerizable carbon-carbon double bond and a polyhydric alcohol, but has a hydroxyl group. It may be a reaction between a polyester polyol and a carboxylic acid having a polymerizable double bond, or a carboxylic acid anhydride. As the carboxylic acid in this case, a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride or fumaric acid, an unsaturated fatty acid such as oleic acid or sorbic acid, or the like can be used. The polyester polyol in this case is preferably a polyester polyol having two or more hydroxyl groups, but it is more preferable to have three or more hydroxyl groups in consideration of molecular elongation due to crosslinking with polyisocyanate. When the polyester polyol has 1 or 2 hydroxyl groups, the polyester polyol (A) obtained by reacting with a carboxylic acid having a polymerizable double bond has 0 or 1 hydroxyl group and reacts with the polyisocyanate (B). It becomes difficult to cause molecular elongation due to, and it becomes difficult to obtain properties such as laminate strength, seal strength, and heat resistance as an adhesive.

These polyester polyols (A) having a number average molecular weight of 450 to 5,000 are particularly preferable because a crosslinking density with an excellent balance between adhesive ability and oxygen barrier ability can be obtained. As the curing agent, the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and oxygen barrier ability. When the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, causing the problem that the film shifts during lamination or the bonded film rises. Conversely, if the molecular weight is higher than 5000, The problem is that the viscosity at the time of construction is too high to be applied, and that the lamination is impossible due to low adhesiveness. The number average molecular weight was obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.

The polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of −30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C. When the glass transition temperature is too higher than 80 ° C., the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to intense molecular motion of the polyester polyol at around room temperature.

It is preferable that the polyester polyol (A) has a hydroxyl value of 20 to 250 mgKOH / g and an acid value of 0 to 100 mgKOH / g. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070. When the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained.

Further, it is characterized in that the monomer component having a polymerizable carbon-carbon double bond is 5 to 60 parts by mass with respect to 100 parts by mass of all monomer components constituting the polyester polyol (A).
If it is lower than this range, the number of crosslinking points between the polymerizable double bonds will be reduced, and it will be difficult to obtain barrier properties. If it is higher, the number of crosslinking points will be increased, and the flexibility of the cured coating will be significantly reduced, resulting in a laminate strength. This is not preferable because it is difficult to be performed. For this reason, the amount of polyvalent carboxylic acid and polyhydric alcohol component used other than the polyvalent carboxylic acid and polyhydric alcohol component having a polymerizable carbon-carbon double bond must be kept below a certain level.

Also, examples of the polyester polyol (A) of the present invention include a drying oil or a semi-drying oil. Examples of the drying oil or semi-drying oil include publicly known and commonly used drying oils having a carbon double bond and semi-drying oils.

Further, a polyol having a number average molecular weight of 1000 to 15000 by urethane elongation by reaction of the polyester polyol (A) with a diisocyanate compound may be used as an adhesive. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has an excellent oxygen barrier property, an excellent initial cohesive force, and is further excellent as an adhesive used during lamination.

3) About the polyester resin composition which concerns on said (III) Next, the resin composition which concerns on said (III) is demonstrated.
First, the polyester polyol (A) according to (III) includes at least one carboxy group obtained by reacting a polyester polyol (I) having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid. It has two or more hydroxyl groups. The polyester polyol (I) having three or more hydroxyl groups can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.

The polyvalent carboxylic acid component and the polyhydric alcohol component of the polyester polyol (A) are preferably a polyvalent carboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neo Carboxylic anhydride or polycarboxylic acid is reacted with polyester polyol (I) having three or more hydroxyl groups comprising at least one polyhydric alcohol component selected from the group consisting of pentyl glycol and cyclohexanedimethanol. And having at least one carboxy group and two or more hydroxyl groups.

(Orthophthalic acid and its anhydride)
Orthophthalic acid and its anhydride have an asymmetric structure in the skeleton. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and it is presumed that this provides excellent oxygen barrier properties. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesion and oxygen barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics.

(Polyvalent carboxylic acid and other components)
The polyester polyol (I) of the present invention may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired. 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, 1,2-bis (phenoxy) ethane-p, p '-Dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- ( Polybasic acids such as 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, and isophthalic acid are preferable. Trivalent or higher polyvalent carboxylic acids include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, a trivalent or higher polyvalent carboxylic acid may be used. A trivalent carboxylic acid is preferred as the divalent carboxylic acid.

(Polyhydric alcohol component)
The polyhydric alcohol used in the present invention preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. Among them, ethylene glycol is most preferably used because it is presumed that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain becomes excessively flexible and the less oxygen permeates.

(Polyhydric alcohol and other ingredients)
In the present invention, the above-mentioned polyhydric alcohol component is preferably used, but other polyhydric alcohol components may be copolymerized within a range not impairing the effects of the present invention. Specifically, aliphatic diols include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and ethylene Examples thereof include an oxide extension product and a hydrogenated alicyclic group. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol and the like. However, in order to prevent gelation during synthesis, the trihydric or higher polyhydric alcohol is preferably a trihydric alcohol.

Next, the reaction between the polyester polyol (I) of the present invention and the carboxylic acid anhydride or polyvalent carboxylic acid is carried out as follows.

That is, it can be obtained by reacting the polyester polyol (I) with a polyvalent carboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol (I). The ratio between the polyester polyol (I) and the polyvalent carboxylic acid is that 1 or more hydroxyl groups of the polyester polyol (A) after the reaction are required, so that the polyvalent carboxylic acid is 1/3 of the hydroxyl groups of the polyester polyol (I). It is preferable to react with: Although there is no restriction | limiting in the carboxylic acid anhydride or polyhydric carboxylic acid used here, when the gelatinization at the time of reaction with polyhydric carboxylic acid and polyester polyol (I) is considered, it is a bivalent or trivalent carboxylic acid anhydride. Is preferably used. Divalent carboxylic acid anhydrides include succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid Anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, and the like can be used, and trimellitic acid anhydride can be used as the trivalent carboxylic acid anhydride.

The number average molecular weight of the polyester polyol (A) is particularly preferably from 450 to 5,000 because a crosslinking density with an excellent balance between adhesion ability and oxygen barrier ability can be obtained. As the curing agent, the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and oxygen barrier ability. When the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, causing the problem that the film shifts during lamination or the bonded film rises. Conversely, if the molecular weight is higher than 5000, The problem is that the viscosity at the time of construction is too high to be applied, and that the lamination is impossible due to low adhesiveness. The number average molecular weight was obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.

The polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of −30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C. When the glass transition temperature is higher than 80 ° C., the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to the intense molecular motion of the polyester polyol near room temperature.

It is preferable that the polyester polyol (A) has a hydroxyl value of 20 to 250 and an acid value of 20 to 200. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070. When the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained. On the other hand, when the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained. When the acid value is less than 20 mgKOH / g, the interaction between molecules becomes small, and good oxygen barrier properties and good initial cohesive force cannot be obtained. On the contrary, when the acid value exceeds 200 mgKOH / g, the reaction between the polyester polyol (A) and the polyisocyanate (B) becomes too fast, and good coating suitability cannot be obtained.

(Curing agent)
The curing agent used in the present invention is not particularly limited as long as it is a curing agent capable of reacting with the hydroxyl group of the polyester resin, and known curing agents such as polyisocyanates and epoxy compounds can be used. Among these, it is preferable to use polyisocyanate from the viewpoints of adhesiveness and retort resistance.

Polyisocyanate compounds 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 Amount 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. .

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.

Further, when carboxylic acid remains at the terminal of the polyester resin used in the present invention, an epoxy compound can be used as a curing agent. Epoxy compounds include bisphenol A diglycidyl ether and oligomers thereof, hydrogenated bisphenol A diglycidyl ether 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 using an epoxy compound as a curing agent, a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the gas barrier property which is the object of the present invention is not impaired.

Among them, the curing agent is preferably the polyisocyanate, and when the polyisocyanate includes the metaxylene skeleton, the gas barrier property can be improved by not only hydrogen bonding of the urethane group but also π-π stacking of aromatic rings. It is preferable because it can be done.

Examples of the polyisocyanate containing a metaxylene skeleton include xylene diisocyanate trimer, burette synthesized by reaction with amine, and adduct formed by reaction with alcohol. The adduct body is more preferable because the solubility of the polyisocyanate in the organic solvent used for the dry laminate adhesive is easily obtained. As the adduct, an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.

In the resin composition according to (I), the ratio of the polyester resin compound having a glycerol skeleton and the curing agent is that the ratio of the polyester resin compound having a glycerol skeleton and the curing agent is a hydroxyl group of the polyester resin compound having a glycerol skeleton and curing. It is preferable to blend such that the reaction component of the agent is 1 / 0.5 to 1/5 (equivalent ratio), more preferably 1/1 to 1/3. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out 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 above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type. 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.

In the resin composition according to (II), the polyester polyol (A) and the curing agent are such that the ratio of the polyester polyol (A) and the curing agent is a hydroxyl group of the polyester polyol (A) and a reaction component of the curing agent. It is preferably blended so as to be 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength may be insufficient. There is.

A known polymerization catalyst can be used as a catalyst for promoting polymerization of a polymerizable double bond. Examples of the polymerization catalyst include transition metal complexes. Although a transition metal complex will not be specifically limited if it is a compound provided with the capability to oxidatively polymerize a polymerizable double bond, A various metal or its complex can be used. For example, metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, A salt with soybean oil fatty acid or the like can be used. The transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to the polyester polyol (A).

In the resin composition according to (III), the polyester polyol (A) and the curing agent are such that the ratio of the polyester polyol (A) and the curing agent is a reaction component of the hydroxyl group of the polyester polyol (A) and the curing agent. Is preferably 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out 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.

(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.

Also, known acid anhydrides can be used in combination as a method for improving the acid resistance of the 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.

Further, if necessary, a compound having an oxygen scavenging function may be added. 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 to various film materials immediately after coating, a tackifier such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin may be added as necessary. When these are added, the range of 0.01 to 5 parts by mass is preferable with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent.

Moreover, an active energy ray can also be used as a method of reacting a polymerizable double bond. A known technique can be used as the active energy ray, and it can be cured by irradiation with ionizing radiation such as electron beam, ultraviolet ray, or γ ray. In the case of curing with ultraviolet rays, a known ultraviolet irradiation device equipped with a high pressure mercury lamp, an excimer lamp, a metal halide lamp or the like can be used.

In the case of curing by irradiating with ultraviolet rays, if necessary, 0.1 to 20 parts by mass of a light (polymerization) initiator that generates radicals and the like by irradiation with ultraviolet rays with respect to 100 parts by mass of the polyester polyol (A). It is preferable to add a certain amount.

Radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzylmethyl ketal, hydroxy Examples include photocleavage types such as cyclohexyl phenyl ketone and 2-hydroxy-2-methylphenyl ketone. These can be used alone or in combination.

In the resin compositions according to (I) to (III), the glass transition temperature of the cured coating film of the polyester polyol (A) and the polyisocyanate (B) is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C. When the glass transition temperature is too higher than 80 ° C., the flexibility of the polyester polyol near the room temperature is lowered, which may reduce the adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to intense molecular motion of the polyester polyol at around room temperature.

The gas barrier multilayer film obtained by curing the polyester resin composition of the present invention is obtained by applying and curing a polyester resin composition coating liquid on a film serving as a base material. 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 where the gas barrier polyester resin composition of the present invention is heated from room temperature to about 120 ° C. so that the viscosity is about 500 to 2500 mPa · s.

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

The gas barrier multilayer film obtained by curing the polyester resin composition of the present invention can be used as a gas barrier multilayer 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 example, for food packaging, 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: Examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. 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.

In addition, the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.

A gas barrier multilayer film obtained by curing the polyester resin composition of the present invention obtained by applying the gas barrier polyester resin composition 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 multilayer film can be obtained by laminating another thermoplastic resin film and laminating them together 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 a dry lamination (dry lamination method) in which the gas barrier polyester resin composition of the present invention is applied to one of the base films by a gravure roll method, and the other base film is stacked. Paste together. The temperature of the laminate roll is preferably about room temperature to 60 ° C. Non-solvent lamination is applied immediately after applying the gas barrier polyester resin composition 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 pasting a new film material on 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 gas barrier polyester resin composition of the present invention is applied to a base film as an adhesion aid (anchor coating agent) with a roll such as a gravure roll, and the solvent is used at room temperature to 140 ° C. After performing the drying and curing reaction, a laminated film can be obtained by laminating the polymer material melted by the extruder. 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.

Further, the gas barrier multilayer film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which the polyester resin and the curing agent react to produce adhesive strength.

In the present invention, in order to give a higher barrier function, a film in which a vapor deposition layer of a metal such as aluminum or a metal oxide such as silica or alumina may be laminated as necessary.

The gas barrier polyester resin composition of the present invention can be preferably used as a gas barrier polyester resin composition 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 as an oxygen and water vapor barrier film. Thus, the use of the gas barrier polyester resin composition of the present invention is not limited to PET / CPP films and can be widely used.

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

The resin composition according to (II) and (III) of the present invention can be used as a gas barrier adhesive.

The adhesive of the present invention may be either a solvent type or a solventless type. In the case of the solvent type, the solvent may be used as a reaction medium during the production of the polyester polyol and the curing agent. Furthermore, it is used as a diluent during painting. Examples of the solvent 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. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone. In addition, when used without a solvent, it is not always necessary to be soluble in an organic solvent, but considering the washing of a reaction kettle during synthesis and the washing of a coating machine during lamination, Sex is necessary.

The adhesive of the present invention can be used by being applied to a substrate film or the like. The coating method 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. 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. In the case of using a roll coater, it is preferable to coat the adhesive of the present invention in a state heated to about room temperature to about 120 ° C. so that the viscosity of the adhesive of the present invention is about 500 to 2500 mPa · s.

The adhesive of the present invention can be used as an oxygen barrier adhesive for various applications that require oxygen barrier properties against polymers, paper, metals, and the like. Hereinafter, an adhesive for film lamination will be described as one of specific applications.

The adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated film is excellent in oxygen barrier properties, it can be used as an oxygen barrier laminated film.

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 example, for food packaging, 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: Examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. 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. However, when a transparent vapor-deposited film having a high oxygen barrier property is used on both sides of the adhesive, polymerization of the polymerizable double bond of the polyester polyol (A) as an adhesive component is inhibited and good barrier properties are not exhibited. There is. Accordingly, the oxygen barrier property of the oxygen barrier laminate film is preferably such that the oxygen permeability of at least one laminate film is 0.1 cc / m ² · day · atm or more.

After applying the adhesive of the present invention to one of the thermoplastic resin films, the other thermoplastic resin film is overlaid and bonded by lamination to obtain the oxygen barrier laminate film of the present invention. As the lamination method, known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.

Specifically, in the dry lamination method, the adhesive of the present invention is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method). The temperature of the laminate roll is preferably about room temperature to 60 ° C.
In addition, non-solvent lamination is applied to the surface immediately after applying the adhesive of the present invention, which has been heated to room temperature to about 120 ° C., with a roll such as a roll coater heated to room temperature to about 120 ° C. A laminate film can be obtained by laminating various film materials. The laminating pressure is preferably about 10 to 300 kg / cm ² .

In the case of the extrusion laminating method, the organic solvent solution of the adhesive of the present invention is applied to the base film as an adhesion aid (anchor coating agent) by a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C. After the reaction, a laminate film can be obtained by laminating the polymer material melted by the extruder. 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.

In addition, the oxygen barrier laminate film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which adhesive strength is generated.

In the present invention, in order to provide an even higher barrier function, a film in which a vapor-deposited layer of a metal such as aluminum or a metal oxide such as silica or alumina is laminated, polyvinyl alcohol, or ethylene / vinyl alcohol as necessary. A barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be used in combination.

The adhesive of the present invention can be preferably used as an adhesive 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 as an oxygen and water vapor barrier film.

Since the adhesive of the present invention is characterized by having a high oxygen barrier property, the laminate film formed by the adhesive is a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer. (EVOH) A very high level of gas barrier properties is achieved without using commonly used gas barrier materials such as film layers, metaxylylene adipamide film layers, and inorganic vapor deposited film layers deposited with alumina, silica, etc. To do. Moreover, the gas barrier property of the obtained film can also be remarkably improved by using together as an adhesive agent which bonds these conventional gas barrier material and sealant material 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.
Production Examples 1 to 12, Examples 1 to 8 and Comparative Examples 1 to 4 relate to the polyester resin composition according to (I).

Production Example 1 Production Method of Polyester Resin “GLY (oPAEG) 1” 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 , 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 became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester resin “GLY (oPAEG) 1” having a number average molecular weight of 284. 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 to obtain a polyester resin “GLY (oPAEG) 2” having a number average molecular weight of 476.43. 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 to obtain a polyester resin “GLY (oPAEG) 3” having a number average molecular weight of 668.60. The mass% of glycerol contained in this polyester resin was 13.32%.

(Production Example 4) Production Method of Polyester Resin “GLY (oPAEG) 6” Consisting of Glycerol, Orthophthalic Acid, and Ethylene Glycol In a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, snider pipe, and condenser, 92.09 parts of glycerol , 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 to obtain a polyester resin “GLY (oPAEG) 6” having a number average molecular weight of 1245.10. 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 A glycerol is placed in a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser. , 309.34 parts of anhydrous 2,3-naphthalenedicarboxylic acid, 124.14 parts of ethylene glycol, and 0.06 part 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 to obtain a polyester resin “GLY (oNAEG) 2” having a number average molecular weight of 592.59. The mass% of glycerol contained in this polyester resin was 15.03%.

Production Example 6 Production Method of Polyester Polyol “TMP (oPAEG) 3” Composed of Trimethylolpropane, Orthophthalic Anhydride, and Ethylene Glycol, except that instead of glycerol 92.09 in Production Example 3, it was replaced 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 7) Polyester polyol "TMP (oPAEG) 6" comprising 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 number average molecular weight of 1287.18 was obtained in the same manner as in Production Example 4 except for the above.
The mass% of glycerol contained in this polyester polyol was 0.0%.

Production Example 8 Production Method of Polyester Resin “EGoPA” Consisting of 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, 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 to obtain a polyester resin “oPAEG” having a number average molecular weight of 600. The mass% of glycerol contained in this polyester resin was 0.0%.

Production Example 9 Production Method of Glycerol, Isophthalic Acid, and Ethylene Glycol Polyester Resin “GLY (iPAEG) 3” 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 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 to obtain a polyester resin “GLY (iPAEG) 3” having a number average molecular weight of 668.6. The mass% of glycerol contained in this polyester resin was 13.32%.

(Production Example 10) Method for producing adduct of 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene and XDI 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene In a reaction vessel equipped with a reflux condenser and a dropping funnel, 105 g of diethanolamine, 69.1 g of potassium carbonate and 2 L of absolute ethanol are added and refluxed. To this reaction vessel, 131.98 g of 1,3-bis (bromomethyl) benzene was slowly dropped over 2 hours using a dropping funnel, and the reflux was further continued for 48 hours. The produced potassium bromide was removed with a glass filter, and ethanol used in the reaction was removed under reduced pressure to obtain 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene.

(Production Example 11) Production of adduct body of 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene and XDI In a reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, cooling condenser, and dropping funnel 790.36 parts of range isocyanate was added and stirred while heating to 70 ° C.
312.40 parts of the 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene was added dropwise over 1 hour. Stirring is continued at 70 ° C. for 3 hours after the dropping, and 473 parts of methyl ethyl ketone dehydrated to 1000 ppm in advance is added and stirred. After slowly cooling to room temperature, the gel substance floating inside is separated with a 100 mesh brass wire mesh. Thus, an XDI adduct of a compound obtained by adding 4 moles of ethylene oxide to metaxylenediamine was obtained. The non-volatile content of the adduct solution determined according to JIS-K-6910 was 70.0%, and the NCO% determined according to JIS-K1603 was 9.6%.

(Production Example 12) Production of adduct of trimethylolpropane and 2,6-tolylene diisocyanate 2,6-tolylene diisocyanate 522.48 in a reaction vessel equipped with a stirrer, nitrogen gas introduction tube, cooling condenser, and dropping funnel A portion was added and stirred while heating to 70 ° C.
134.17 parts of trimethylolpropane was added dropwise over 1 hour. Stirring is continued at 70 ° C. for 3 hours after dropping, and 284 parts of methyl ethyl ketone dehydrated to 1000 ppm in advance is added and stirred. After slowly cooling to room temperature, the gel substance floating inside is separated with a 100 mesh brass wire mesh. An adduct of trimethylolpropane and 2,6-tolylene diisocyanate was obtained. The non-volatile content of the adduct body solution determined according to JIS-K-6910 was 70.0%, and the NCO% determined according to JIS-K1603 was 13.40%.

(Curing agent a)
“Takenate D-110N” manufactured by Mitsui Chemicals (trimethylolpropane adduct of metaxylylene diisocyanate, nonvolatile component 75.0% NCO% 11.5%) and “Takenate 500” (metaxylylene diisocyanate nonvolatile content> 99 by Mitsui Chemicals) %, NCO% 44.6%) at a ratio of 50/50 (mass ratio) to obtain a curing agent a.
The non-volatile content of the curing agent a is 87.5% and NCO% 28.05%.

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

(Curing agent c)
The adduct body of trimethylolpropane synthesized in Production Example 12 and 2,6-tolylene diisocyanate (nonvolatile content: 70.0%, NCO%: 9.4%) was used as the curing agent c.

(Curing agent d)
The adduct body of 1,3-bis {bis- [2-hydroxyethyl] aminomethyl} benzene and XDI synthesized in Production Example 10 (nonvolatile content: 70%, NCO%: 9.6%) was used as the curing agent d. .

Examples 1 to 8 Comparative Examples 1 to 4
The polyester polyol obtained by the above production method is diluted with methyl ethyl ketone to obtain a resin solution having a non-volatile content of 50%, and further, curing agents a, b, c, d are blended as shown in Tables 1 to 3, and will be described later. A polyester resin coating solution used in the coating method was obtained.

(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 a gas barrier multilayer film of the present invention.

(Oxygen permeability)
The gas barrier multilayer film that has been aged is used in an atmosphere of 23 ° C., 0% RH and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. It was measured.

(Reference example)
The oxygen transmission rate of a 12 μm thick PET (biaxially stretched polyethylene terephthalate) film (E-5100 manufactured by Toyobo Co., Ltd.) was measured. The results are shown in Tables 1 to 3.

*: Since it was not dissolved in methyl ethyl ketone and ethyl acetate, it could not be used as a coating solution and oxygen permeability could not be measured.

As a result, the oxygen barrier multilayer films coated with the resin compositions of Examples 1 to 8 all had an oxygen permeability of 30 cc / m ² · day · atm or less.

On the other hand, since Comparative Examples 1 to 3 did not contain glycerol, the oxygen permeability remained at 35 to 45 cc / m ² · day · atm. Further, in Comparative Example 4, when the phthalic acid of the polyester resin was changed to isophthalic acid, the solvent solubility was lost and the film could not be applied to the film.

Production Examples 13 to 22, Examples 9 to 15 and Comparative Examples 5 to 8 relate to the polyester resin composition according to (II).
(Production Example 13) Polyester polyol (A): Production example of EGMA In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 98.1 parts of maleic anhydride, 78. 5 parts and titanium tetraisopropoxide were charged in an amount corresponding to 100 ppm with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and gradually heated so that the upper temperature of the rectifying tube did not exceed 100 ° C. The internal temperature was maintained at 205 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 600, a hydroxyl value of 182 mgKOH / g, and an acid value of 0.9 mgKOH / g.

(Production Example 14) Production Example of Polyester Polyol (A): Gly (OPAEG) 2MA In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 1316.8 parts of phthalic anhydride, Ethylene glycol (573.9 parts), glycerin (409.3 parts) and titanium tetraisopropoxide were charged in an amount corresponding to 100 ppm with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and the rectifying tube upper temperature was 100. The internal temperature was kept at 220 ° C by gradually heating so as not to exceed ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol.

Next, the temperature was lowered to 120 ° C., and 421.8 parts of maleic anhydride was added thereto, and maintained at 120 ° C. When the acid value is approximately half of the acid value calculated from the charged amount of maleic anhydride, the esterification reaction is terminated to obtain a polyester polyol having a number average molecular weight of about 500, a hydroxyl value of 216 mgKOH / g, and an acid value of 96 mgKOH / g. It was.

(Production Example 15) Production Example of Polyester Polyol (A): THEI (OPAEG) 2MA 1316.8 parts of phthalic anhydride in Production Example 14 is 992.4 parts, and 573.9 parts of ethylene glycol is 432.5 parts. The number average was obtained in the same manner as in Production Example 14 except that 409.3 parts of glycerin was changed to 875.1 parts of tris (2-hydroxyethyl) isocyanurate and 421.8 parts of maleic anhydride was changed to 343.2 parts. A polyester polyol having a molecular weight of about 720, a hydroxyl value of 156 mgKOH / g, and an acid value of 77.8 mgKOH / g was obtained.

(Production Example 16) Polyester Polyol (A) Production Example of EGMA-XDI To 1228.0 parts of the polyester polyol obtained in Production Example 13, 188.0 parts of metaxylylene diisocyanate was added and heated to 80 ° C. to release. The urethanization reaction was carried out until the isocyanato group (hereinafter abbreviated as NCO group) substantially disappeared to obtain a polyester polyol having a number average molecular weight of about 1420 and a hydroxyl value of 79 mgKOH / g.

(Production Example 17) Production Example of Polyester Polyol: THEI (OPAEG) 3 In Production Example 13, 98.1 parts of maleic anhydride is 1136.5 parts of phthalic anhydride, 84.2 parts of ethylene glycol is 495.3 parts, Tris A number average molecular weight of about 860, a hydroxyl value of 195 mgKOH / g, an acid was obtained except that the amount of (2-hydroxyethyl) isocyanurate was 668.1 parts and the internal temperature was changed from 205 ° C. to 220 ° C. A polyester polyol having a value of 0.8 mg KOH / g was obtained.

(Production Example 18) Production Example of Polyester Polyol: Gly (OPAEG) 2 In Production Example 13, 98.1 parts of maleic anhydride is 131.80 parts of phthalic anhydride, 84.2 parts of ethylene glycol is 573.9 parts, and glycerin. A polyester having a number average molecular weight of about 500, a hydroxyl value of 340 mgKOH / g, and an acid value of 0.5 mgKOH / g was carried out in the same manner as in Production Example 13 except that 409.3 parts and the internal temperature was changed from 205 ° C to 220 ° C. A polyol was obtained.

(Production Example 19) Production Example of Polyester Polyol: THEI (OPAEG) 2 In Production Example 13, 98.1 parts of maleic anhydride is 992.4 parts of phthalic anhydride, 84.2 parts of ethylene glycol is 432.5 parts, Tris The number average molecular weight was about 420, the hydroxyl value was 269 mgKOH / g, acid was used except that the amount of (2-hydroxyethyl) isocyanurate was 875.1 parts and the internal temperature was 205 ° C. was changed to 220 ° C. A polyester polyol having a value of 0.9 mg KOH / g was obtained.

(Production Example 20) Polyester polyol: Production example of EGSucA In Production Example 13, 98.1 parts of maleic anhydride is 118.1 parts of succinic acid, 78.5 parts of ethylene glycol is 71.6 parts, and the internal temperature is 205 ° C. A polyester polyol having a number average molecular weight of about 1000, a hydroxyl value of 112.2 mgKOH / g, and an acid value of 0.4 mgKOH / g was obtained in the same manner as in Production Example 13 except that the temperature was 220 ° C.

(Production Example 21) Production Example of Polyester Polyol: EGAA In Production Example 13, 98.1 parts of maleic anhydride is 146.2 parts of adipic acid, 78.5 parts of ethylene glycol is 81.9 parts, and the internal temperature is 205 ° C. A polyester polyol having a number average molecular weight of about 600, a hydroxyl value of 185 mgKOH / g, and an acid value of 0.8 mgKOH / g was obtained in the same manner as in Production Example 13 except that the temperature was 220 ° C.

(Production Example 22) Polyester polyol (A): EGMA: THEI (o-PAEG) 3 (3: 7)
Polyester polyol (A) of Production Example 14: 70 parts of EGMA and polyester polyol of Production Example 16: THEI (OPAEG) 3 were mixed at a ratio of 30 parts while heating to 100 ° C. to obtain a polyester polyol.

(Curing agent)
"Takenate D-110N" manufactured by Mitsui Chemicals, Inc. (trimethylolpropane adduct of metaxylylene diisocyanate, non-volatile content 75%, NCO approx. 11.5%)
“Takenate 500” manufactured by Mitsui Chemicals, Inc. (metaxylylene diisocyanate, nonvolatile content 100%, NCO approx. 45%)
"Death module N3200" manufactured by Sumika Bayer Urethane Co., Ltd. (hexuremethylene diisocyanate biuret, non-volatile content 100%, NCO approx. 23%)
(catalyst)
“DICnate Co 8% L” (Co compound (transition metal complex) -containing polymerization catalyst) manufactured by DIC Corporation

(Example 9) to (Example 15)
According to the examples in Table 4 to Table 6, polyester polyol, curing agent, catalyst and solvent were mixed to obtain an adhesive. The coating method and the evaluation method were as follows.

(Comparative Example 5) to (Comparative Example 8)
According to the comparative examples in Tables 4 to 6, polyester polyol, curing agent, catalyst and solvent were mixed to obtain an adhesive. The coating method and the evaluation method were as follows.

(Coating method 1)
Using a bar coater, the solvent-type adhesive is a corona of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount is 5.0 g / m ² (solid content). It was applied to the treated surface, and the solvent was volatilized and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film on which the adhesive was applied, and a 70 μm thick CPP film (“ZK93KM, manufactured by Toray Industries, Inc.) ]) Was laminated with the corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / CPP film. Next, this composite film was aged at 40 ° C. for 3 to 5 days to cure the adhesive, and the oxygen barrier laminate film of the present invention was obtained.

(Coating method 2)
The solventless adhesive is heated to about 100 ° C. and applied to a PET film so that the coating amount is 5.0 g / m ² using a roll coater manufactured by Polytype Co., Ltd. A composite film having a layer structure of PET film / adhesive layer / CPP film was prepared by laminating with the film. Subsequently, this composite film was subjected to aging at 40 ° C. for 3 days to cure the adhesive, thereby obtaining the oxygen barrier laminate film of the present invention.

(Evaluation methods)
(1) Adhesive strength The oxygen barrier laminate film after aging was cut into a width of 15 mm parallel to the coating direction, and a PET / CPP film was used with a Tensilon universal testing machine manufactured by Orientec Co., Ltd. Then, the atmospheric temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeling by the 180 ° peeling method was defined as the adhesive strength. The unit of adhesive strength was N / 15 mm.

(2) Oxygen transmission rate Oxygen barrier laminated film after aging was used in an atmosphere of 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen transmission rate measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured below. Note that RH represents humidity.

(Measurement of glass transition temperature of cured coating)
In accordance with Tables 4 to 6, polyester polyol, curing agent, catalyst and solvent are mixed, and the non-corona-treated surface of the CPP film is applied using an applicator, dried at reduced pressure, and then treated at 40 ° C. for 3 days. went. The cured coating film is peeled off from the CPP film, and the range from -50 ° C to 200 ° C, 1 Hz, and the temperature increase rate is 3 ° C / min. With Rheometric System Analyzer RSAIII manufactured by TA Instruments Japan Co., Ltd. The elastic modulus was measured under the following conditions. Tan δ was calculated from the obtained dynamic storage elastic modulus and dynamic loss elastic modulus according to the following formula, and the temperature showing the peak value of tan δ was defined as the glass transition temperature.

(Solubility)
The polyester polyol shown in the production example was mixed with ethyl acetate and methyl ethyl ketone (described as MEK) so as to have a nonvolatile content of 50%, and the solubility was confirmed. When the state of the liquid became transparent, it was judged that the solubility was good and judged as “◯”, and when turbidity occurred, the solubility was judged as poor and judged as “x”.

(Double bond component ratio)
In the component of the polyester polyol shown in the production example, the mass ratio of all components of the polymerizable double bond component was calculated.

Here, the monomer refers to the polyvalent carboxylic acid and polyhydric alcohol.

(aging)
The period carried out at an aging temperature of 40 ° C. is shown.
The results are shown in Tables 4-6.

As a result, when Examples 9-13 and Comparative Examples 5-6 were compared, and when Examples 14-15 were compared with Comparative Examples 7-8, an oxygen barrier using an adhesive of polyester polyol (A) was used. The laminated film exhibited an oxygen barrier property with a high oxygen permeability under 90% RH as compared with a polyester polyol not containing a polymerizable double bond, and had a good laminate strength. That is, by introducing a polymerizable double bond, it was possible to lower the oxygen permeability and to impart oxygen barrier properties.

Production Examples 23 to 29, Examples 16 to 22 and Comparative Examples 9 and 10 relate to the polyester resin composition according to (III).
Production Example 23 Production Example of Polyester Polyol (A): Gly (OPAEG) 2MA In the same manner as in Production Example 13, the title compound was obtained.

Production Example 24 Production Example of Polyester Polyol (A): Gly (OPAEG) 2OPA 1316.8 parts of phthalic anhydride in Production Example 23 is 1023.7 parts, 573.9 parts of ethylene glycol is 446.2 parts, and glycerin A polyester polyol having a hydroxyl value of 309.8 mgKOH / g was obtained in the same manner as in Production Example 23 except that 409.3 parts was changed to 318.2 parts.

Next, the temperature was lowered to 120 ° C., and 511.9 parts of phthalic anhydride was added thereto to maintain 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the charged amount of phthalic anhydride, and the number average molecular weight was about 620, the hydroxyl value was 183.9 mgKOH / g, and the acid value was 94.7 mgKOH / g. A polyester polyol was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group

(Production Example 25) Production Example of Polyester Polyol (A): THEI (OPAEG) 2MA 1316.8 parts of phthalic anhydride in Production Example 23 is 992.4, 573.9 parts of ethylene glycol is 432.5 parts, and glycerin A polyester polyol having a hydroxyl value of 269.4 mgKOH / g was obtained in the same manner as in Production Example 23 except that 409.3 parts were changed to 875.1 parts of tris (2-hydroxyethyl) isocyanurate.

Next, the temperature was lowered to 120 ° C., and 343.2 parts of maleic anhydride was added thereto, and the temperature was maintained at 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the charged amount of maleic anhydride, and the polyester polyol had a number average molecular weight of about 720, a hydroxyl value of 156 mgKOH / g, and an acid value of 77.8 mgKOH / g. Got. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group

(Production Example 26) Production Example of Polyester Polyol (A): THEI (OPAEG) 2OPA 1316.8 parts of phthalic anhydride in Production Example 23 is 816.3 parts, and 573.9 parts of ethylene glycol is 355.7 parts. A polyester polyol having a hydroxyl value of 207.7 mgKOH / g was obtained in the same manner as in Production Example 22 except that 409.3 parts of glycerin was changed to 719.8 parts of tris (2-hydroxyethyl) isocyanurate.

Next, the temperature was lowered to 120 ° C., and 408.2 parts of phthalic anhydride was added thereto to maintain 120 ° C. The esterification reaction was terminated when the acid value was approximately half of the acid value calculated from the charged amount of phthalic anhydride, and had a number average molecular weight of about 780, a hydroxyl value of 143.3 mgKOH / g, and an acid value of 69.2 mgKOH / g. A polyester polyol was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group

Production Example 27 Production Example of Polyester Polyol (A): Gly (OPAEG) 2TMT 1316.8 parts of phthalic anhydride in Production Example 23 is 274.0 parts, 573.9 parts of ethylene glycol is 119.4 parts, and glycerin A polyester polyol having a hydroxyl value of 306.8 mgKOH / g was obtained in the same manner as in Production Example 1 except that 409.3 parts were changed to 85.2 parts.

Next, the temperature was lowered to 80 ° C., and 192.1 parts of trimellitic anhydride dissolved in 192 parts of methyl ethyl ketone was added thereto to maintain the reflux temperature. When the acid value was approximately 2/3 of the acid value calculated from the amount of trimellitic anhydride charged, the esterification reaction was terminated, methyl ethyl ketone was removed under reduced pressure, the number average molecular weight was about 640, and the hydroxyl value was 174.9 mgKOH / g, A polyester polyol having an acid value of 174.5 mgKOH / g was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 2 carboxyl groups

(Production Example 28) Production Example of Polyester Polyol: THEI (OPAEG) 3 In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. .3 parts, tris (2-hydroxyethyl) isocyanurate 668.1 parts and titanium tetraisopropoxide in an amount corresponding to 100 ppm with respect to the total amount of polycarboxylic acid and polyhydric alcohol, The internal temperature was maintained at 220 ° C. by gradually heating so that the upper temperature did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 860, a hydroxyl value of 195.4 mgKOH / g, and an acid value of 0.9 mgKOH / g. Polyester polyol (A) Number of functional groups designed per molecule Hydroxyl groups: 3, carboxy groups: 0

(Production Example 29) Production Example of Polyester Polyol: Gly (OPAEG) 3 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc. .3 parts, glycerin 253.2 parts and titanium tetraisopropoxide in an amount corresponding to 100 ppm with respect to the total amount of polyvalent carboxylic acid and polyhydric alcohol, and the upper temperature of the rectifying 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 to obtain a polyester polyol having a number average molecular weight of about 650, a hydroxyl value of 261.2 mgKOH / g, and an acid value of 0.8 mgKOH / g. Polyester polyol (A) Number of functional groups designed per molecule Hydroxyl groups: 3, carboxy groups: 0

(Curing agent)
"Takenate D-110N" manufactured by Mitsui Chemicals (Trimethylolpropane adduct of metaxylylene diisocyanate, non-volatile content 75%, NCO approx. 11.5%)
"Takenate 500" manufactured by Mitsui Chemicals (metaxylylene diisocyanate, nonvolatile content 100%, NCO approximately 45%)
Sumika Bayer Urethane "Desmodur N3200" (hexamethylene diisocyanate biuret, non-volatile content 100%, NCO approx. 23%)

(Adhesive manufacturing method)
The resin and curing agent obtained in the above production example were blended to obtain an adhesive. Formulation examples are shown in Tables 1 to 3.

(Coating method 1)
Using a bar coater, the solvent-type adhesive is a corona of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 μm so that the coating amount is 5.0 g / m ² (solid content). It was applied to the treated surface, and the solvent was volatilized and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film on which the adhesive was applied, and a 70 μm thick CPP film (“ZK93KM, manufactured by Toray Industries, Inc.) ]) Was laminated with the corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / CPP film. Next, this composite film was aged at 40 ° C. for 3 days to cure the adhesive, and the oxygen barrier laminate film of the present invention was obtained.

(Coating method 2)
The solventless adhesive is heated to about 100 ° C., and a corona of a 12 μm thick PET film (“E-5102” manufactured by Toyobo Co., Ltd.) using a roll coater manufactured by Polytype Co., Ltd. After coating the treated surface so that the coating amount is 5.0 g / m ² , the coated surface is laminated with a corona-treated surface of a 70 μm thick CPP film (“ZK93KM” manufactured by Toray Industries, Inc.), and a PET film / adhesive layer / A composite film having a layer structure of a CPP film was produced. Subsequently, this composite film was subjected to aging at 40 ° C. for 3 days to cure the adhesive, thereby obtaining the oxygen barrier laminate film of the present invention.

(2) Initial cohesion force The adhesive was coated with a 50 μm-thick PET film A (“E-5100” manufactured by Toyobo Co., Ltd.) using a bar coater to give a coating amount of 5.0 g / m ² (solid content). )) Was applied to the corona-treated surface, and then the diluting solvent was evaporated and dried. Laminate the adhesive surface of the PET film A to which the adhesive has been applied and the corona-treated surface of the PET film B (“E-5100” manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm to obtain a PET film A / adhesive layer A composite film having a layer structure of / PET film B was produced. Without performing aging for curing, the obtained composite film was immediately cut into a width of 15 mm and a length of 25 mm to prepare a test piece.

Next, using the Tensilon universal testing machine manufactured by Orientec Co., Ltd., the atmosphere temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and one end in the length direction of the obtained test piece was PET film A and the other end was Fixed the PET film B, conducted a tensile test, and determined the obtained strength as the initial cohesive force. The unit was N / cm ² . The evaluation value was the maximum measured intensity, and the results are shown in the table.

(3) Laminate suitability As an assessment of laminate suitability, the appearance of the film immediately after lamination was evaluated according to the following criteria.
○: Uniformly wet and good appearance.
(Triangle | delta): Although it gets wet uniformly, a coating film has a slight wave | undulation.
X: The coating film has a large amount of undulation.

(4) Oxygen transmission rate Oxygen barrier laminate film after aging was measured at 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen transmission rate measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured under atmosphere.

(Measurement of glass transition temperature of cured coating)
According to Table 7 and Table 8, polyester polyol, a curing agent, and a solvent were mixed, and the non-corona-treated surface of the CPP film was coated using an applicator, and then treated at a reduced pressure dryer of 40 ° C./3 days. The cured coating film was peeled off from the CPP film, and the range from -50 ° C to 200 ° C, 1 Hz, and the temperature increase rate of 3 ° C / min were measured with RAEmetric System Analyzer RSAIII manufactured by TA Instruments Japan Co., Ltd. The elastic modulus was measured under the following conditions. Tan δ was calculated from the obtained dynamic storage elastic modulus and dynamic loss elastic modulus according to the following formula, and the temperature showing the peak value of tan δ was defined as the glass transition temperature.

The results are shown in Tables 7 and 8.

As a result, the oxygen barrier laminated film using the adhesives of Examples 16 to 22 has a high oxygen barrier property and initial cohesive strength under 90% RH compared with the polyester polyol (A) not containing a carboxy group. And also had good adhesive strength. In Comparative Examples 9 to 10, the oxygen permeability was relatively good but not at a sufficient level, and the initial cohesion was also at a significantly low level. By introducing a carboxy group and adjusting the acid value to an appropriate range, it was possible to impart oxygen barrier properties, high initial cohesive strength, and high adhesive strength.

Since the gas barrier multilayer film of the present invention has gas barrier properties, it can be suitably used as various packaging materials. Further, since the barrier coating material and the gas barrier adhesive constituting the gas barrier multilayer film of the present invention have gas barrier properties, in the case of the gas barrier coating material, in addition to the film laminating primer for the packaging material, for display elements In addition to coating agents for electronic materials such as coating agents for gas barrier substrates, coating materials for building materials, coatings for industrial materials, and gas barrier properties can be suitably used. In addition, in the case of gas barrier adhesives, it is suitable for adhesives for film laminates for packaging materials, primers for film laminates, adhesives for protective films for solar cells, sealing materials for display elements, etc. Can be used for

Claims

In a gas barrier multilayer film having a gas barrier layer obtained by curing a polyester resin composition obtained by reacting a polyester polyol and a curing agent,
A gas barrier multilayer film in which the polyester resin composition is any one selected from the following (I) to (III).
(I) A polyester resin composition obtained by reacting a polyester polyol represented by the general formula (1) with a curing agent.

(In the formula (1), R 1 to R 3 each independently represents a hydrogen atom, or a compound represented by the general formula (2)

(In the formula (2), 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 Represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group, and Y represents an alkylene group having 2 to 6 carbon atoms. However, at least one of R 1 to R 3 represents a group represented by the general formula (2). )
(II) containing a polyester polyol (A) having a polymerizable carbon-carbon double bond in the molecule and having two or more hydroxyl groups, and a polyisocyanate (B) having two or more isocyanate groups. A resin composition for an oxygen barrier adhesive.
(III) A resin composition for an oxygen barrier adhesive comprising a polyester polyol (C) and a polyisocyanate (D) having two or more isocyanate groups,
The polyester polyol (C) has at least one carboxy group and two or more hydroxyl groups obtained by reacting a carboxylic anhydride or a polyvalent carboxylic acid with a polyester polyol having three or more hydroxyl groups. Resin composition for oxygen barrier adhesive.
In the polyester resin composition according to (I),
The gas barrier multilayer film according to claim 1, wherein the polyester resin composition contains a glycerol residue of the polyester polyol in an amount of 5% by mass or more.
The gas barrier multilayer film according to claim 2, wherein the curing agent is an isocyanate compound.
The gas barrier multilayer film according to claim 3, wherein the isocyanate compound is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and a polyhydric alcohol having at least three hydroxyl groups in the molecule.
In the polyester resin composition according to (II),
2. The gas barrier multilayer film according to claim 1, wherein the monomer component having a polymerizable carbon-carbon double bond constituting the polyester polyol (A) is maleic acid, maleic anhydride, or fumaric acid.
The gas barrier multilayer film according to claim 5, wherein the monomer component having a polymerizable carbon-carbon double bond is 5 to 60 parts by mass with respect to 100 parts by mass of the total monomer components constituting the polyester polyol (A).
The gas barrier multilayer film according to claim 5 or 6, wherein the polyisocyanate (B) contains a polyisocyanate having an aromatic ring.
The gas barrier multilayer film according to claim 7, wherein the polyisocyanate having an aromatic ring is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and an alcohol having two or more hydroxyl groups.
The gas barrier multilayer film according to any one of claims 5 to 8, further comprising an oxidation polymerization catalyst.
The gas barrier multilayer film according to claim 1, wherein the polyester polyol (C) has an aromatic ring.
The gas barrier multilayer film according to claim 10, wherein the polyester polyol (C) has a hydroxyl value of 20 to 250 and an acid value of 20 to 200.
The gas barrier multilayer film according to claim 10 or 11, wherein the polyisocyanate (D) contains a polyisocyanate having an aromatic ring.
The gas barrier multilayer film according to claim 12, wherein the polyisocyanate having an aromatic ring is metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and an alcohol having two or more hydroxyl groups.
A gas barrier coating material obtained by curing the polyester resin composition (I) of the polyester resin composition according to claim 1.
A gas barrier adhesive obtained by curing the polyester resin composition of (II) or (III) among the polyester resin composition according to claim 1.
The gas barrier coating material according to claim 14, which is a solvent-free type.
The gas barrier adhesive according to claim 15, which is a solventless type.
The gas barrier coating material according to claim 14, wherein the polyester polyol (A) or the polyester polyol (C) is dissolved in a ketone solvent, an ester solvent, or a mixed solvent containing a ketone solvent or an ester solvent.
The gas barrier adhesive according to claim 15, wherein the polyester polyol (A) or the polyester polyol (C) is dissolved in a ketone solvent, an ester solvent, or a mixed solvent containing a ketone solvent or an ester solvent.
16. The oxygen gas barrier multilayer film comprising the gas barrier adhesive according to claim 15 and a laminate film, wherein the oxygen permeability of at least one laminate film is 0.1 cc / m 2 · day · atm or more. Oxygen barrier multilayer film.
A polyester resin composition obtained by reacting the polyester polyol used in the gas barrier multilayer film according to any one of claims 1 to 13 with a curing agent.
A packaging material using the gas barrier multilayer film according to any one of claims 1 to 13.