JP5861923B2 - Gas barrier multilayer film - Google Patents

Description

  The present invention relates to a gas barrier multilayer film.

  Packaging materials such as food and beverages not only 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, etc. Various 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.

  For these reasons, a composite flexible film in which different polymer materials are combined is widely used as the packaging material. In general, a composite flexible film is composed of a thermoplastic film layer as an outer layer having product protection and various functions, a thermoplastic film layer as a sealant layer, and the like. There is also a method in which an adhesive and a thermoplastic resin for a sealant layer are melt-extruded in three layers and an unstretched laminated sheet is molded and then stretched (for example, see Patent Document 1). A dry laminating method for producing a multilayer film by adhering layers (for example, see Patent Document 2) is simple and has become mainstream. However, the adhesive used in this application generally has only a function of adhering between different films.

In recent years, there has been a demand for further enhancement of functionality for multilayer films.
In addition to the conventional oxygen barrier properties, ethyl alcohol is one of the methods for extending the shelf life and expiry date of foods to prevent the growth of microorganisms and molds that cause food deterioration and spoilage. It has been widely practiced to enclose transpiration material or ethyl alcohol vapor in a package together with food. In the case of such packaging, an alcohol barrier function is also required in order to maintain the state of food by preventing leakage of ethyl alcohol. 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.

  Moreover, in order to reduce the influence on the food, it is widely performed to enclose an inert gas such as nitrogen gas or carbon dioxide gas in the package.

  For the purpose as described above, a gas barrier barrier laminated film is generally used. As such a container, for example, in Patent Document 3 and Patent Document 4, a thermoplastic film layer that is an outer layer, and a thermoplastic plastic that is a sealant layer. A gas barrier laminate film is described in which a film layer is bonded with an epoxy resin composition comprising an epoxy resin and an epoxy resin curing agent.

  On the other hand, a method of imparting a gas barrier function to an adhesive used at the time of lamination is also known. This method has an advantage that a multi-layer film for gas barrier can be produced without using a film having a special gas barrier function imparted by a process and configuration essential for producing a laminated film. On the other hand, the flexible molecular structure essential for adhesives generally has high gas permeability. For this reason, the adhesive ability and the gas barrier function are often in a trade-off relationship, and this elimination increases the technical difficulty.

  However, epoxy adhesives are hardly used as laminate adhesives for multilayer films, while reaction systems of polyester polyols and polyisocyanates are most widely used. Therefore, in the case of switching the product number from a general-purpose adhesive, there has been a strong demand for non-epoxy adhesives from the viewpoints of commonality of solvents, mixing properties when materials remain, and the like. In addition, in the case of a bag-like container containing food as a content, materials other than epoxy-based materials have been demanded from the viewpoint of compound safety. In addition, in these documents, there is a description about the oxygen transmission rate, but there is no mention of being able to block other components.

Japanese Laid-Open Patent Publication No. 2006-341423 JP 2003-13032 A Japanese Patent No. 4092549 Japanese Patent No. 4366563 JP 2011-224921 A

  In the multilayer film described in the background art, the adhesive layer to be used often does not have a gas barrier property, and it is necessary to apply a layer having a gas barrier property separately in order to shut off gas etc. to the package contents. there were. However, polyvinylidene chloride (PVDC film), which is generally used as a film constituting the gas barrier layer, is colored by absorption of ultraviolet rays, or the generated decomposition product reaches the contents through the sealant layer. In other words, there is a problem that foreign matters such as decomposition products are mixed in the contents.

  Therefore, the problem to be solved by the present invention is a component that can be used for packaging materials and the like mainly for foods, has a specific adhesive layer and a sealant layer excellent in gas barrier properties, and constitutes a layer to the above contents Alternatively, it is an object of the present invention to provide a gas barrier multilayer film having a multilayer structure capable of preventing mixing of decomposition products of components.

In the gas barrier multilayer film having a gas barrier adhesive layer comprising a polyester polyol (A) having two or more hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups. ,
The gas barrier multilayer film further has a sealant layer, and the gas barrier multilayer film has a multilayer structure in which the sealant layer and the gas barrier adhesive layer are in contact with each other.

  According to the present invention, it is possible to provide a multilayer film that is excellent in gas barrier properties and can prevent mixing of components constituting the layer or decomposition products of components. Moreover, it becomes possible to provide a multilayer film for oxygen gas barrier, a multilayer film for water vapor barrier, a multilayer film for inert gas barrier, a multilayer film for alcohol barrier, and a multilayer film for aroma preservation using the multilayer film.

  Further, the gas barrier multilayer film of the present invention is structurally simpler than conventional films because the adhesive used in the present invention has a barrier property, and the complicated production process can be simplified. .

[Resin having two or more hydroxyl groups in one molecule as a functional group (A)]
The resin (A) used in the present invention is a resin having a hydroxyl group in one molecule as a functional group, and the main skeleton contains polyester, polyester polyurethane, polyether, or polyether polyurethane. There is no particular limitation as long as the adhesive strength or gas barrier property of the present invention can be exhibited.

  For the polyester used in the present invention, a known technique can be used. For example, the polyester can be obtained by a reaction between a polyhydric alcohol and a polycarboxylic acid. Polyester polyurethane can be obtained by a known technique, for example, by reaction of polyester polyol and diisocyanate. For the polyether, known techniques can be used. For example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator. Obtained by polymerization. The polyether polyurethane can be obtained by a known technique, for example, by reaction of polyether with diisocyanate.

(Polyvalent carboxylic acid)
The resin (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. Examples of the polyvalent carboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and examples of the aromatic polyvalent carboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, and 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 acid and Anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy B) Polybasic acids such as 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 them, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, an acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable in order to obtain barrier properties.

(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, cyclohexane dimethanol, 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 preferred, and ethylene glycol is more preferred. The polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by a known and commonly used method.

More specifically, as the resin (A) having two or more hydroxyl groups of the present invention,
A polyester polyol (A1) obtained by reacting a carboxylic acid anhydride or a polycarboxylic acid with a polyester polyol having three or more hydroxyl groups,
A polyester polyol (A2) having a polymerizable carbon-carbon double bond,
A polyester polyol (A3) having a glycerol skeleton,
A polyester polyol (A4) obtained by polycondensation of an ortho-oriented polyvalent carboxylic acid component and a polyhydric alcohol component,
-Polyester polyol (A5) having an isocyanuric ring,
Etc.
Hereinafter, each polyester polyol will be described.

[Polyester polyol (A1) obtained by reacting carboxylic acid anhydride or polycarboxylic acid with polyester polyol having 3 or more hydroxyl groups]
The polyester polyol (A1) used in the present invention has at least one carboxy group and two 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 the above 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.

  As the polyhydric alcohol component and polyhydric alcohol component of the polyester polyol (A1), preferably, a polycarboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neopentyl Reacting a carboxylic acid anhydride or a polyvalent carboxylic acid with a polyester polyol (I) having three or more hydroxyl groups composed of a polyhydric alcohol component containing at least one selected from the group consisting of 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 thus it is presumed that the gas barrier property is excellent. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesion and gas 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)
When synthesizing a polyester polyol (I) having three or more hydroxyl groups, when a branched structure is introduced by a polyvalent carboxylic acid component, it is necessary to have at least a part of a trivalent or higher carboxylic acid. Examples of these compounds include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, trivalent or higher polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.

  As 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- ( - it can be used in hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

(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)
When synthesizing a polyester polyol (I) having three or more hydroxyl groups, when a branched structure is introduced by a polyhydric alcohol component, it is necessary to have at least part of a trihydric or higher polyhydric alcohol. Examples of these compounds include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol. In order to prevent gelation, trihydric alcohol is preferable as the trihydric or higher polyhydric alcohol.

  As other components, in the present invention, the above-mentioned polyhydric alcohol component 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 diol, 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.

Next, the reaction of the polyester polyol (I) of the present invention with a carboxylic acid anhydride or a polyvalent carboxylic acid is carried out as follows.
That is, the polyester polyol (I) can be obtained by reacting 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 at least two hydroxyl groups of the resin (A) after the reaction are required, so the polyvalent carboxylic acid is 1/3 or less of the hydroxyl groups of the polyester polyol (I). It is preferable to make it react with. Although there is no restriction | limiting in the carboxylic acid anhydride or polyhydric carboxylic acid used here, when 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 and the like can be used as the trivalent carboxylic acid anhydride.

  The polyester polyol (A1) preferably 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 gas 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 resin (A) and the isocyanate compound (B) becomes too fast, and good coating suitability cannot be obtained.

[Polyester polyol (A2) having a polymerizable carbon-carbon double bond]
Further, examples of the polyester polyol (A2) of the present invention include those having a polymerizable carbon-carbon double bond in the molecule.

  The polyester polyol (A2) used in the present invention is obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, and has a polymerizable carbon-carbon double bond as a component of the polyvalent carboxylic acid and polyhydric alcohol. Can be used to introduce a polysynthetic carbon-carbon double bond into the molecule of the polyester polyol (A2).

(Polyvalent carboxylic acid)
The polyester polyol (A2) 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. Examples of the aromatic polycarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and examples of the aromatic polyvalent carboxylic acid include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimethyl Merit 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 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. These acid anhydrides can also be used. Among them, succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, an acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable in order to obtain barrier properties.

(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 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, cyclohexane dimethanol, 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.

  Moreover, in the said polyester polyol (A2), although the polymerizable double bond was introduce | transduced into the polyester polyol (A2) by using the polyhydric carboxylic acid and polyhydric alcohol which have a polymerizable carbon-carbon double bond, It may be a reaction between a polyester polyol having 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 by crosslinking with an isocyanate compound. When the polyester polyol has 1 or 2 hydroxyl groups, the polyester polyol (A2) obtained by reacting with a carboxylic acid having a polysynthetic double bond has 0 or 1 hydroxyl group and reacts with the isocyanate compound (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.

  The polyester polyol (A2) preferably has a hydroxyl value of 20 to 250 mgKOH / g and an acid value of 0 to 200 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.

  Moreover, it has the characteristics that the monomer component which has a polymerizable carbon-carbon double bond is 5-60 mass parts with respect to 100 mass parts of all the monomer components which comprise polyester polyol (A2).

  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.

  In the present application, the monomer component amount (double bond component ratio) having a polymerizable carbon-carbon double bond in the polyester polyol (A2) is calculated using the formula (a).

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

  Moreover, as polyester polyol (A2) of this invention, a drying oil or a semi-drying oil can be mentioned. Examples of the drying oil or semi-drying oil include publicly known and commonly used drying oils having a carbon-carbon double bond, and semi-drying oils.

[Polyester polyol having glycerol skeleton (A3)]
Examples of the polyester polyol (A3) of the present invention further include a polyester polyol having a glycerol skeleton represented by the general formula (1).

(In the formula (1), R1 to R3 are each independently a hydrogen atom or 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). )

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

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

The content of the glycerol backbone in this application, with respect to gas barrier adhesive organic resin composition total solids of the mass of the present application, residues obtained by removing R ₁ to R ₃ in the general formula (1) (C _{The amount of 3} H ₅ O ₃ = 89.07) is calculated using equation (b).

    P: represents a polyester polyol (A3) having a glycerol skeleton.

  The present invention is characterized by having a glycerol residue of 5% by mass or more in the organic resin composition for gas barrier adhesives in order to exhibit high barrier properties.

(Method for calculating mass of solid content of organic resin composition for gas barrier adhesive)
The mass excluding the dilution solvent mass, the volatile component mass contained in the curing agent, and the inorganic component from the mass part of the resin composition for gas barrier adhesive is the mass of the total solid content of the organic resin for gas barrier adhesive.

  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 polyol (A3) 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 polyol (A3) 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 in a range not impairing the effects of the present invention. Other polyvalent carboxylic acid components may be copolymerized. Specifically, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc., as the unsaturated bond-containing polyvalent carboxylic acid, maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc. as alicyclic polyvalent carboxylic acid, terephthalic acid, isophthalic acid, pyromellitic as aromatic polyvalent carboxylic acid Acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its anhydride, 1,2-bis ( Phenoxy) ethane-p, p′-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; Polybasic acids such as droxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.

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

[Polyester polyol (A4) obtained by polycondensation of ortho-oriented polyvalent carboxylic acid component and polyhydric alcohol component]
The polyester polyol (A4) used in the present invention comprises a polyvalent carboxylic acid component containing at least one orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. It consists of a polyhydric alcohol component containing at least one selected from the group. In particular, a polyester polyol having a content of 70 to 100% by mass of the orthophthalic acid and its anhydride with respect to all the components of the polyvalent carboxylic acid is preferable.

(Polyvalent carboxylic acid and other components)
The polyester polyol (A4) of the present invention essentially comprises the above-mentioned orthophthalic acid and its anhydride as a polyvalent carboxylic acid component. However, other polyvalent carboxylic acid components may be copolymerized within a range that does not impair the effects of the present invention. May be. 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- (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. Of these, succinic acid, 1,3-cyclopentanedicarboxylic acid, and isophthalic acid are preferable.

  Examples of the polyhydric alcohol component and other components include those described above.

[Polyester polyol having an isocyanuric ring (A5)]
The resin (A) of the present invention further preferably includes a polyester polyol (A5) having an isocyanuric ring represented by the following general formula (3).

(In General Formula (3), R _{1 to} R ₃ are each independently — (CH ₂ ) n 1 -OH (where n1 represents an integer of 2 to 4), or General Formula (4)

(In General Formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X represents a 1,2-phenylene group, a 1,2-naphthylene group, or a 2,3-naphthylene group. , 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, an arylene group which may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms. Represents.)
Represents a group represented by However, at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4))

In Formula (3), - (CH 2 ) alkylene group represented by _n1- may be branched be linear. n1 is preferably 2 or 3, and most preferably 2.

In the said General formula (4), n2 represents the integer of 2-4, n3 represents the integer of 1-5.
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, and has a substituent. Represents an arylene group which may be substituted.

  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.

  The substituent of X is preferably a hydroxyl group, a cyano group, a nitro group, an amino group, a phthalimide group, a carbamoyl group, an N-ethylcarbamoyl group, or a phenyl group, preferably a hydroxyl group, a phenoxy group, a cyano group, a nitro group, or a phthalimide group. A phenyl group is most preferred.

  In the general formula (4), Y represents ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl-1,5-pentylene group, 1,6-hexylene group, methylpentylene. Represents an alkylene group having 2 to 6 carbon atoms, such as a len group or a dimethyl butylene group; Among them, Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.

In the general formula (3), at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). Among these, it is preferable that all of R ₁ , R ₂ and R ₃ are groups represented by the general formula (4).

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

  The polyester polyol (A5) having an isocyanuric ring represented by the general formula (3) includes a triol having an isocyanuric ring, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted at the ortho position, or an anhydride thereof, It is obtained by reacting a monohydric alcohol component as an essential component.

  Examples of the triol having an isocyanuric ring include alkylene oxide adducts of isocyanuric acid such as 1,3,5-tris (2-hydroxyethyl) isocyanuric acid and 1,3,5-tris (2-hydroxypropyl) isocyanuric acid. Etc.

  In addition, aromatic polyvalent carboxylic acids in which the carboxylic acid is substituted in the ortho position or anhydrides thereof include orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid. Or its anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, 2,3-anthracene carboxylic acid or its anhydride, etc. are mentioned. These compounds may have a substituent on any carbon atom of the aromatic ring.

  Examples of the substituent include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.

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

  Among them, 1,3,5-tris (2-hydroxyethyl) isocyanuric acid or 1,3,5-tris (2-hydroxypropyl) isocyanuric acid is used as the triol compound having an isocyanuric ring, and the carboxylic acid is in the ortho position. Polyester polyol compounds having an isocyanuric ring using orthophthalic anhydride as the aromatic polyvalent carboxylic acid substituted with or an anhydride thereof and ethylene glycol as the polyhydric alcohol are particularly excellent in gas barrier properties and adhesion. .

  The isocyanuric ring is highly polar and trifunctional. Therefore, the entire system can be made highly polar and the crosslinking density can be increased. From such a viewpoint, it is preferable to contain 5 mass% or more of the isocyanuric ring with respect to the total solid content of the adhesive resin.

  The reason why the adhesive of the present invention having an isocyanuric ring can secure gas barrier properties and dry laminate adhesiveness is presumed as follows.

  The isocyanuric ring is highly polar and does not form hydrogen bonds. In general, as a technique for improving adhesiveness, a method in which a highly polar functional group such as a hydroxyl group, a urethane bond, a ureido bond or an amide bond is blended is known, but a resin having these bonds forms intermolecular hydrogen bonds. Easily and may damage the solubility in ethyl acetate and 2-butanone solvent often used in dry laminate adhesives, but polyester resins with an isocyanuric ring do not impair the solubility and can be easily diluted It is.

  In addition, since the isocyanuric ring is trifunctional, a polyester polyol compound having the isocyanuric ring as the center of the resin skeleton and a polyester skeleton having a specific structure in the branched chain can obtain a high crosslinking density. It is presumed that the gap through which a gas such as oxygen can be reduced by increasing the crosslinking density. Thus, since the isocyanuric ring is highly polar and does not form an intermolecular hydrogen bond and a high crosslink density is obtained, it is presumed that gas barrier properties and dry laminate adhesiveness can be secured.

The content of isocyanuric rings in this application should be noted, with respect to the adhesive resin total solid mass of the present application, except for _R 1 to R ₃ in the general formula (3) residues _{(C 3} N ₃ O 3 = 126 .05) is calculated using equation (c).

    P: represents a polyester polyol (A5) having an isocyanuric ring.

(Method for calculating mass of resin composition organic total solid content of gas barrier adhesive)
The mass excluding the dilution solvent mass, the volatile component mass contained in the curing agent, and the inorganic component from the mass part of the resin composition for gas barrier adhesive is the mass of the total solid content of the organic resin for gas barrier adhesive.

  The polyester polyol having an isocyanuric ring can be obtained by a known polyester production method. Specifically, it can be synthesized by a production method in which the reaction is carried out while removing produced water from the system at a reaction temperature of 200 to 220 ° C. in the presence of a catalyst.

  As a specific example, after the triol having an isocyanuric ring 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 Then, the temperature is increased while stirring and mixing to cause a dehydration condensation reaction. 1 mgKOH / g or less by the acid value measurement method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measurement method described in JIS-K0070 is a numerical value on the right side of the following formula (d) (mgKOH / The target polyester polyol can be obtained by continuing the reaction until it falls within ± 5% of g).

(In formula (d), Mn represents the 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.

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

  As the polyether polyol, active hydrogen such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Addition polymerization of one or more monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, cyclohexylene, etc. by a conventional method using one or more compounds having two atoms as initiators If necessary, an alkyl alcohol having 1 to 4 carbon atoms as an initiator, ethylene oxide as an essential component, further propylene oxide, butylene oxide, styrene oxide, Pikuroruhidorin, may be used in combination of at least one and block or polyoxyalkylene monoalkyl ether obtained by random copolymerization of monomers such as cyclohexylene. Furthermore, polytetramethylene glycol is also exemplified as the polyether polyol. Here, polytetramethylene glycol is a polyol obtained by ring-opening polymerization of tetrahydrafuran. In the synthesis of polytetramethylene glycol, an analogous compound in which a part of tetrahydrofuran is substituted with ethylene oxide or propylene oxide can be used, or it can be used in combination with polytetramethylene glycol.

  The number average molecular weight of these resins (A) is particularly preferably from 450 to 5,000 because a crosslinking density with an excellent balance between adhesive ability and oxygen barrier ability can be obtained. More preferably, the number average molecular weight is 500 to 3000. 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 resin (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 degreeC-60 degreeC. More preferably, it is 25 degreeC-60 degreeC. 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 too lower than −30 ° C., there is a possibility that sufficient gas barrier properties may not be obtained due to intense molecular motion of the polyester polyol near normal temperature.

  Furthermore, you may use the polyester polyurethane polyol and polyether polyurethane polyol which made the number average molecular weight 1000-15000 by urethane expansion | extension by reaction with a diisocyanate compound (A) as an adhesive agent. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has excellent gas barrier properties, excellent initial cohesive force, and is further excellent as an adhesive used during lamination. Moreover, the terminal can be made into an isocyanate group by making the ratio of the hydroxyl group and the isocyanato group in the resin (A) and the diisocyanate compound excessive in isocyanate, and this may be used as a curing agent.

(Adhesive hardener)
The curing agent used in the present invention is not particularly limited as long as it can react with the hydroxyl group of the resin (A), and known curing agents such as diisocyanate compounds, polyisocyanate compounds, and epoxy compounds can be used. Especially, it is preferable to use a polyisocyanate compound from a viewpoint of adhesiveness or retort resistance.

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

  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 the isocyanate blocking agent to an addition reaction by a known and appropriate method.

  Among these, xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate are preferable, and metaxylylene diisocyanate and metahydrogenated xylylene diisocyanate are most preferable in order to obtain good gas barrier properties.

  The glass transition temperature of the cured coating film of the resin (A) and the isocyanate compound (B) of the present invention is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is 0 degreeC-70 degreeC. More preferably, it is 25 degreeC-70 degreeC. When the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature becomes low, 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 fear that sufficient gas barrier properties may not be obtained due to intense molecular motion of the cured coating film at around room temperature, and there is a risk that adhesive strength may be reduced due to insufficient cohesive force.

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

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

  Among them, it is preferable that the curing agent is a polyisocyanate compound having an aromatic ring. If the polyisocyanate compound includes the metaxylene skeleton, a gas barrier is formed not only by hydrogen bonding of the urethane group but also by π-π stacking of aromatic rings. It is preferable because the property can be improved.

  Examples of the polyisocyanate compound containing the meta-xylene skeleton include a trimer of xylylene diisocyanate, a burette synthesized by reaction with an amine, and an adduct obtained by reacting with an alcohol. The adduct body is more preferable because the solubility of the polyisocyanate compound in the organic solvent used for the dry laminate adhesive is easily obtained as compared with the body. 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 (A) and the curing agent, the ratio of the resin (A) and the curing agent is such that the hydroxyl group of the resin (A) and the reaction component of the curing agent are 1 / 0.5 to 1/10 (equivalent ratio). It is preferable to mix | blend so that it may become, More preferably, it is 1 / 1-1 / 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.

  A known polymerization catalyst can be used as a catalyst for promoting polymerization of a polymerizable carbon-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. 0-10 mass parts is preferable with respect to resin (A), and, as for a transition metal complex, More preferably, it is 0-3 mass parts.

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

(Adhesive and other ingredients)
The adhesive of the present invention may contain various additives as long as the adhesive strength and gas barrier properties are not impaired. Examples of additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and antiblocking agents. Examples include agents, colorants, fillers, crystal nucleating agents and the like.

(Plate-like inorganic compound)
The resin composition for adhesives of the present invention is characterized by containing a plate-like inorganic compound.
The plate-like inorganic compound used in the present invention has an effect of improving the laminate strength and gas barrier properties of an adhesive obtained by curing a resin composition for an adhesive.

  The plate-like inorganic compound used in the present invention has a feature that the laminate strength and the barrier property are improved by the plate-like shape. The charge between the layers of the plate-like inorganic compound does not greatly affect the barrier property directly, but the dispersibility to the resin composition is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water, and the amount added is increased. As a result, the resin composition becomes thicker and thixotropic. On the other hand, in the case of being uncharged (nonionic) or non-swelling with respect to water, even if the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be ensured. Examples of the plate-like inorganic compound used in the present invention include, for example, hydrous silicate (phyllosilicate mineral etc.), kaolinite-serpentine clay mineral (halloysite, kaolinite, ende Light, dickite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kerorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, Sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (muscovite, phlogopite etc. mica, margarite, tetrasilic mica, teniolite, etc.), chlorite group (kukeite, sudite , Clinocroix, sha Site Nimaito etc.), hydrotalcite, tabular barium sulfate, boehmite, and aluminum polyphosphate and the like. These minerals may be natural clay minerals or synthetic clay minerals. An inorganic layered compound is used individually or in combination of 2 or more types.

  Moreover, it is preferable that the plate-like inorganic compound used in the present invention is nonionic without intercalation.

  Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite and chrysotile), and pyrophyllite. -The talc family (pyrophyllite, talc, kerolai, etc.) can be mentioned.

  Moreover, it is preferable that the plate-shaped inorganic compound used by this invention is non-swelling with respect to water.

  Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite and chrysotile), and pyrophyllite. -Talc (pyrophyllite, talc, kerolai, etc.), mica or mica clay mineral (mica, muscovite, phlogopite, etc.), margarite, tetrasilic mica, teniolite, etc. (Clinochlor, chamosite, nimite, etc.), hydrotalcite, plate-like barium sulfate and the like.

  The average particle diameter in the present invention means a particle diameter having the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering measurement device. The average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, but is preferably 0.1 μm or more, and more preferably 1 μm or more. If the average particle size is 0.1 μm or less, the length of the long side is short, so that the detour path of oxygen molecules does not become long, and there are problems that it is difficult to improve the oxygen barrier ability and adhesion force. . The side with a large average particle diameter is not particularly limited. When a large plate-like inorganic compound is contained by the coating method and a defect such as a streak occurs on the coated surface, a material having an average particle diameter of 100 μm or less, more preferably 20 μm or less is preferably used.

  The aspect ratio of the plate-like inorganic compound used in the present invention is preferably higher in order to improve the barrier ability due to the maze effect of oxygen. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.

In the present invention, when the total mass of the resin (A), the polyisocyanate compound (B), and the plate-like inorganic compound (C) is 100 parts by mass, the content of the plate-like inorganic compound is improved if the oxygen barrier ability is improved. Although there is no limitation in particular, it is preferable that it is 5-50 mass parts. In the case of 5 parts by mass or less, the barrier ability is difficult to improve, and in the case of 50 parts by mass or more, there is a possibility that the laminating operation becomes difficult due to a decrease in the adhesiveness of the coating surface, or the adhesive force may be insufficient. It is.
The content of the inorganic compound (PWC of the blended grains) can be obtained from the following formula (e).

  As a method for dispersing the inorganic compound prepared in the present invention in the resin (A) or the gas barrier adhesive resin composition, a known dispersion method can be used. For example, an ultrasonic homogenizer, a high-pressure homogenizer, a paint conditioner, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, a nano mill, an SC mill, a nanomizer, and the like can be mentioned, and even more preferably, a high shear force is generated. Examples of equipment that can be used include Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, two-roll, three-roll. One of these may be used alone, or two or more devices may be used in combination.

  Moreover, as a method for improving the acid resistance of the adhesive layer, a known acid anhydride can be used in combination as an additive. Examples of the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.

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

  Moreover, in order to improve the adhesiveness with respect to various film materials immediately after application | coating, you may add tackifiers, such as a xylene resin, a terpene resin, a phenol resin, and a rosin resin, as needed. When adding these, the range of 0.01-5 mass parts is preferable with respect to 100 mass parts of resin (A) and the total amount of a hardening | 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, a light (polymerization) initiator that generates radicals and the like by irradiation with ultraviolet rays is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A). It is preferable to add.

  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.

(Adhesive form)
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 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, it is preferable to apply in a state of heating from 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 adhesive for various applications that require gas barrier properties against polymers, paper, metals, etc. as a gas barrier adhesive.

  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 gas barrier properties, it can be used as a gas 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: Polyolefin film such as biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, and the like. These may be subjected to stretching treatment. As the stretching treatment method, it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used. However, when a transparent vapor-deposited film having a high gas barrier property is used on both sides of the adhesive using the polyester polyol (A2) as the adhesive component, polymerization of the polymerizable double bond of the polyester polyol (A2) of the adhesive component is not possible. It may be inhibited and good barrier properties may not be exhibited. Therefore, when the polyester polyol (A2) is used as the adhesive component, the oxygen barrier property of the gas barrier laminate film is that the oxygen permeability of at least one laminate film is 0.1 cc / m ² · day · atm or more. Is preferred.

  The adhesive of the present invention can be preferably used as an adhesive for laminated films 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 The four-layer composite film using the thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material as a gas barrier film.

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

  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 gas barrier laminated 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 substrate film with a roll such as a roll coater heated to room temperature to 120 ° C., and then immediately applied to the surface after the adhesive of the present invention, which has been heated to room temperature to 120 ° C. in advance, is applied. 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 a bonding aid (anchor coating agent) with 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 gas 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.

  Since the adhesive of the present invention is characterized by having a high gas 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) Film layer, metaxylylene adipamide film layer, inorganic vapor deposited film layer deposited with alumina, silica, etc. .

  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 gas barrier multilayer film of the present invention is characterized by having a sealant layer in addition to the gas barrier adhesive, and having a multilayer structure in which the sealant layer and the gas barrier adhesive layer are in contact with each other.
As the film used for the sealant layer used in the multilayer film of the present invention, a known and conventional film can be used, and examples thereof include an unstretched polypropylene film (CPP) film and a polyethylene film (PE). it can.

  In the multilayer film structure of the present invention, since the sealant layer and the gas barrier adhesive layer are in contact with each other, components from other layers than the sealant layer and the gas barrier adhesive layer constituting the multilayer film are contained through the sealant layer. It becomes possible to prevent reaching an object.

  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 Example 1 Production of Barrier Adhesive “A” In a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., 148.1 parts of phthalic anhydride, 84.2 ethylene glycol And 0.03 part of titanium tetraisopropoxide were charged, and the inner temperature was maintained at 205 ° C. by gradually heating so that the temperature of the upper part 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 an amorphous polyester polyol having a number average molecular weight of 600. This polyester polyol (PAEG) had a hydroxyl value of 190 mgKOH / g and an acid value of 1.0 mgKOH / g. The number of functional groups designed per polyester polyol molecule: hydroxyl group: 2 and carboxy group: 0, and the content of ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all polycarboxylic acid components Is 100 mass%.

  “Takenate D-110N” manufactured by Mitsui Chemicals (trimethylolpropane adduct of metaxylylene diisocyanate) and “Takenate 500” (non-volatile content of metaxylylene diisocyanate) manufactured by Mitsui Chemicals were mixed at a ratio of 50/50 (mass ratio). A curing agent for adhesive was used. The non-volatile content of the curing agent is 87.5% and NCO% 28.1%.

  30 parts of an adhesive curing agent was dissolved in 50 parts of the polyester polyol (PAEG), and 50 parts of ethyl acetate as a diluent solvent was dissolved and dispersed with a stirrer to obtain a barrier adhesive “A”.

(Manufacture example 2) Adjustment of solvent type functional coating material "B" For 100 parts of Dick Dry LX-703VL (manufactured by DIC Graphics: Polyester polyol, non-volatile content / about 62%), which is an adhesive main agent for solvent type laminating, After 9 parts of the adhesive curing agent was mixed, methyl cellosolve, which is an ether-based high boiling point slow-drying solvent, was mixed by 5% by weight to obtain a volatile VOC layer.

(Production Example 3) Adjustment of Non-Barrier Adhesive Adhesive for 100 parts of Dick Dry LX-703VL (DIC Graphics, Polyester Polyol, Non-volatile content / about 62%), which is a solvent-based laminating adhesive main agent 9 parts of the curing agent was mixed to obtain a non-barrier adhesive “C”.
The adhesive was applied and laminated by the following coating method 1 to obtain a comparative film for the present invention.

Example 1
Using a bar coater, the barrier adhesive “A” was coated on a polyester film (PET) film having a thickness of 12 μm so that the coating amount was 5.0 g / m ² (solid content): Toyobo “E-5100” ( It was applied to the corona-treated surface of the single-sided corona treatment for general packaging, and the diluting solvent was volatilized and dried with a dryer set at a temperature of 70 ° C.
Laminated with the adhesive surface of the PET film coated with the adhesive and the corona-treated surface of CP film: Toray “ZK-93KM” 70 μm (single-sided corona treatment), and has a layer structure of PET film / adhesive layer / CP film A composite film was prepared.
Next, this composite film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a test film of the present invention.

(Example 2)
Using a bar coater, the solvent-type functional paint “B” is a polyester film (PET) film having a thickness of 12 μm and a coating amount of 2.0 g / m ² (solid content): Toyobo “E-5100” ( It was applied to the corona-treated surface of the single-sided corona treatment for general packaging, and the diluting solvent was volatilized and dried with a dryer set at a temperature of 70 ° C.
After confirming that the tack was sufficiently removed, in the same manner as in Example 1, the barrier adhesive “A” was applied to the solvent-type functional paint and then the bar coater was used to apply 5.0 g / m ^2. (Solid content) was applied, and the diluted solvent was volatilized and dried with a dryer set at a temperature of 70 ° C. The adhesive surface of the film coated with this adhesive and the corona-treated surface of CP film: Toray “ZK-93KM” 70 μm (single-sided corona treatment) are laminated, and PET film / solvent type functional paint / barrier adhesive layer A test film having a layer structure of / CP film was prepared.

(Comparative Example 1)
Using a bar coater, the barrier adhesive “A” was coated with a 12 μm thick polyester film (PET) film, Toyobo “E-5100” (solid content) of 5.0 g / m ² (solid content). The PET barrier film was prepared by coating the corona-treated surface of the single-sided corona treatment for general packaging) and evaporating the diluting solvent with a dryer set at a temperature of 70 ° C.
Next, CP film: Toray “ZK-93KM” 70 μm (single-sided corona treatment) corona treatment surface, “solvent type functional paint B” using a bar coater, coating amount 2.0 g / m ² (solid content ), Volatilize the diluting solvent with a drier set at a temperature of 70 ° C., dry it, and then laminate with “PET barrier film 3” to obtain a PET film / barrier adhesive layer / solvent type functional paint / CP film. A test film having a multilayer structure of

(Comparative Example 2)
Using a bar coater, the non-barrier adhesive “C” is a 12 μm thick polyester film (PET) film, Toyobo “E-5100” with a coating amount of 5.0 g / m ² (solid content). This was applied to the corona-treated surface (one-sided corona treatment for general packaging), and the solvent was evaporated and dried with a dryer set at a temperature of 70 ° C.
Laminate the adhesive surface of the PET film coated with the adhesive and the corona-treated surface of CP film: Toray “ZK-93KM” 70 μm (single-sided corona treatment) to form a layer structure of PET film / adhesive layer / CP film. The composite film which has was produced.
Next, this composite film was aged at 40 ° C. for 3 days, and the adhesive was cured to obtain a test film of the present invention.

(Comparative Example 3)
Using a bar coater, the solvent-type functional paint “B” is a polyester film (PET) film having a thickness of 12 μm so that the coating amount is 2.0 g / m ² (solid content), Toyobo “E-5100” ( It was applied to the corona-treated surface of the single-sided corona treatment for general packaging, and the diluting solvent was volatilized and dried with a dryer set at a temperature of 70 ° C.
After confirming that the tack was sufficiently removed, in the same manner as in Example 1, the non-barrier adhesive “C” was applied to the solvent-type functional paint and then applied using a bar coater. ² (solid content) was applied, and the diluted solvent was volatilized and dried with a dryer set at a temperature of 70 ° C. Laminate the adhesive side of the film coated with this adhesive with the corona-treated surface of CP film, Toray “ZK-93KM” 70 μm (single-sided corona treatment), PET film / solvent type functional paint / non-barrier adhesive A test film having a layer structure of layer / CP film was prepared.

(Comparative Example 4)
Using a bar coater, the non-barrier adhesive “C” is a polyester film (PET) film having a thickness of 12 μm so that the coating amount is 5.0 g / m ² (solid content): Toyobo “E-5100” It was applied to the corona-treated surface (one-side corona treatment for general packaging), and the diluted solvent was volatilized and dried with a drier set at a temperature of 70 ° C. to prepare a PET normal film.
Next, CP film: Toray “ZK-93KM” 70 μm (single-sided corona treatment) corona-treated surface, solvent-type functional paint “B” using a bar coater, coating amount 2.0 g / m ² (solid content ), Evaporate the diluting solvent with a drier set at a temperature of 70 ° C. and dry it, and then laminate with “PET normal film 4” to obtain a PET film / non-barrier adhesive layer / solvent type functional paint / A test film having a multilayer structure of CP film was prepared.

(Evaluation method)
Cut out the produced “test films 1-6” at 15 cm × 30 cm, bend it in half in the length direction, and heat laminate so that the three-way mouth (inner dimensions 13 × 13.5 cm) is at a pressure of 210 ° C. and 1N. To make bags,
-60 mL of purified water was internally added, and the insertion port was similarly sealed at 210 ° C. and 1 N to obtain a test packaging material (1 pouch).
A total of 4 pouches were produced, and a test at N = 4 was performed.
Each pouch was boiled with a 95% aqueous ethanol solution (ethanol / water = 95/5: volume ratio) at 121 ° C./2 hours (retort), and then allowed to stabilize at 40 ° C. for about 10 days (extraction stabilization).
・ The extract eluted in the contents was sampled from the inside with a cylinder, and the methyl cellosolve component was analyzed by gas chromatography.

As a result, the samples that brought the barrier adhesive layers of Examples 1 and 2 to the sealant side were below the detection limit, whereas all other components were detected at 20 ppm or more.
It was revealed that the barrier adhesive directly contacting the sealant side in the multilayer film structure of the present invention has a high function of protecting the internal additive from the volatile components applied to the outside and the PET film.

  The multilayer film of the present invention can be used as a packaging material for various foods that require excellent gas barrier properties and prevent the components from the layer from being mixed into the contents, so that the gas barrier properties are required.

Claims (22)

It has a gas barrier adhesive layer containing a resin (A) having two or more hydroxyl groups in one molecule as a functional group and an isocyanate compound (B) having two or more isocyanate groups in one molecule as a functional group. In gas barrier multilayer film,
The gas barrier multilayer film further has a sealant layer, and has a multilayer structure in which the sealant layer and the gas barrier adhesive layer are in contact with each other.
The resin (A) is a group consisting of a polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or anhydride thereof, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol. A gas barrier multilayer film which is a polyester polyol (A4) obtained by polycondensation of a polyhydric alcohol component containing at least one selected. Ortho-oriented aromatic dicarboxylic acid or its anhydride is orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its anhydride, anthraquinone 2,3-dicarboxylic acid 2. The gas barrier multilayer film according to claim 1, which is at least one polyvalent carboxylic acid selected from the group consisting of 2,3-anthracene dicarboxylic acid or an anhydride thereof, or an anhydride thereof, or an anhydride thereof. The main skeleton of the resin (A) has a polyester or polyester polyurethane structure, and the use rate of the ortho-oriented aromatic dicarboxylic acid or its anhydride is 70 to the total polyvalent carboxylic acid component of the polyester constituent monomer component. The gas barrier multilayer film according to claim 1 or 2, wherein the content is 100% by mass. Polyester polyol (A1) having at least one carboxy group and two or more hydroxyl groups obtained by reacting a carboxylic acid anhydride or polycarboxylic acid with a polyester polyol having a resin (A) having three or more hydroxyl groups The gas barrier multilayer film according to claim 1. The gas barrier multilayer film according to claim 4, wherein the polyester polyol (A1) has a hydroxyl value of 20 to 250 and an acid value of 20 to 200. The gas barrier multilayer film according to claim 1, wherein the polyester polyol (A) is a polyester polyol (A3) represented by the general formula (1).

(In Formula (1), R < ₁ > -R < ₃ > is respectively independently a hydrogen atom or 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). ) The gas barrier multilayer film according to claim 6, wherein a glycerol residue of the polyester polyol (A3) represented by the general formula (1) is contained in an amount of 5% by mass or more in the polyester resin composition. The gas barrier multilayer film according to claim 1, wherein the resin (A) is a polyester polyol (A5) having an isocyanuric ring represented by the general formula (3).

(In General Formula (3), R _{1 to} R ₃ are each independently — (CH ₂ ) _n1 —OH (where n1 represents an integer of 2 to 4), or General Formula (4)

(In General Formula (4), n2 represents an integer of 2 to 4, n3 represents an integer of 1 to 5, and X represents a 1,2-phenylene group, a 1,2-naphthylene group, or a 2,3-naphthylene group. , 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group, an arylene group which may have a substituent, and Y represents an alkylene group having 2 to 6 carbon atoms. Represents a group represented by: However, at least one of R ₁ , R ₂ and R ₃ is a group represented by the general formula (4). ) The gas barrier multilayer film according to any one of claims 1 to 8, wherein the polyisocyanate (B) contains a polyisocyanate having an aromatic ring. The gas barrier multilayer film according to claim 9, 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 1 to 10, wherein the gas barrier adhesive layer further contains a crystalline polyester. The gas barrier property according to any one of claims 1 to 11, wherein the gas barrier adhesive layer further contains a plate-like inorganic compound (C) which is nonionic between layers or non-swellable with respect to water. Multilayer film. When the total mass of the polyester polyol (A), polyisocyanate (B), and plate-like inorganic compound (C) is 100 parts by mass, the content of the plate-like inorganic compound (C) is 5 to 50 parts by mass. Item 13. A gas barrier multilayer film according to Item 12. The gas barrier multilayer film according to claim 12 or 13, wherein the plate-like inorganic compound (C) contains particles having a particle size of 0.1 µm or more. The gas barrier adhesive layer obtained by dissolving the polyester polyol (A) in a ketone solvent, an ester solvent, or a mixed solvent containing a ketone solvent or an ester solvent, according to any one of claims 1 to 14. The gas barrier multilayer film as described. The gas barrier multilayer film according to claim 1, wherein the gas barrier adhesive is a solventless type. The gas barrier multilayer film according to any one of claims 1 to 16, further comprising a base film layer in addition to the gas barrier adhesive layer and the sealant layer. The gas barrier multilayer film according to any one of claims 1 to 17, which is used as a multilayer film for an oxygen gas barrier. The gas barrier multilayer film according to any one of claims 1 to 17, which is used as a multilayer film for a water vapor barrier. The gas barrier multilayer film according to claim 1, which is used as a multilayer film for an inert gas barrier. The gas barrier multilayer film according to any one of claims 1 to 17, which is used as a multilayer film for an alcohol barrier. The gas barrier multilayer film according to any one of claims 1 to 17, which is used as a multilayer film for incense retention.