JP6191904B1 - Gas barrier adhesive, film, and gas barrier film - Google Patents

Abstract

Polyester polyol (A) which is a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or its acid anhydride and a polyol component (D), and a diluent (C ) And a curing agent containing the polyisocyanate compound (B), and the viscosity of the main agent is 10000 mPa.s at 60 ° C. A gas barrier adhesive that is s or less, a film coated with the gas barrier adhesive, and a gas barrier film using the film.

Description

  The present invention relates to a gas barrier adhesive, a film, and a gas barrier film.

  In many cases, packaging materials used for packaging foods and beverages are required to have oxygen or water vapor barrier properties in order to protect the contents and extend the shelf life. In order to satisfy these needs, a transparent film formed by depositing an inorganic material such as silica or alumina or a laminated film in which an aluminum foil is combined is used for the structure of the soft packaging material.

  However, since the deposited film usually has slight deposition defects, there are problems such as poor barrier properties and poor handling properties such as cracking. In addition, the aluminum foil has a problem that the inert gas barrier is perfect, but it is difficult to use from the viewpoint of recycling and is expensive.

  On the other hand, as an adhesive used for laminating the laminated film for food packaging, a reactive adhesive of a polyester material excellent in oxygen barrier property is also known, and 70 to 100% by mass of ortho-oriented aromatic dicarboxylic acid. Or an adhesive containing an amorphous polyester polyol obtained by polycondensation of a polyvalent carboxylic acid component containing at least one of its anhydrides and a polyhydric alcohol component, and a curing agent capable of reacting therewith (for example, Patent Document 1) Gas barrier adhesive layer comprising polyester polyol (A) having two or more hydroxyl groups and polyisocyanate (B) having two or more isocyanate groups, and an aluminum vapor deposition layer or aluminum A gas barrier multilayer film having a layer containing a foil (for example, see Patent Document 2) is described. However, the polyester polyols disclosed in these documents have a very high viscosity, and as disclosed in Patent Document 2, unless they are diluted with an organic solvent such as ethyl acetate, coating on a metal surface such as a vapor-deposited film or an aluminum foil is required. Was difficult. In recent years, there has been a great demand for so-called solvent-free adhesives that do not contain volatile organic solvents, particularly from the viewpoints of reducing the environmental burden and improving the working environment. Since the polyester polyol was applied as a solventless adhesive, there was room for improvement.

  On the other hand, solvent-free adhesives have a problem that the ink re-dissolution resistance is poor because the ratio of low molecular weight ester components that easily dissolve ink is poor, and the film appearance is impaired.

WO11 / 162160 JP 2013-147014 A

  The problem to be solved by the present invention is to provide a gas barrier adhesive that can also be applied to laminate adhesion of a vapor deposition film, an aluminum foil or the like.

  The present inventors are a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof, which is a polyester polyol disclosed in Patent Documents 1 and 2, and a polyol component (D). As a means for maintaining the film appearance and barrier properties of a certain polyester polyol and lowering the viscosity, the above-mentioned problems have been solved by using a difunctional or higher functional liquid alcohol as a diluent (C). That is, the present inventors have found that the bifunctional or higher functional liquid alcohol used as the diluent (C) is excellent in ink re-dissolution resistance and excellent in solubility of the polyester polyol, and can effectively lower the viscosity. . Furthermore, since the liquid alcohol has a high volatility temperature, it reacts with the polyisocyanate compound (B) at the time of laminating, so there is no risk of elution from the film after laminating, and it has been found that an optimal gas barrier film for food packaging can be provided. It was.

  That is, the present invention is a polyester polyol (A) which is a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or its acid anhydride and a polyol component (D), and a liquid alcohol having a bifunctional or higher functionality. It has a main agent containing a certain diluent (C) and a curing agent containing a polyisocyanate compound (B), and the viscosity of the main agent is 10000 mPa.s at 60 ° C. Provided is a gas barrier adhesive that is s or less.

  The present invention also provides a film coated with the gas barrier adhesive described above.

  Moreover, this invention provides the gas barrier film which uses the said film.

  The gas barrier adhesive of the present invention can also be applied to laminate adhesion such as vapor deposition films and aluminum foils, and a gas barrier film giving excellent adhesive strength and appearance can be obtained.

(Polyester polyol (A))
The polyester polyol (A) used in the present invention is a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof and a polyol component (D). Specifically, the amount of the acid component (E1) containing the ortho-oriented aromatic dicarboxylic acid or acid anhydride thereof as a raw material is preferably in the range of 10 to 90 mol%. Within this range, the polyester polyol (A) having the above viscosity range can be obtained.

  The ortho-oriented aromatic dicarboxylic acid or its acid anhydride is specifically orthophthalic acid or its acid 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.

Examples of other acid components include maleic acid or its acid anhydride, fumaric acid or its acid anhydride, and succinic acid or its acid anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid It is preferably at least one carboxylic acid or acid anhydride selected from the group consisting of (hereinafter, these carboxylic acids or acid anhydrides are referred to as “acid component (E2)”). The molar ratio of the acid component (E1) to the acid component (E2) is in the range of 1: 9 to 9: 1, more preferably in the range of 3: 7 to 7: 3.
As the acid component (E2), adipic acid is particularly preferable.

  On the other hand, as the polyol component (D), for example, a simple polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, 1,6-hexanediol, glycerin, and trishydroxyethyl isocyanurate. One component or a mixed component can be mentioned.

  The acid component (E2) contributes to the low viscosity of the gas barrier adhesive of the present invention. Moreover, maintaining the high barrier property by setting the amount of the acid component (E1) containing the ortho-oriented aromatic dicarboxylic acid or its acid anhydride to the total acid component in the range of 10 to 90 mol% as described above. Can do. This is presumed that orthophthalic acid and its anhydride have an asymmetric structure in the skeleton, and that rotation suppression of the molecular chain of the resulting polyester occurs, thereby presuming excellent barrier properties. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesive strength and barrier properties.

  The polyester polyol (A) used in the present invention preferably has a number average molecular weight in the range of 600 to 2,000. More preferably, the number average molecular weight is in the range of 600 to 1,000. When the number average molecular weight is higher than 2000, the viscosity is too high and it may not be used for the gas barrier adhesive. On the other hand, when the number average molecular weight is lower than 600, the proportion of the low molecular weight ester component that easily dissolves the ink increases, and the ink re-dissolution resistance may deteriorate.

(Acid component and other components)
The polyester polyol (A) of the present invention may copolymerize the acid component (E1) and other acid component (E3) other than the acid component (E2) within a range not impairing the effects of the present invention. For example, as the aliphatic polyvalent carboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid or the like is used, and as the alicyclic polyvalent carboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or the like is used as the aromatic. As group polyvalent carboxylic acids, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Dicarboxylic acids, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and Polybasic acids such as ester-forming derivatives of these dihydroxycarboxylic acids are used alone Or it can be used in a mixture of two or more. Of these, 1,3-cyclopentanedicarboxylic acid and isophthalic acid are preferable. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, and the like. The acid component (E3) is preferably 20% by mass or less, and most preferably 10% by mass or less, based on the total acid component amount.

  The viscosity of the polyester polyol (A) is 50000 mPa.s at 60 ° C. s or less, preferably 500 to 10,000 mPa.s. A range of s is still preferred. The viscosity is a value measured by blending polyester polyol (A) and diluent (C) and using an MCR rheometer manufactured by Anton Paar under conditions of cone plate CP-50, rotation speed 5 rpm, temperature 60 ° C. is there.

(Polyol component (D))
The polyol component (D) used in the present invention is preferably at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and glycerin. Most preferably, is used.

(Polyol component (D) Other components)
In the present invention, the above-mentioned polyhydric alcohol is preferably used, but other polyols may be copolymerized within a range not impairing the effects of the present invention. 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, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxides An elongated product and a hydrogenated alicyclic group can be exemplified. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol and the like. .

In the present invention, the reaction between the total acid component including the acid component (E1) and the polyol component (D) is performed as follows.
After all the acid components including the acid component (E1) and the polyol component (D) are charged all at once, the temperature is increased while stirring and mixing to cause a dehydration condensation reaction. The acid value measurement method described in JIS-K0070 is 5.0 mgKOH / g or less, 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 (b) ( The target polyester resin can be obtained by continuing the reaction until it is within ± 5% of mgKOH / g).

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

(In formula (b), Mn represents a predetermined number average molecular weight of a predetermined N (N is a natural number of 1 or more) functional polyester resin)
Alternatively, each raw material may be reacted in multiple stages. Moreover, you may prepare so that a hydroxyl value may enter into less than +/- 5%, adding the polyol component (D) 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. Several kinds of the catalysts can be used in combination. 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, there is a tendency to inhibit the subsequent reaction with urethane.

  The polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of −50 ° C. to 80 ° C. More preferably, it is −20 ° C. to 60 ° C. When the glass transition temperature is higher than 80 ° C., the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. In addition, since polycarboxylic acid contains orthophthalic acid or its anhydride, if the glass transition temperature is lower than −50 ° C., there is a risk that sufficient gas barrier properties may not be obtained due to intense molecular motion of polyester polyol near normal temperature. There is.

(Diluent (C))
Diluent (C) used in the present invention is a bifunctional or higher functional liquid alcohol. “Liquid” means liquid at room temperature. Specifically, ethylene glycol, propylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpentane-2,4-diol, 3-methyl-1 , 5-pentanediol, polyethylene glycol, or polypropylene glycol is preferred.
As described above, these liquid alcohols are excellent in the solubility of the polyester polyol (A) and can effectively lower the viscosity. In addition, since the volatilization temperature is high and it reacts with the polyisocyanate compound (B) at the time of lamination, there is no fear of elution from the film after lamination, and an optimal gas barrier film for food packaging can be provided. Furthermore, even when printing is performed on the film to be laminated, problems such as dissolving the printing ink hardly occur, and a laminated film having an excellent appearance can be obtained.

  It is preferable that the usage-amount of the said diluent (C) is 3-50 mass% with respect to the said polyester polyol (A). When the amount used is less than 3% by mass, the viscosity may not be lowered to the 60 ° C. viscosity. Moreover, when there is more usage-amount than 50 mass%, there exists a possibility that barrier property may be reduced. More preferably, it is the range of 5-40 mass%, More preferably, it is the range of 10-30 mass%.

In the present invention, the polyester polyol (A), which is a reaction product of the acid component (E1) and the polyol component (D) containing the ortho-oriented aromatic dicarboxylic acid or acid anhydride thereof, and a liquid alcohol having two or more functions. The viscosity of the main agent containing the diluent (C) is 10000 mPa.s at 60 ° C. It is the characteristic that it is below s. By adjusting the viscosity within the above range, the resin composition for an adhesive of the present invention can be used for a solventless adhesive.
100-5000 mPa.s. A range of s is still preferred.
The viscosity is a value measured by blending polyester polyol (A) and diluent (C) and using an MCR rheometer manufactured by Anton Paar under conditions of cone plate CP-50, rotation speed 5 rpm, temperature 60 ° C. is there.

(Polyisocyanate compound (B))
The isocyanate compound (B) used in the present invention is also called a curing agent for a reactive adhesive, and can be used without particular limitation as long as it is used for general purposes. Among them, a polyol component, a dibasic acid, The isocyanate compound (B) which has an isocyanate group at the terminal of the polyester compound which is the reaction product of is preferable. Specifically, the isocyanate used for the reaction with the polyester compound includes tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and the like. Can be mentioned. Moreover, you may use an isocyanate monomer in the range which does not impair the effect of this invention.

  In particular, a polyisocyanate having an aromatic ring is more preferable because of excellent gas barrier properties. In particular, in the case of a polyisocyanate containing a xylene skeleton, the reaction between a polyol component and a dibasic acid is possible because gas barrier properties can be improved not only by hydrogen bonding of urethane groups but also by π-π stacking between aromatic rings. Particularly preferred is a compound having a metaxylene diisocyanate group, a diphenylmethane diisocyanate group, or a hexamethylene diisocyanate group at the terminal of the polyester compound.

  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 is obtained by subjecting the isocyanate compound and the isocyanate blocking agent to an addition reaction by a known and appropriate method.

  As a polyol component which is a raw material of the polyisocyanate compound (B), it is preferable to use ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, glycerin and the like, and it is most preferable to use ethylene glycol.

Examples of the dibasic acid that is a raw material of the polyisocyanate compound (B) 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, and 2,3-anthracenecarboxylic acid or its anhydride, maleic acid or its anhydride, succinic acid or its anhydride, fumaric acid and the like. 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.

  The polyester polyol (A) and the polyisocyanate compound (B) are such that the ratio of the polyester polyol (A) and the polyisocyanate compound (B) is a reaction component of the hydroxyl group of the polyester polyol (A) and the polyisocyanate compound (B). Is preferably 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1/1 to 1/5. If the polyisocyanate component is excessive beyond this range, the excess polyisocyanate component may remain, so that it may bleed out from the adhesive layer after bonding. On the other hand, if the polyisocyanate component is insufficient, the adhesive strength may be insufficient. There is.

  The polyisocyanate compound (B) can be used in combination with a known curing agent or accelerator. Examples of the curing agent include carbodiimide-modified diphenylmethane diisocyanate, hexamethylene diisocyanate (abbreviated as HDI) / nurate, HDI / burette, HDI / allophanate, HDI / uretdione, and the like. 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 strength to various film materials.

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

  Moreover, 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 total amounts of an epoxy resin and an epoxy resin hardening | curing agent.

  The glass transition temperature of the cured coating film of the polyester polyol (A) and the polyisocyanate compound (B) of the present invention is preferably in the range of −30 ° C. to 80 ° C. More preferably, it is −20 ° C. to 60 ° C. When the glass transition temperature is higher than 80 ° C., the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate. On the other hand, when the temperature is lower than −30 ° C., there is a possibility that sufficient gas barrier properties may not be obtained due to intense molecular motion of the polyester polyol near room temperature, and sufficient adhesive strength, sealing due to insufficient cohesive strength of the cured coating film. There is a possibility that strength and the like cannot be obtained.

(Adhesive form)
As described above, the gas barrier adhesive of the present invention is a polyester polyol (A) which is a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof and a polyol component (D). And a main agent containing a diluent (C) which is a liquid alcohol having a bifunctional or higher functionality, and a curing agent containing a polyisocyanate compound (B), which are mixed and used as necessary.
The gas barrier adhesive of the present invention is a reactive two-component laminate adhesive utilizing a reaction between a polyester polyol (A) and a polyisocyanate compound (B). In general, when a conventional volatile organic solvent is not used, it is also referred to as a “solventless adhesive”, and the present invention is a “solventless gas barrier adhesive”. The “solvent” of the solventless adhesive referred to in the present invention refers to a highly soluble and volatile organic solvent capable of dissolving the polyisocyanate and polyol used in the present invention. "" Refers to the absence of these highly soluble organic solvents. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, and xylol. , N-hexane, cyclohexane and the like. Of these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.
On the other hand, a liquid alcohol having a bifunctional or higher functionality as the diluent (C) used in the present invention dissolves the polyester polyol (A) and polyisocyanate compound (B) of the present invention, but has low volatility and is also a polyisocyanate compound (B). React with. Therefore, it is different from the “solvent” of the “solventless adhesive” here.

  The gas barrier adhesive of the present invention can be used by coating on a substrate film or the like. The coating method is not particularly limited and may be performed by a known method. In the case of a solventless adhesive, the viscosity at room temperature is high and gravure roll coating is often unsuitable. In this case, coating is performed 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. When used as a solvent-type adhesive, it is often applied by a gravure roll coating method after being diluted with an appropriate solvent and adjusted to an appropriate viscosity.

  The gas barrier adhesive of the present invention can be used as an adhesive for various applications that require gas barrier properties against polymers, paper, metals, and the like. For example, as packaging materials used for packaging foods and beverages, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: linear low density polyethylene film, HDPE: high density polyethylene film) And polyolefin films such as polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cycloolefin copolymer film, and the like. These films can be preferably used with or without stretching treatment. Films that have been subjected to a stretching treatment have the advantage that the coating operation is easier and easier to use than dimensional stability and rigidity. In addition, in the unstretched film, the substrate is inferior in dimensional stability, rigidity, and heat resistance, so the vapor deposition layer has many defects and the gas barrier is often not stable, so by using the gas barrier adhesive of the present invention, There is an advantage that it can have a great effect on strengthening the barrier function.

Moreover, when using soft metal foils, such as a vapor deposition film and aluminum foil which vapor-deposited aluminum, a silica, an alumina, etc., since barrier property improves further, it is preferable.
Specific examples of the vapor deposition film and the soft metal foil include metal vapor deposition and metal oxide vapor deposition that are currently widely used for packaging. As metal vapor deposition, aluminum which is particularly inexpensive and widely used is preferable. As the metal oxide, aluminum oxide (AlOx) and silicon oxide (SiOx) are preferably exemplified as materials having high versatility. In addition to this, a film in which various organic compounds and inorganic compounds are vapor-deposited, and a film in which a plurality of types of materials are vapor-deposited may be used. There is no restriction | limiting in particular as a vapor deposition method, The vacuum evaporation method which is a physical vapor deposition method, and the CVD method which is a chemical vapor deposition method can be illustrated. As for the thickness of the vapor deposition layer, a certain gas barrier function can be exhibited even with the vapor deposition layer alone, and a higher barrier property can be obtained by laminating the gas barrier adhesive of the present invention thereon.

  These films are subjected to desired printing depending on the application, and in the case of a laminate film, the printed surface is often provided on the surface opposite to the surface which is the surface layer side after lamination. In this case, the printing surface is in direct contact with the adhesive, but since the gas barrier adhesive of the present invention has a small proportion of low molecular weight ester components that easily dissolve the ink, part of the ink dissolves and the printing surface collapses. There are few, and it is excellent in what is called ink re-dissolution property. These inks are particularly useful as an adhesive for bonding a film using a printing layer.

That is, as an example of the configuration of the gas barrier film of the present invention, for example,
・ Evaporated stretched film / laminate adhesive / sealant film ・ Ink / deposited stretch film / laminate adhesive / sealant film ・ Deposited stretch film / ink / laminate adhesive / sealant film ・ Ink / deposited stretch film / laminate adhesive / ink / Examples include sealant film / ink / evaporated stretched film / laminate adhesive / sealant film / ink. Of course, the present invention is not limited to this configuration, and can be suitably used as an adhesive for various laminates.

(Gas component types that can block permeation)
Gases that can be shut off by the gas barrier film using the gas barrier adhesive of the present invention include oxygen, water vapor, inert gases such as carbon dioxide, nitrogen and argon, alcohol components such as methanol, ethanol and propanol, phenol, In addition to phenols such as cresol, fragrance components composed of low-molecular compounds, for example, scent components such as soy sauce, sauce, miso, lemonene, menthol, methyl salicylate, coffee, cocoa shampoo, and rinse can be exemplified.

<Example of production of polyester polyol (A)>
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) Polyester polyol consisting of ethylene glycol, phthalic anhydride and maleic acid (A) “EGoPA3MA7 0.9K” Production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, Snyder tube and condenser. Of phthalic anhydride, 474.15 parts of phthalic anhydride, 732.3 parts of maleic anhydride, and 0.10 parts of titanium tetraisopropoxide, and gradually adjusted so that the upper temperature of the rectification tube does not exceed 100 ° C. The internal temperature was kept at 200 ° C. by heating. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 125, the theoretical number average molecular weight 900 calculated from the hydroxyl value, and the viscosity at 60 ° C. was 25,000 mPa · s. s polyester polyol (A) “EGoPA3MA7 0.9K” was obtained.

(Production Example 2) Polyester polyol consisting of ethylene glycol, phthalic anhydride and adipic acid (A) “EGoPA1AA9 0.85K” Production method Ethylene glycol in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser 703.62 parts, 131.22 parts of phthalic anhydride, 1165.19 parts of adipic acid and 0.10 parts of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 135, the theoretical number average molecular weight calculated from the hydroxyl value 850, and the viscosity at 60 ° C. was 850 mPa · s. s polyester polyol (A) “EGoPA1AA9 0.85K” was obtained.

(Production Example 3) Polyester polyol (A) "EGoPA9AA1 0.6K" made of ethylene glycol, phthalic anhydride and adipic acid Production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser. Was charged with 783.42 parts, 109.41 parts of phthalic anhydride, 120.20 parts of adipic acid and 0.10 parts of titanium tetraisopropoxide and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 185, the theoretical number average molecular weight 600 calculated from the hydroxyl value, and the viscosity at 60 ° C. was 4070 mPa · s polyester polyol (A) “EGoPA1AA9 0.85K” was obtained.

(Production Example 4) Polyester polyol (A) “EGoPA7AA3 0.85K” made of ethylene glycol, phthalic anhydride and adipic acid Production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser. Was charged with 798.1 parts, 1036.8 parts of phthalic anhydride, 438.4 parts of adipic acid and 0.10 parts of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated. The designed functional group number N = 2, the hydroxyl value = 135, the theoretical number average molecular weight calculated from the hydroxyl value 850, and the viscosity at 60 ° C. was 3950 mPa · s polyester polyol (A) “EGoPA1AA9 0.85K” was obtained.

(Production Example 5) Polyester polyol consisting of ethylene glycol, phthalic anhydride and adipic acid (A) “EGoPA5AA5 0.85K” Production method Ethylene glycol in a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser 791.0 parts, 740.6 parts of phthalic anhydride, 730.7 parts of adipic acid and 0.10 parts of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 135, the theoretical number average molecular weight calculated from the hydroxyl value 850, and the viscosity at 60 ° C. was 1300 mPa · s polyester polyol (A) “EGoPA5AA5 0.85K” was obtained.

(Production Example 6) Polyester polyol consisting of ethylene glycol, phthalic anhydride and suberic acid (A) "EGoPA5SA5 0.85K" Production method Ethylene glycol in a polyester reaction vessel equipped with a stirrer, nitrogen gas inlet tube, Snyder tube and condenser 66.81 parts, 613.59 parts of phthalic anhydride, 721.63 parts of suberic acid, and 0.10 parts of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube does not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 135, the theoretical number average molecular weight calculated from the hydroxyl value 850, and the viscosity at 60 ° C. was 830 mPa · s. s polyester polyol (A) “EGoPA5SA5 0.85K” was obtained.

(Production Example 7) Polyester polyol (A) consisting of ethylene glycol, phthalic anhydride and sebacic acid (A) “EGoPA5SeA5 0.85K” Production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, snider tube, and condenser. Was charged with 634.42 parts, 577.32 parts of phthalic anhydride, 788.30 parts of sebacic acid, and 0.10 parts of titanium tetraisopropoxide, and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. The internal temperature was kept at 200 ° C. When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated, the designed functional group number N = 2, the hydroxyl value = 135, the theoretical number average molecular weight calculated from the hydroxyl value 850, and the viscosity at 60 ° C. was 610 mPa · s. polyester polyol (A) “EGoPA5SeA5 0.85K” was obtained.

(Production Example 8) Polyester polyol comprising ethylene glycol and phthalic anhydride (A) “EGoPA 0.9K” production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser at 879. 37 parts, 1580.52 parts of phthalic anhydride, and 0.10 parts of titanium tetraisopropoxide were charged, and the inner temperature was maintained at 200 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. . The esterification reaction was terminated when the acid value became 5.0 mgKOH / g or less, the designed functional group number N = 2, the hydroxyl value = 125, the theoretical number average molecular weight 900 calculated from the hydroxyl value, and the viscosity at 60 ° C. was 91000 mPa · s. s polyester polyol (A) “EGoPA 0.9K” was obtained.

(Production Example 9) Polyester polyol comprising ethylene glycol and phthalic anhydride (A) “EGoPA 0.4K” Production method Ethylene glycol was added to a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction pipe, snider pipe, condenser, and 859. 95 parts, 1100.08 parts of phthalic anhydride, and 0.10 parts of titanium tetraisopropoxide were charged, and the inner temperature was kept at 200 ° C. by gradually heating so that the upper temperature of the rectifying tube did not exceed 100 ° C. . When the acid value became 5.0 mgKOH / g or less, the esterification reaction was terminated. The designed functional group number N = 2, the hydroxyl value = 295, the theoretical number average molecular weight calculated from the hydroxyl value 380, and the viscosity at 60 ° C. was 580 mPa · s. polyester polyol (A) “EGoPA 0.4K” was obtained.

Production Example 10 Production Method of Polyester Polyol “EG2oPA” Comprising Phthalic Anhydride and Ethylene Glycol In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, 134.86 parts of ethylene glycol and 148 of phthalic anhydride .12 parts were charged, and the inner temperature was kept at 220 ° 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 a polyester polyol “EG2oPA” having a design functional group number N = 2, a hydroxyl value = 445, and a theoretical number average molecular weight 252 calculated from the hydroxyl value. .

<Production example of polyisocyanate compound (B)>
Production Example 11 Production Example of Polyisocyanate Compound (B) “(EG2oPA) XDI2” Polyester resin “EG2oPA” in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser. 252 parts and 752.72 parts of xylylene diisocyanate (abbreviated as XDI) were charged and reacted at 60 ° C. for 3 hours under a nitrogen stream. When the NCO% becomes 26 or less, the urethanization reaction is terminated, and the polyisocyanate compound (B) “(EG2oPA) XDI2” having a design functional group number N = 2, an NCO% of 23.2%, and a viscosity at 60 ° C. of 50 mPa · s. Got.

Production Example 12 Production Example of Polyisocyanate Compound (B) “(EGoPA5AA5) XDI2” Polyester resin “EGoPA5AA5” in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet, and reflux condenser. 540 parts and XDI 522.14 parts were charged and reacted at 60 ° C. for 3 hours under a nitrogen stream. When the NCO% became 17% or less, the urethanization reaction was terminated, and the polyisocyanate compound (B) “(EGoPA5AA5) XDI2 having a design functional group number N = 2, an NCO% of 15.8%, and a viscosity at 60 ° C. of 280 mPa · s. "

(Production Example 13) Production Example of Polyisocyanate Compound (B) “XDI (EG2oPA) HDI-CDMDI” Polyester in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser 128.29 parts of resin “EG2oPA”, 172.1 parts of XDI, and 227.24 of hexamethylene diisocyanate burette were charged and reacted at 60 ° C. for 3 hours in a nitrogen stream. When NCO% became 15.5% or less, carbodiimide-modified diphenylmethane diisocyanate (abbreviated as CDMDI) 417.36 parts was charged to complete the urethanation reaction. The number of designed functional groups N = 2.24 and NCO% was 21.5%. %, A polyisocyanate compound (B) “(XDI (EG2oPA) HDI-CDMDI”) having a viscosity of 280 mPa · s at 60 ° C.

(Production Example 14) Production Example of Polyisocyanate Compound (B) "XDI (EGoPA5AA5) HDI-CDMDI" Polyester in a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, air inlet and reflux condenser Resin “EGoPA5AA5” (389.23 parts), XDI (172.1 parts) and hexamethylene diisocyanate allophanate 268.64 were charged and reacted at 60 ° C. for 3 hours in a nitrogen stream. When NCO% became 9.0% or less, 729.48 parts of CDMDI was charged to complete the urethanization reaction, and the polyisocyanate having a designed functional group number N = 2, NCO% 18.2%, and 60 ° C. viscosity 310 mPa · s. Compound (B) “(XDI (EGoPA5AA5) HDI-CDMDI”) was obtained.

(Method for measuring viscosity at 60 ° C. of main agent)
The polyester polyol (A) and diluent (C) obtained by the above production method were blended as shown in Table 1, Table 2 and Table 3 to obtain a main agent. The viscosity of the main agent was measured under the conditions of a cone plate CP-50, a rotation speed of 5 rpm, and a temperature of 60 ° C. using an MCR rheometer manufactured by Anton Paar.

(Evaluation method of ink re-solubility of main agent)
The main ingredient which mix | blended the polyester resin and diluent which were obtained by the said manufacturing method as shown in Table 1, Table 2, and Table 3 was diluted to 70% of resin solid content with ethyl acetate. Next, the diluted main agent was applied to a film coated with the ink “XS-878 R793 White No. 3” manufactured by DIC Corporation using a bar coater (No. 4). Thereafter, it was put into a dryer at 50 ° C., and the printed matter was taken out every 5 minutes. Immediately after this, the test of rubbing the ink part once with a cotton swab was repeated three times, and the ink re-dissolvability was evaluated in the following 6 stages.
Ink melts 95-100%: 0-point ink melts 60-95%: 1-point ink melts 30-60%: 2-point ink melts 10-30%: 3-point ink melts 5-10%: 4 points Ink dissolves 0-5%: 5 points

(Examples 1 to 11)
According to the composition of Tables 1 and 2, a main component containing polyester polyol (A) and diluent (C) and a curing agent containing polyisocyanate compound (B) were mixed to obtain a gas barrier adhesive.

(Comparative Examples 1-5)
Adhesives were obtained according to the compositions in Table 3.

(Methods for producing gas barrier films using the adhesives of Examples 1 to 11 and Comparative Examples 1 to 5)
The adhesives obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were heated to about 60 ° C., and a 30 μm thick OPP film (Futamura Chemical ( After applying to the corona-treated surface of “FOR” manufactured by Co., Ltd. so that the coating amount is 2.0 g / m ² , the coated surface is 24 μm thick aluminum evaporated CPP (VM-CPP film) (Toray Film Processing Co., Ltd.) “2203”) was laminated with the VM treated surface to prepare a laminated film having a layer structure of OPP film / adhesive layer / VM-CPP film. Subsequently, the obtained laminated film was aged at 40 ° C. for 3 days to cure the adhesive, and a gas barrier film was obtained.

(Lamination strength evaluation method)
The obtained gas barrier film was cut into a width of 15 mm in parallel with the coating direction, and the atmosphere temperature was 25 ° C. between the OPP film and the VM-CPP film using a Tensilon universal testing machine manufactured by Orientec Co., Ltd. The peeling rate was set to 300 mm / min, and the tensile strength when peeling by the 180 ° peeling method was defined as the laminate strength. The unit of laminate strength was N / 15 mm. When the film was broken during the measurement, F and the peak value were described in the result.

(Oxygen permeability evaluation method)
The obtained gas barrier film was measured for oxygen permeability under an atmosphere of 23 ° C. and 0% RH in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. .

(Reference example)
The oxygen permeability of a VM-CPP film having a thickness of 24 μm (“2203” manufactured by Toray Film Processing Co., Ltd.) was measured and converted to a transmittance of a film thickness of 5 g / m ² . As a result, it was 50 cc / m ² · day · atm.

(Method for evaluating ink re-solubility of adhesive)
The adhesives obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were diluted with ethyl acetate to a resin solid content of 70%. Next, the diluted main agent was applied to a film coated with the ink “XS-878 R793 White No. 3” manufactured by DIC using a bar coater (No. 4). Thereafter, it was put into a dryer at 50 ° C., and the printed matter was taken out every 5 minutes. Immediately after this, the test of rubbing the ink part once with a cotton swab was repeated three times, and the ink re-dissolvability was evaluated in the following 6 stages.
Ink melts 95-100%: 0-point ink melts 60-95%: 1-point ink melts 30-60%: 2-point ink melts 10-30%: 3-point ink melts 5-10%: 4 points Ink dissolves 0-5%: 5 points

  The results of Examples and Comparative Examples are shown in Table 1, Table 2, and Table 3.

In the table, abbreviations are as follows.
EGOPA3MA7 0.9K: Polyester polyol EgoPA1AA9 having a theoretical number average molecular weight of about 900 consisting of ethylene glycol, orthophthalic acid and maleic acid (molar ratio of orthophthalic acid to maleic acid 3: 7) 0.85K: ethylene glycol, orthophthalic acid and adipic acid Polyester polyol EGoPA9AA1 having a theoretical number average molecular weight of about 850 consisting of (orthophthalic acid and adipic acid molar ratio 1: 9) 0.6K: ethylene glycol, orthophthalic acid and adipic acid (molar ratio of orthophthalic acid and adipic acid 9: 1) Polyester polyol EGoPA7AA3 0.85K having a theoretical number average molecular weight of about 600. The theory consisting of ethylene glycol, orthophthalic acid and adipic acid (molar ratio of orthophthalic acid to adipic acid 7: 3) Polyester polyol EGoPA5AA5 having an average molecular weight of about 850 0.85K: Polyester polyol EgoPA5SA5 having a theoretical number average molecular weight of about 850 consisting of ethylene glycol, orthophthalic acid and adipic acid (molar ratio of orthophthalic acid to adipic acid 5: 5) 0.85K: ethylene Polyester polyol EGoPA5SeA5 having a theoretical number average molecular weight of about 850 consisting of glycol, orthophthalic acid and suberic acid (molar ratio of orthophthalic acid and suberic acid 5: 5) 0.85K: ethylene glycol, orthophthalic acid and sebacic acid (orthophthalic acid and sebacic acid) Polyester polyol EGoPA 0.9K having a molar ratio of 5: 5) of about 850 and a theoretical number average molecular weight of about 90 consisting of ethylene glycol and orthophthalic acid. Polyester polyols EGoPA 0.4K: polyester polyol theoretical number average molecular weight of about 400 comprising ethylene glycol and orthophthalic HA500B: DIC (Corporation) a polyester polyol resin

EG: ethylene glycol 1,3BD: 1,3 butanediol 1,4BD: 1,4 butanediol GLY: glycerin PPG400: polypropylene glycol, average molecular weight of about 400
PEG400: Polyethylene glycol, average molecular weight of about 400
Carbonate diol: Daicel's Plaxel CD205PL, average molecular weight of about 500
(EG2oPA) XDI2: Isocyanate compound (B) obtained by adding xylylene diisocyanate to the end of the polyester resin “EG2oPA”
(EGoPA5AA5) XDI2: Isocyanate compound (B) obtained by adding xylylene diisocyanate to the end of the polyester resin “EGoPA5AA5”
XDI (EG2oPA) HDI-CDMDI: Isocyanate compound (B) in which a burodi of xylylene diisocyanate and hexamethylene diisocyanate is added to the end of the polyester resin “EG2oPA” and then carbodiimide-modified diphenylmethane diisocyanate is added.
XDI (EGoPA5AA5) HDI-CDMDI: Isocyanate compound (B) in which allophanate of xylylene diisocyanate and hexamethylene diisocyanate is added to the end of the polyester resin “EGoPA5AA5” and then carbodiimide-modified diphenylmethane diisocyanate is added
NS5000A: Isocyanate compound (B) manufactured by DIC Corporation

* 1 The viscosity at 60 ° C of the main agent is the viscosity of the blend (main agent) of polyester polyol (A) and diluent (C).
* 2 The 40 ° C viscosity of the adhesive is the viscosity of the blend (adhesive) of polyester polyol (A), diluent (C) and polyisocyanate compound (B).

  As a result, the 60 ° C. viscosities of the polyol components of Examples 1 to 11 were all 10,000 mPa.s. The resin compositions of Examples 1 to 11 exhibited good laminate viscosity suitability.

  The laminated films using the gas barrier adhesives of Examples 1 to 11 as adhesives exhibited good adhesion performance with a laminate strength of 1.0 N / 15 mm or more.

All the laminated films using the gas barrier adhesives of Examples 1 to 11 as the adhesive exhibited an excellent barrier performance with an oxygen permeability of 2.0 cc / m ² · day or less.

The ink resolubility evaluation of the polyol components of Examples 1 to 11 was all good, and the laminate adhesives of Examples 1 to 11 also had good ink resolubility evaluation.
As described above, the gas barrier adhesives of Examples 1 to 4 have good laminate viscosity appropriateness, barrier performance, laminate adhesive strength, and ink solubility resistance.

On the other hand, Comparative Examples 1-2 are examples of adhesives that do not use a diluent. The adhesive of Comparative Example 1 has a good ink resolubility evaluation, and the laminated film using the adhesive of Comparative Example 1 has an oxygen permeability (23 ° C. 0% RH) of 1 cc / m ² · day · atm or less. The laminate strength is as good as 1.0 N / 15 mm or more, but the viscosity of the polyol component is 10,000 mPa.s. s or more, which is a result of poor laminating viscosity suitability.
In the adhesive of Comparative Example 2, the viscosity of the polyol component is 10,000 mPa.s. s or less, the laminate viscosity suitability is good, the laminate strength is 1.0 N / 15 mm or more, and the oxygen permeability (23 ° C. 0% RH) is 1 cc / m ² · day · atm or less. The ink re-dissolution property evaluation was poor, and the ink re-dissolution property evaluation of the adhesive itself was also a bad result.

Further, the adhesives of Comparative Examples 3 to 4 are examples in which the bifunctional or higher functional liquid alcohol described in the present invention is not used as a diluent. In any case, the viscosity of the polyol component is 50000 mPa.s. s or less, the laminate viscosity suitability is good, the laminate strength is 1.0 N / 15 mm or more, and the oxygen permeability (23 ° C. 0% RH) is 1 cc / m ² · day · atm or less. The ink re-dissolution property evaluation was poor, and the ink re-dissolution property evaluation of the adhesive itself was also a bad result.

The adhesive of Comparative Example 5 is a polyester polyol (A) which is a reaction product of an acid component (E1) containing an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof and a polyol component (D) as a polyester polyol. ) And a liquid alcohol having a bifunctional or higher functionality is not used as a diluent. The viscosity of the polyol component is 50000 mPa.s. Less than s, laminating viscosity suitability is good, laminating strength is good at 1.0 N / 15 mm or more, but oxygen permeability (23 ° C. 0% RH) is 1 cc / m ² · day · atm or more, bad result Met.

Claims (10)

Ortho directing aromatic dicarboxylic acid or acid component (E) and the polyol component (D) and the reactant der Ri number average molecular weight of 600 to 2000 der Ru polyester polyols containing an acid anhydride (A) and 2 It has a main agent containing a diluent (C) that is a functional or higher liquid alcohol and a curing agent containing a polyisocyanate compound (B), and the viscosity of the main agent is 1000 mPa · s or less at 60 ° C. A gas barrier adhesive characterized by The polyester polyol (A) comprises an ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof (E1), maleic acid or an acid anhydride thereof, fumaric acid or an acid anhydride thereof, and succinic acid or An acid component (E2) which is at least one carboxylic acid or acid anhydride selected from the group consisting of acid anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and polyol component (D The gas barrier adhesive according to claim 1, wherein the molar ratio of the acid component (E1) and the acid component (E2) is in the range of 1: 9 to 9: 1. The said polyisocyanate compound (B) has either a metaxylene diisocyanate group, a diphenylmethane diisocyanate group, a hexamethylene diisocyanate group at the terminal of the polyester compound which is a reaction product of a polyol component and a dibasic acid component. The gas barrier adhesive described in 1. The diluent (C) is ethylene glycol, propylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpentane-2,4-diol, 3- The gas barrier adhesive according to any one of claims 1 to 3, which is methyl-1,5-pentanediol, polyethylene glycol, or polypropylene glycol. The dibasic acid component of the polyisocyanate compound (B) is an acid component (E1) containing ortho-oriented aromatic dicarboxylic acid or acid anhydride thereof, maleic acid or acid anhydride thereof, fumaric acid or acid anhydride thereof. And acid component (E2) which is at least one carboxylic acid or acid anhydride selected from the group consisting of succinic acid or acid anhydrides, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid The gas barrier adhesive according to any one of claims 1 to 4, wherein the gas barrier adhesive is a mixture thereof. The gas barrier adhesive according to any one of claims 1 to 5, which is applied to a film having a printed surface on a surface opposite to a surface which is a surface layer side after lamination. The gas barrier adhesive according to any one of claims 1 to 6, wherein the polyester polyol (A) has a number average molecular weight of 850 or more. Film gas barrier adhesive is coated according to any of claims 1-7. A film in which a printed surface is provided on the surface opposite to the surface layer side after lamination, and the gas barrier adhesive according to any one of claims 1 to 7 is applied to the printed surface. A gas barrier film comprising the film according to claim 8 or 9 .